Persistent Organic Pollutants in Mountainous Areas · Persistent Organic Pollutants in Mountainous Areas Nov. 26–27, 2007 1 Understanding Air and Soil Concentration Changes with

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Persistent Organic Pollutants in Mountainous Areas

An international symposium

Nov. 26–27, 2007 Salzburg, Austria, Europe

Book of Abstract

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Table of contents 1. Understanding air and soil concentration changes with altitude in

mountains at different latitude Frank WANIAa, Gillian L. DALYa, John N. WESTGATEa, Chubashini SHUNTHIRASINGHAMa, Catherine E. OYILIAGUa, Steve HAYWARDa, Ying Duan LEIa, Camilla TEIXEIRAb, Derek C.G. MUIRb, Luisa E. CASTILLOc, Ricardo BARRAd, Gonzalo MENDOZAd, Hayley HUNGe

aDepartment of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military Trail, Toronto, Ontario, Canada M1C 1A4, bAquatic Ecosystem Protection Research Division, Environment Canada, 867 Lakeshore Road, Burlington, Ont., Canada L7R 4A6, cInstituto Regional de Estudios en Sustancias Toxicas, Campus Omar Dengo, Universidad Nacional, Heredia, Costa Rica, d Aquatic Systems Research Unit EULA-Chile Environmental Sciences Center University of Concepción Chile, eScience and Technology Branch, Environment Canada, 4905 Dufferin Street, Toronto, Ontario, Canada M3H 5T4 ……………………………………………………………………………………………1

2. Ambient air and deposition sampling - A new approach for Alpine sites

Wolfgang Moche1, Rodolfo Bassan2, Claudio Belis3, Gert Jakobi4, Manfred Kirchner4, Norbert Kräuchi5, Walkiria Levy-Lopez4, Teresa Magnani3, Ivo Offenthaler1, Karl-Werner Schramm4, Isabella Sedivy5, Primož Simončič6, Maria Uhl1, Peter Weiss1 1 Umweltbundesamt GmbH, Spittelauer Lände 5, 1090 Vienna, Austria; 2 ARPA Veneto, Via F. Tomea 5, I-32100 Belluno, Italy; 3 ARPA Lombardia, Via Stelvio 35, I-23100 Sondrio, Italy; 4 GSF, Institut für ökologische Chemie, Ingolstädter Landstraße 1, D-85764 Neuherberg, Germany ;5 WSL, Abt. Waldökosysteme und ökologische Risiken, Zürcherstrasse 111, CH-8903 Birmensdorf, Switzerland; 6 Slovenian Forest Institute, Vecna pot 2, 1000 Ljubljana, Slovenia ……………………………………………………………………………………………3

3. Determination of organochlorine pesticides, polychlorinated biphenyls and

polycyclic aromatic hydrocarbons in the free troposphere over Europe

Gerhard LAMMEL a,b *, Jana KLANOVA a, Jiří KOHOUTEK a, Ivan HOLOUBEK a a Masaryk University, Research Centre for Environmental Chemistry and Ecotoxicology, Kamenice 3, CZ-62500 Brno, b Centre for Marine and Atmospheric Sciences, Max Planck Institute for Meteorology, Bundesstrasse 53, D-20146 Hamburg, * [email protected] ……………………………………………………………………………………...………5

4. Seasonal and altitudinal trends of chlorinated pesticides in the central

Himalayan atmosphere

Loewen MD1,2, Sharma S3, Fuchs C2, Wang F1, Wania F4, Muir DCG5, Tomy GT2 1Department of Environment & Geography and Department of Chemistry, University of Manitoba, Winnipeg, MB R3T 2N2; 2Freshwater Institute, Department of Fisheries and Oceans, 501 University Crescent Winnipeg, MB R3T 2N6; 3Department of Environmental Sciences, Kathmandu University, Dhulikhel, Kavre, Nepal; 4Department of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military Trail, Toronto, ON M1C 1A4; 5National Water Research Institute, 867 Lakeshore Rd., PO Box 5050 Burlington, ON L7R 4A6. ……………………………………………………………………………………...………7

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5. What goes up must come down. The atmospheric transport and deposition of semi-volatile organic compounds to high elevation ecosystems in the Western US

Staci L. Simonich 1,2, Kim Hageman1, Sascha Usenko2, Luke Ackerman2, Don Campbell3, and Dixon Landers4 1Department of Environmental and Molecular Toxicology, Oregon State University, Corvallis, OR USA; 2Department of Chemistry, Oregon State University, Corvallis, OR USA; 3US Geological Survey, Denver, CO, USA; 4US Environmental Protection Agency, Corvallis, OR USA ……………………………………………………………………………………..……….9

6. Long-Term Studies with semi permeable membrane devices (SPMD) in

mountainous areas

Schramm K-W1,2, Levy W1, Henkelmann B1, Pfister G1, Bernhöft S1, Niklaus A1, Jakobi G1, R. Bassan3, C. Belis4, N. Kräuchi8, T. Magnani3, W. Moche9, P Schröder1, I. Sedivy8, P. Simončič10, P. Vannini4, U. Vilhar10, P. Weiss9, Kirchner M1 1GSF-National Research Centre for Environment and Health, Ingolstädter Landstrasse 1, D-85764 Neuherberg, Germany, [email protected], 2TUM-Technische Universität München, Department für Biowissenschaftliche Grundlagen Weihenstephaner Steig 23, D-85350 Freising, Germany, [email protected], 3Regional Agency for Environmental Prevention and Protection of Veneto, 4Regional Agency for Environmental Protection of Lombardia, 7Austrian Ministry for Agriculture, Forestry, Environment and Water Resource, 8WSL-Swiss Federal Institute for Forest, Snow and Landscape Research, 9Federal Environment Agency Ltd. – Austria, 10Slovenian Forestry Institute …………………………………………………………………………………………….11

7. Observation of organochlorine pesticides in Tibetan plateau

Tong ZHUa, Feng WANGa, Jing LIa, Baiqing XUb, Xinghua QIUa, Weili LINa aCollege of Environmental Sciences and Engineering, Peking University, Beijing 100871, China; bInstitute of Tibetan Plateau, Research, CAS, Beijing 100085, China, [email protected] …………………………………………………………………………………………….13

8. Photochemical degradation of POPs in snow Klánová J,a Matykiewiczová N,a and Klán P b a RECETOX, Masaryk University, Kamenice 126/3, 625 00 Brno, Czech Republic;b Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno, Czech Republic. …………………………………………………………………………………………….15

9. The photolytic degradation of organophosphorus pesticides in simulated ice and snow: implications for mountain environments Jan WEBERa, Romana KURKOVAb, Crispin HALSALLa, Jana KLANOVAb, Petr KLANc aLancaster Environment Centre, Environmental Science Dept., Lancaster University, Lancaster LA1 4YQ, UK, bRECETOX, Masaryk University, Kamenice 3/126, 625 00 Brno, Czech Republic, cDepartment of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno, Czech Republic …………………………………………………………………………………………….18

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10. Concentration changes of organohalogen compounds along Vertical Mountain transect. Biotic and abiotic processes Joan O. Grimalt‡, Mireia Bartrons†‡, Eva Gallego‡, Jordi Catalan† and Pilar Fernandez‡ ‡ Department of Environmental Chemistry. Institute of Chemical and Environmental Research (IIQAB-CSIC).Barcelona, Catalonia, Spain, † Limnology Unit (CSIC-UB). Centre for Advanced Studies of Blanes (CEAB-CSIC). Blanes, Catalonia, Spain. …………………………………………………………………………………………….20

11. Are POPs a threat to the aquatic alpine ecosystems? Bizzotto E.C., Villa S., Vighi M. Department of Environmental Sciences, University of Milano-Bicocca, Piazza della Scienza 1, 20126, Milano, Italy …………………………………………………………………………………………….22

12. Chlorinated paraffin’s in the alpine region Iozza S a,b*, Müller CE a, Bogdal C a, Schmid P a, Oehme M b, Bassan R c, Belis C d, Jakobi G e, Kirchner M e, Schramm K-W e, Sedivy I f, Kräuchi N f, Uhl M g, Moche W g, Offenthaler I g, Weiss P g, Simončič P h a Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for Analytical Chemistry, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland; b University of Basel, Department of Chemistry, St. Johanns-Ring 19, CH-4056 Basel, Switzerland; c Regional Agency for Environmental Prevention and Protection of Veneto, Italy; d Regional Agency for Environmental Protection of Lombardia, Italy; e GSF-National Research Centre for Environment and Health, Germany; f Swiss Federal Institute for Forest, Snow and Landscape Research, Switzerland; g Federal Environment Agency Ltd., Austria; h Slovenian Forestry Institute, Slovenia,* corresponding author: [email protected] …………………………………………………………………………………………….24

13. Possible role of the exposure to the sun of the different mountain sides on the POP distribution Paolo Tremolada1*, Sara Villa2, Antonio Finizio2, Elisa Bizzotto2, Roberto Comolli2 and Marco Vighi2 1 Department of Biology, University of Milan, Via Celoria 26, Milan, I-20133 Italy, 2 Department of Environmental and Land Sciences (DISAT), University of Milan Bicocca, Piazza della Scienza 1, Milan, I-20126 Italy. …………………………………………………………………………………………….26

14. Distribution of halogenated organic pollutants across the Alps Ivo Offenthaler1, , Rodolfo Bassan3,Claudio Belis4, Peter Futterknecht1, Saverio Iozza2, Gert Jakobi5, Manfred Kirchner5, Wilhelm Knoth8, Norbert Kräuchi6, Walkiria Levy-Lopez5,Wolfgang Moche1,Bernhard Schwarzl1, Gerhard Thanner1, Maria Uhl1, Karin Van Ommen1, Karl-Werner Schramm5, Isabella Sedivy6, Primoz Simoncic7, Peter Weiss1 1Austrian Environment Agency; 2Eidgenössische Materialprüfungsanstalt, Switzerland; 3Regional Agency for Environmental Prevention and Protection of Veneto, Italy; 4Regional Agency for Environmental Protection of Lombardia, Italy; 5GSF-National Research Centre for Environment and Health, Germany; 6WSL Swiss Federal Institute for Forest, Snow and Landscape Research; 7Slovenian Forestry Institute; 8Umweltbundesamt, Germany; ivo.offenthaler umweltbundesamt.at …………………………………………………………………………………………….28

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15. POPs in the Czech boarder mountains ecosystem– occurrence and long-term trends Ivan Holoubek, Jana Klanová, Jiří Jarkovský, Milan Sáňka, Jakub Hofman, Pavel Čupr RECETOX, Masaryk university, Central and Eastern European POPs Centre, National POPs Centre CR, Kamenice 126/3, 625 00 Brno, Czech Republic, [email protected], http://recetox.muni.cz …………………………………………………………………………………………….30

16. Modelling the orographic cold-trapping of persistent organic pollutants

John N. WESTGATEa, Frank WANIAb a,bDepartment of Chemistry, University of Toronto Scarborough, 1265 Military Trail, Toronto, Ontario, Canada, M1C 1A4, [email protected], [email protected], bcorresponding author ……………………………………………………………………………………………32

17. A comparison of emissions vs. masses of semivolatile organic compounds

in the Alpine forests Claudio Belis4, Rodolfo Bassan3, Gert Jakobi5, Manfred Kirchner5, Wilhelm Knoth8, Norbert Kräuchi6, Wolfgang Moche1, Nurmi-Legat J. 1, Raccanelli St.2, Karl-Werner Schramm5, Isabella Sedivy6, Primoz Simoncic7, Maria Uhl1, Peter Weiss1 1Austrian Environment Agency; 2INCA, Italy; 3Regional Agency for Environmental Prevention and Protection of Veneto, Italy; 4Regional Agency for Environmental Protection of Lombardia, Italy; 5GSF-National Research Centre for Environment and Health, Germany; 6WSL Swiss Federal Institute for Forest, Snow and Landscape Research; 7Slovenian Forestry Institute; 8Umweltbundesamt, Germany; …………………………………………………………………………………………….34

18. Origin of polluted air masses in the Alps

August Kaiser, Central Institute for Meteorology and Geodynamics, Hohe Warte 38, 1190 Vienna, Austria,

[email protected]

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Persistent Organic Pollutants in Mountainous Areas Nov. 26–27, 2007

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Understanding Air and Soil Concentration Changes with Altitude in Mountains

at Different Latitude

Frank WANIAa, Gillian L. DALYa, John N. WESTGATEa, Chubashini SHUNTHIRASINGHAMa, Catherine E.

OYILIAGUa, Steve HAYWARDa, Ying Duan LEIa, Camilla TEIXEIRAb, Derek C.G. MUIRb, Luisa E.

CASTILLOc, Ricardo BARRAd, Gonzalo MENDOZAd, Hayley HUNGe

aDepartment of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military Trail, Toronto, Ontario,

Canada M1C 1A4, bAquatic Ecosystem Protection Research Division, Environment Canada, 867 Lakeshore Road, Burlington, Ont.,

Canada L7R 4A6, cInstituto Regional de Estudios en Sustancias Toxicas, Campus Omar Dengo, Universidad Nacional, Heredia, Costa

Rica, d Aquatic Systems Research Unit EULA-Chile Environmental Sciences Center University of Concepción Chile, eScience and

Technology Branch, Environment Canada, 4905 Dufferin Street, Toronto, Ontario, Canada M3H 5T4

Introduction. Air and soil samples have been, or are currently being, taken along 13 elevational gradients along

the Western American Cordillera and are being analysed for the concentrations of organochlorine pesticides in

past and present use, polychlorinated biphenyls, as well as polycyclic aromatic hydrocarbons. The sampling

transects range from Patagonia in Southern Chile to Southern Alaska, and encompass a wide variety of mountain

systems in boreal, temperate, subtropical and tropical climates. The mountains vary in terms of altitudinal range,

vegetation cover, temperature gradients, precipitation gradients, exposure to large scale and local wind systems,

and proximity to organic contaminant sources. Ultimate aim of the interpretation of the concentration gradients is

to understand the mechanism of organic contaminant accumulation at high altitudes in particular, and the factors

controlling spatial concentration differences along environmental gradients in general (Daly and Wania, 2005).

Results and Discussion. In the absence of local contaminant sources, annual mean air concentrations measured

with XAD-resin based passive air samplers generally displayed relatively minor differences along an altitudinal

transect. This indicates relatively efficient atmospheric mixing on the scale of a mountain slope. However, even

relatively minor local sources, such as vehicular traffic, can dominate concentration gradients in otherwise remote

regions. For example, PAH concentrations in air and soil from Western Canadian mountains are strongly

correlated with the proximity to major roadways.

In contrast to the atmosphere, soil concentrations can display considerable variability along an elevational gradient

even in the absence of local sources, and often increase with altitude. For example, soil concentrations of

endosulfan-I and II, dacthal, lindane and dieldrin increased significantly with altitude along the westfacing slope

of Mount Revelstoke in the Selkirk Mountains (Daly et al. 2007a). Similarly, in Costa Rica, highest concentrations

of the fungicides chlorothalonil, and the insecticide metabolite endosulfan sulphate were detected in soils sampled

in montane cloud forests at high altitude (Daly et al. 2007b), despite being further removed from agricultural use

areas than many other sampling sites at lower elevations.

Preliminary conclusions drawn from a selected number of concentration gradients are:

Nov. 26–27, 2007 Persistent Organic Pollutants in Mountainous Areas

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- Changes in the amount and temperature of the precipitation falling along a mountain slope appear to be

important factors in determining variations in atmospheric deposition rates with altitude.

- In tropical mountains, rain is the dominant mode of precipitation up to very high altitudes, and highest

orographic cold-trapping appears to occur for substances with an air-water partition coefficient log KAW

between -3 and -5. Such substances are not efficiently rain scavenged at the temperature prevailing in

tropical lowlands, but are subject to efficient rain-out at the lower temperature of tropical mountains (Daly

et al. 2007b).

- In temperate mountains, the relative efficiency of rain and snow scavenging (Lei and Wania, 2004) will

influence changes in the rate of atmospheric deposition with altitude, and high deposition at high altitudes

is expected for substances that are efficiently scavenged by snow. In such mountains, temperature and

often also the precipitation rate undergoes seasonal changes, leading to complex temporal and spatial

variations of atmospheric deposition with altitude.

- Not all of the atmospherically deposited contaminants will be retained on the surface. Some snow-

scavenged contaminants will already evaporate during snow metamorphosis (Herbert et al., 2005), and

further volatilisation losses will occur during snow-free period from alpine areas with little vegetation

cover and low organic matter soils. Dense vegetation cover extending to high elevations within tropical

mountains suggests that the retentive capacity of tropical soils only drops substantially at very high

altitudes.

- Whereas the deposition rates are generally hypothesised to increase with elevation (because temperatures

drop and precipitation rates increase), the soil organic matter content in mountains at medium and high

latitudes tends to decrease with elevation and in particular will drop strongly above the tree line.

Accordingly, temperate mountain soils from intermediate elevations may often display the highest

concentrations of organic contaminants (Daly et al., 2007a).

Acknowledgements. This work was and is funded through a Canon National Parks fellowship, the Canadian

Natural Sciences and Engineering Research Council, the United Nations Environmental Program (UNEP

Chemicals), and Environment Canada.

References

Daly, G. L., F. Wania. Organic contaminants in mountains. Environ. Sci. Technol. 2005, 39, 385-398.

Daly, G.L., Y.D. Lei, C. Teixeira, D.C.G. Muir, F. Wania. Pesticides in Western Canadian mountain air and soil. Environ. Sci. Technol.2007a, 41, 6020-6025.

Daly, G. L., Y. D. Lei, C. Teixeira, D. C. G. Muir, L. E. Castillo, F. Wania. Accumulation of current-use pesticides in neotropical montane forests. Environ. Sci. Technol. 2007b, 41, 1118-1123.

Herbert B.M.J., C.J. Halsall, S. Villa, K.C. Jones, R. Kallenborn. Rapid changes in PCB and OC pesticide concentrations in Arctic snow. Environ. Sci. Technol. 2005, 39, 2998-3005.

Lei, Y. D., F. Wania. Is rain or snow a more efficient scavenger of organic chemicals? Atmos. Environ. 2004, 38, 3557-3571.


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Ambient Air and Deposition sampling - A New Approach for Alpine Sites

Wolfgang Moche1, Rodolfo Bassan2, Claudio Belis3, Gert Jakobi4, Manfred Kirchner4, Norbert Kräuchi5, Walkiria Levy-Lopez4, Teresa Magnani3, Ivo Offenthaler1, Karl-Werner

Schramm4, Isabella Sedivy5, Primož Simončič6, Maria Uhl1, Peter Weiss1 1 Umweltbundesamt GmbH, Spittelauer Lände 5, 1090 Vienna, Austria; 2 ARPA Veneto, Via F. Tomea 5, I-

32100 Belluno, Italy; 3 ARPA Lombardia, Via Stelvio 35, I-23100 Sondrio, Italy; 4 GSF, Institut für ökologische Chemie, Ingolstädter Landstraße 1, D-85764 Neuherberg, Germany ;5 WSL, Abt. Waldökosysteme und

ökologische Risiken, Zürcherstrasse 111, CH-8903 Birmensdorf, Switzerland; 6 Slovenian Forest Institute, Vecna pot 2, 1000 Ljubljana, Slovenia

Abstract A novel ambient air sampling technique has been developed within the project MONARPOP, which affords the opportunity to attribute measured concentrations of different POPs to four predefined source regions which are important for the alpine area. Such ambient air samplers and in addition bulk deposition samplers have been installed at three high altitude sampling sites Weissfluhjoch (CH; 2663 m), Zugspitze (D; 2650 m) and Sonnblick (A; 3106 m). Since the start of the project sampling was done for five trimonthly periods. For most of the analysed POPs no predominant source region could be detected so far, but clear seasonal differences were obvious. The concentration levels for ambient air and deposition as well were in the same range as those measured in the rural lowlands indicating long-range transport of PCDD/F and PCBs to these sites.

1. Introduction The project Interreg III B Project MONARPOP was initiated to get a more detailed picture of the fate of POPs within the alpine region. Needle, SPMD (semi permeable membrane devices), humus and soil samples have been taken at 40 sites and seven height profiles across the alpine region to get more information about regional and altitudinal concentration gradients for those toxic substances. Ambient air, deposition and SPMD samples at three high altitude sites have been taken to get information about long range transport of POPs, predominant source regions and the impact on the alpine region. This paper gives information with the thematic priority on the ambient air and the deposition part of the project, in particular the novel sampling approach for source region depending sampling.

2. Material and Methods One aim of the project was to look for source regions of POPs which are predominant for the Alps. For this reason it was planned to carry out ambient air measurements for various POPs with the additional requirement to attribute the measured concentrations to source regions. This means the sampled air masses have to correlated with their way to the sampling sites and possible influences by POP emissions during this way.

In contrast to gaseous pollutants like NOx for which the attribution to air masses can be done after the onsite and online monitoring, this is not possible for POPs. Long lasting sampling periods are necessary for POPs due to their typical low concentration ranges. Using traditional sampling methods in most of the cases weather situations will change during sampling, deleting all source region related information.

A possible way out is the predefinition of possible source regions and the separated, source region specific sampling of air masses arriving at the sampling site. This means the correlation of measured concentrations to source regions at the sampling stage.


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Three source regions have been selected which are known as important for the Alps from NOx investigations.

Existing sampling techniques for POPs have been modified for the planned investigations. Ambient air samplers have been equipped with four filter cartridges. Three are attributed to one of the predefined source regions, the fourth was chosen for undefined weather situations. The selection of the corresponding filter cartridge was done by remote control based on meteorological trajectory forecasts. All filter cartridges and moving parts have to be heated due to the hard weather conditions at the selected sites. In addition to the ambient air samplers also deposition samplers for bulk deposition have been installed at the three high altitude sites. The deposition samplers are built according to DIN 19739-1, “Measurement of atmospheric deposition of organic trace substances – funnel adsorber method”, but necessarily in a heated version.

Three high altitude measure-ment sites have been installed at three mountain summits which provide well equipped infrastructures of meteoro-logical stations necessary for the operation of POP samplers. The three sites are Weissfluhjoch (CH; 2663 m), Zugspitze (D; 2650 m) and Sonnblick (A; 3106 m). All these three sites are well staffed all around the year to ensure a daily support of the sampling equipment and short reaction times in the case of malfunctions.

At all three high altitude sites an array of samplers has been installed. As an example the arrangement at the sampling site at “Zugspitze”, is shown in the picture above:

(1) a low volume sampler for the collection of organochloropesticides (OCP) and polyaromatic hydrocarbons (PAH)

(2) a high volume sampler for the collection of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) and polybrominated diphenylethers (PBDE)

(3) 7 identical deposition samplers, each used for the collection of one of these four groups of pollutants completed by chlorinated paraffins (CP), Nitrophenols and trichloroacetic acid.

(4) A meteorological cabin for SPMD sampling

3. Results and Discussion Since the start of the project sampling was done for five trimonthly periods. For most of the analysed POPs no source region which was predominant in all sampling periods could be detected so far, but clear seasonal differences were obvious. A continuation of these measurements is planned to clarify if these detected seasonal differences are periodical.

The concentration levels for ambient air and deposition as well are in the same range as those measured in the rural lowlands indicating clearly a long-range transport of POPs to these sites and to the whole alpine region.


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Determination of Organochlorine Pesticides, Polychlorinated Biphenyls and Polycyclic Aromatic Hydrocarbons

in the Free Troposphere Over Europe

Gerhard LAMMEL a,b *, Jana KLANOVA a, Ji í KOHOUTEK a, Ivan HOLOUBEK a

a Masaryk University, Research Centre for Environmental Chemistry and Ecotoxicology, Kamenice 3, CZ-62500 Brno,b Centre for Marine and Atmospheric Sciences, Max Planck Institute for Meteorology, Bundesstrasse 53, D-20146 Hamburg, * [email protected]

Introduction Persistent organic pollutants (POPs), i.e. organochlorine pesticides (OCPs), polychlorinated

biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), are a concern for the ecosystems of

remote areas (such as alpine and polar regions) and human health as they are bioaccumulative, resist

degradation and cycle for long time in the environment. Most POPs are considered to be ubiquitous in the

global atmosphere (e.g. Holoubek et al., 2002) and concentrations expected to decrease with height,

which, however, has hardly been addressed so far. Samples with free tropospheric only have been

collected in the Himalayans and have been analysed for PAHs (Ciccioli et al., 1996). Recent model results

suggest transport of OCPs and PAHs in the upper troposphere and lower stratosphere (Semeena et al.,

2006).

Methods High volume (Digitel) air samples were taken 19.-29.6.2007 on the terrace of the UFS

Observatory, which is located on a steep, southern slope some 300 m below Mt. Zugspitze summit,

Bavarian Alps, 2650 m a.s.l.. Gas and particulate phases were collected separately (glass fibre filters and

polyurethane foam plugs in series). Using pollution level (visibility > 5 km, particle number concentration

N3-800nm < 2000 cm-3) and meteorological criteria (wind, negative evening atmospheric relative humidity

trend rhevening < -3%) we identified episodes of advection of free tropospheric (FT) air, 2-7 h, during

several nights. 2 FT samples have been collected (by combining several such episodes) and 6 samples of

mostly BL air (eventually mixed with free tropospheric air to some, though limited extent). BL air

samples were collected during day-time. In addition, each 5 PUF and GFF field blanks were taken. The

samples were extracted (dichloromethane), fractionated (silica gel columns) and analyzed (GC-ECD or

GC-MS). Limits of quantification after consideration of field blanks were 0.02-0.35 pg m-3.


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Results and discussion Concentration levels were orders of magnitude below typical polluted air levels.

Surprisingly, samples of FT air and BL air did not differ significantly with regard to POP concentrations

(Table 1) or other indicators for pollution: The concentration ranges of most OCPs (including DDT) and

PCBs, as well as N3-800nm were lower in tropospheric air but the concentration ranges of the FT and BL air

sample subsets were overlapping. HCHs and most PAHs were even higher concentrated in FT air.

Pollutant ratios indicate less influence of primary emissions of DDT and HCH in FT air and faster

degradation of PAHs in BL air (Table 1). The latter can be explained by photochemistry (day-time vs.

night-time sample subsets). OCPs, most PCBs and 3-ring PAHs were higher concentrated in the gas-

phase, while PCB 180 and the more heavy PAHs were predominantly associated with particulate matter.

Further data analysis will encompass air mass origin and trace compound patterns.

Table 1: OCP, PCB and PAH total (gas and particulate) concentrations in the FT and BL sample subsets, as time-weighted mean (min-max).

Free tropospheric air

(night-time)

Boundary layer or mixed air(day-time)

HCBHCHs (sum of 3) PCBs (sum of 7) DDTs (sum of 6)

-HCH/ -HCHC6Cl6 + C6HCl5DDT/total DDTs PAHs (sum of 27) ANT/(PHE+ANT)BAA/(CHR+BAA)

0.7 (0.4-1.6) 5.0 (3.7-8.4) 1.1 (1.0-1.3) 1.2 (1.1-1.3) 0.96 (0.7-1.3) 0.75 (0.36-1.9)

0.31 (<0.2-0.41) 99 (85-235)

0.027 (0.023-0.029) 0.83 (0.76-0.86)

1.8 (1.1-4.3) 3.3 (1.2-10.2) 1.8 (0.9-4.4) 1.5 (0.4-7.0)

0.54 (<0.02-12) 2.4 (1.3-2.6)

0.56 (<0.2-0.69) 79 (62-289)

0.015 (0.004-0.11) 0.74 (0.68-0.90)

unit: pg m-3

Acknowledgements We thank Steffen Knabe and Ralf Sohmer (Umweltbundesamt) and Manfred Kristen (German Weather Service, DWD, Zugspitze) for providing data.

ReferencesCiccioli P, Cecinato A, Brancaleoni E, Frattoni M, Zacchei P, Miguel AH, de Castro Vasconcelos P (2002):

Formation and transport of 2-nitrofluoranthene and 2-nitropyrene of photochemical origin in the troposphere. J. Geophys. Res. 101:19576-19582.

Holoubek I, Alcock R, Brorström-Lundén E, (and 37 other authors) (2002): Regionally Based Assessment of Persistent Toxic Substance - European Regional Report. UNEP Chemicals, Geneva, 147 p.

Semeena V S, Feichter J, Lammel G (2006): Significance of regional climate and substance properties on the fate and atmospheric long-range transport of persistent organic pollutants – examples of DDT and -HCH. Atmos. Chem. Phys. 6: 1231-1248.


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SEASONAL AND ALTITUDINAL TRENDS OF CHLORINATED PESTICIDES

IN THE CENTRAL HIMALAYAN ATMOSPHERE

Loewen MD1,2

, Sharma S3, Fuchs C

2, Wang F

1, Wania F

4, Muir DCG

5, Tomy GT

2

1Department of Environment & Geography and Department of Chemistry, University of

Manitoba, Winnipeg, MB R3T 2N2; 2Freshwater Institute, Department of Fisheries and

Oceans, 501 University Crescent Winnipeg, MB R3T 2N6; 3Department of

Environmental Sciences, Kathmandu University, Dhulikhel, Kavre, Nepal; 4Department

of Physical and Environmental Sciences, University of Toronto Scarborough, 1265

Military Trail, Toronto, ON M1C 1A4; 5National Water Research Institute, 867

Lakeshore Rd., PO Box 5050 Burlington, ON L7R 4A6.

Abstract

XAD-resin based passive air samplers were used to measure the concentrations of

hexachlorobenzene (HCB), endosulfan I, α-hexachlorocyclohexane (α-HCH), γ-

hexachlorocyclohexane (γ-HCH), p,p’-DDE and p,p’-DDT over an altitudinal transect

from 2638 to 5605m a.s.l in the Central Himalaya (27º44’-27º60’N, 86º43’-86º50’E).

Whereas there is no known usage of these chemicals in this high altitude region, they are

used extensively on the Indian Subcontinent. Air concentrations were similar to those

found in North American mountains1. Concentration gradients with altitude displayed

large differences between summer (May to October) and winter (November to April). In

summer concentrations of all the chemicals increased with elevation up to a maximum at

5000 m a.s.l and then declined above that elevation. Winter time concentration of all

chemicals declined with altitude, except for HCB which had similar elevational trends

year-round. This indicates that during the summer monsoon lower tropospheric air

contaminated with pesticides is being driven by thermal and mechanical forcing from the

Indian subcontinent into the central Himalaya2. During winter high altitude sites are well

above the boundary layer. For HCB global sources appear to be more important than

regional transport with the monsoon.

1) Daly, G.L., et al. Environ. Sci. Technol. 2007, 41, 6020-6025.

2) Arndt, R.L., et al. Atmos. Environ. 1998, 32, 1398–1406.


8

Figure 1: Seasonal atmospheric concentrations of chlorinated pesticides in the Central

Himalaya as a function of altitude. Air concentrations were corrected for changes in

sampler uptake rate due to atmospheric pressure and temperature changes caused by

increasing altitude.

2000 2500 3000 3500 4000 4500 5000 5500 6000

0

2

4

6

8

10

2000 2500 3000 3500 4000 4500 5000 5500 6000

0

5

10

15

20

25

30

0

20

40

60

80

100

120

0

10

20

30

40

0

100

200

300

400

500

0

20

40

60

80

100

120

winter (november-april)

summer (may-october)

Conce

ntr

ation

(pg

/m-3

)

HCB

Endosulfan I

α−HCH γ−HCH

p,p'-DDT p,p'-DDE


9

WHAT GOES UP MUST COME DOWN: THE ATMOSPHERIC TRANSPORT AND DEPOSITION

OF SEMI-VOLATILE ORGANIC COMPOUNDS TO HIGH ELEVATION ECOSYSTEMS IN THE

WESTERN U.S.

Staci L. Simonich 1,2, Kim Hageman1, Sascha Usenko2, Luke Ackerman2, Don Campbell3, and Dixon

Landers4

1Department of Environmental and Molecular Toxicology, Oregon State University, Corvallis, OR USA; 2Department of Chemistry, Oregon State University, Corvallis, OR USA; 3US Geological Survey, Denver, CO

USA; 4US Environmental Protection Agency, Corvallis, OR USA

Introduction Previous studies suggest that some anthropogenic semi-volatile organic compounds (SOCs)

undergo long-range atmospheric transport and redeposition to colder areas such as high-elevations and high-

latitudes. Snow is an efficient scavenger of SOCs from the

atmosphere and is the dominant form of precipitation for some

high-elevation ecosystems in North America. During annual

snowmelt, SOCs may be released from the snow pack into high-

elevation and high-latitude perched lakes.

Although the deposition of SOCs to high elevation

ecosystems has been studied in the Canadian Rockies and in the

European High Mountains, there is limited data on the

deposition of SOCs to high elevation ecosystems in the

Western U.S. The Western Airborne Contaminant Assessment

Project (WACAP) was developed to study the atmospheric

deposition of SOCs to, and their environmental fate in, high-

elevation and high-latitude ecosystems located in national

parks in the Western U.S., from 2003-2005. These national

parks, their general locations, and the elevation and average

mean temperature of each of the lake catchments under study are given in Figure 1.

Results and discussion To date, the WACAP snow samples have been analyzed for the target SOCs listed in

Figure 2. These data can be used to understand the current deposition of SOCs to the respective WACAP parks

and lake catchments. These data suggest that historic use SOCs, as well as current use SOCs, are being

deposited to the high elevation lake catchments within the Parks via snow.

SEQUOIASEQUOIA1. Pear L.: 2904m, 2.7 °C2. Emerald L.*: 2800m, 3.4 °C

ROCKY MTNROCKY MTN1. Lone Pine L.: 3024m, 2.7°C2. Mills L.: 3030m, 2.6 °C3. L. Irene*: 3567m, 1.3 °C

GLACIERGLACIER1. Aster Park: 2026m, 0.6 °C2. Snyder L.: 1600m, 3.4 °C

NOATAK&GATESNOATAK&GATES1. Burial L.: 427m, 6.6 °C2. Matcherak L.: 488m, 7.0°C

DENALIDENALI1. Kahiltna Camp: 2100m, 11°C2. McLeod L.: 609m, 1.2 °C3. Wonder L.: 610m, 1.2 °C

RAINIERRAINIER1. Alta Vista: 1730m, 2.5 °C2. Alta Vista: 1730m, 2.5 °C







Figure 1. Location, elevation, and mean annual temperature of WACAP lake catchments.













Figure 1. Location, elevation, and mean annual temperature of WACAP lake catchments.

PCBs:PCB 74 (2,4,4’,5-Tetrachlorobiphenyl), PCB 101 (2,2’,4,5,5’-Pentachlorobiphenyl), PCB 118 (2,3’,4,4’,5-Pentachlorobiphenyl), PCB 138 (2,2’,3,4,4’,5’-Hexachlorobiphenyl), PCB 153 (2,2’,4,4’,5,5’-Hexachlorobiphenyl), PCB 183* (2,2’,3,4,4’,5’,6-Heptachlorobiphenyl), and PCB 187 (2,2’,3,4’,5,5’,6-Heptachlorobiphenyl)

Pesticides and degradation products:Hexachlorocyclohexanes (HCH) - *, , -(lindane), and

, Chlordanes – cis*, trans*, oxy*, Nonachlor – cis, trans, Heptachlor*, Heptachlor Epoxide*, Endosulfans - I, II, and sulfate, Dieldrin, Aldrin, Endrin, Endrin Aldehyde, Hexachlorobenzene, Dacthal, Chlorothalonil, Chlorpyrifos and oxon, Trifluralin, Metribuzin, Triallate, Mirex

Polybrominated Diphenyl EthersSurrogates: 13C12 PCB 101 (2,2’,4,5,5’-

Pentachlorobiphenyl), 13C12 PCB 180 (2,2’, 3,4,4’,5,5’-Heptachlorobiphenyl), d10 - Chlorpyrifos, 13C6-HCB, d6- -HCH, d4-Endosulfan I, d4-Endosulfan II

Internal Standards: d14-Trifluralin

PAHs: Acenaphthylene, Acenaphthene, Fluorene, Phenanthrene, Anthracene, Fluoranthene, Pyrene, Retene, Benz[a]anthracene, Chrysene, Triphenylene, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[e]pyrene, Benzo[a]pyrene, Indeno[1,2,3-cd]pyrene, Dibenz[a,h]anthracene, Benzo[ghi]perylene

Pesticides and degradation products:o,p’-DDT*, p,p’-DDT, o,p’-DDD*, p,p’-DDD, o,p’-DDE, p,p’-DDE, Diazinon, Demeton S, Ethion, Etradiazole, Malathion*, Parathion and Methyl -Parathion, Phorate, Metolachlor*, Methoxychlor, Acetochlor*, Alachlor, Prometon, Pebulate, EPTC, Carbofuran, Carbaryl, Propachlor, Atrazine and degradation products, Simazine, Cyanazine

Surrogates: d10-Fluorene, d10-Phenanthrene, d10-Pyrene, d12-Triphenylene, d12-Benzo[a]pyrene, d12-Benzo[ghi]perylene, d14-EPTC, d10-Phorate, d5-Atrazine, d10-Diazinon, d7-Malathion, d10-Parathion, d8-p,p’-DDE, d8-p,p’-DDT, d6-Methyl Parathion, d13-Alachlor, d11-Acetochlor

Internal Standards: d10-Acenaphthene, d10-Fluoranthene, d12-Benzo[k]fluoranthene

Electron Capture Negative IonizationElectron Impact Ionization












Figure 2. Target SOCs, surrogates, and internal standards























Figure 2. Target SOCs, surrogates, and internal standards


10

Figure 3 shows the 2003 snow flux of two representative pesticides to the WACAP lake catchments

(described in Figure 1). Endosulfan continues to be used as a pesticide in the U.S., while dieldrin use in the

U.S. was discontinued in 1974. In general, our 2003 snow data suggests

that current use pesticides (such as endosulfan, dacthal, and

chlorpyrifos) have higher snow fluxes to the WACAP lake catchments

located in Sequoia and Rocky Mountain National Parks because of the

Park’s proximity to U.S. agriculture. More volatile historic use

pesticides (such as the hexachlorocyclohexanes - HCHs) show a more

even distribution of snow flux to all of the WACAP lake catchments,

regardless of proximity to U.S. agriculture. However, less volatile

historic use pesticides (such as dieldrin – Figure 3) have elevated snow

fluxes in Sequoia and Rocky Mountain National Parks because of their

continued slow volatilization from U.S. agricultural soils historically

contaminated from their use. In addition, the a-HCH to g-HCH ratio in

2003 snow suggests that Glacier National Park is influenced by the use of g-HCH (Lindane) in the near by

Canadian Prairies. These data can be used to estimate the current input of SOCs into the WACAP lake

catchments via snow deposition.

Dated sediment cores collected from the respective WACAP lake

catchments provide a historical perspective on the flux of SOCs to the lake

catchment over the past 100-150 years. For example, the Pear Lake

sediment core (Sequoia National Park) flux data (shown in Figure 4) for

representative pesticides (dieldrin and endosulfan) suggest that the flux of

banned pesticides (such as dieldrin and the DDTs) to the high elevation

lake catchments is decreasing from high fluxes in the 1950s-1960s, while

the flux of current use pesticides (such as endosulfan) has been highest in

recent years. The sediment core flux data shown in Figure 4 is consistent

with the initial use of these representative pesticides (dieldrin was first used

in 1948 and endosulfan was first used in 1956) as well as their current

status (dieldrin was banned in 1974 and endosulfan continues to be used in

the U.S.). The sediment core data confirms that both historic and current use pesticides continue to be

deposited to high elevation ecosystems located in western U.S. national parks.

Noatak & Gates

ENDOSULFANS (current-use)

0.011

0.00064

Denali

0.017

<QL<QL

Rainier

0.00940.013

Sequoia

0.16

0.081

Glacier

0.021

0.0073

Rocky Mtn

0.0690.12

0.038

ng/cm2/yr 2003 Data

Noatak & Gates


0.011

0.00064

Denali

0.017

<QL<QL

Rainier

0.00940.013

Sequoia

0.16

0.081

Glacier

0.021

0.0073

Rocky Mtn

0.0690.12

0.038

ng/cm2/yr 2003 Data

Noatak & Gates

DIELDRIN (historic-use)

0.0032

0.00045

Denali

0.0068

<QL<QL

Rainier<QL

<QL

Sequoia

0.017

0.16

Glacier

0.024

0.0083

Rocky Mtn

0.0200.031

0.0086

ng/cm2/yr 2003 Data

Noatak & Gates


0.0032

0.00045

Denali

0.0068

<QL<QL

Rainier<QL

<QL

Sequoia

0.017

0.16

Glacier

0.024

0.0083

Rocky Mtn

0.0200.031

0.0086

ng/cm2/yr 2003 Data

Figure 3. 2003 snow flux to WACAP lake catchments for representative pesticides

Noatak & Gates


0.011

0.00064

Denali

0.017

<QL<QL

Rainier

0.00940.013

Sequoia

0.16

0.081

Glacier

0.021

0.0073

Rocky Mtn

0.0690.12

0.038

ng/cm2/yr 2003 Data

Noatak & Gates


0.011

0.00064

Denali

0.017

<QL<QL

Rainier

0.00940.013

Sequoia

0.16

0.081

Glacier

0.021

0.0073

Rocky Mtn

0.0690.12

0.038

ng/cm2/yr 2003 Data

Noatak & Gates


0.0032

0.00045

Denali

0.0068

<QL<QL

Rainier<QL

<QL

Sequoia

0.017

0.16

Glacier

0.024

0.0083

Rocky Mtn

0.0200.031

0.0086

ng/cm2/yr 2003 Data

Noatak & Gates


0.0032

0.00045

Denali

0.0068

<QL<QL

Rainier<QL

<QL

Sequoia

0.017

0.16

Glacier

0.024

0.0083

Rocky Mtn

0.0200.031

0.0086

ng/cm2/yr 2003 Data

Figure 3. 2003 snow flux to WACAP lake catchments for representative pesticides

ng/cm2*yr*g(lipid)

0.0 2.0e+4 4.0e+4 6.0e+4 8.0e+4 1.0e+5 1.2e+5 1.4e+5

Dth

()

0

2

4

6

8

10

12

14Endosulfan II Endosulfan Sulfate

2003 2001

1992

1970 1963

1959

Below Quantitation Limit 1932


1998

1982

Endosulfans

ng/cm2*yr*g(lipid)

0 2e+4 4e+4 6e+4 8e+4 1e+5

0

2

4

6

8

10

12

14

2003 2001

1992

1982

1970

19631959



1998 Dieldrin

ng/cm2*yr*g(lipid)

0.0 2.0e+4 4.0e+4 6.0e+4 8.0e+4 1.0e+5 1.2e+5 1.4e+5

Dth

()

0

2

4

6

8

10

12


2003 2001

1992

1970 1963

1959



1998

1982

Endosulfans

ng/cm2*yr*g(lipid)

0.0 2.0e+4 4.0e+4 6.0e+4 8.0e+4 1.0e+5 1.2e+5 1.4e+5

Dth

()

0

2

4

6

8

10

12


2003 2001

1992

1970 1963

1959



1998

1982

Endosulfans

ng/cm2*yr*g(lipid)

0 2e+4 4e+4 6e+4 8e+4 1e+5

0

2

4

6

8

10

12

14

2003 2001

1992

1982

1970

19631959



1998 Dieldrin

ng/cm2*yr*g(lipid)

0 2e+4 4e+4 6e+4 8e+4 1e+5

0

2

4

6

8

10

12

14

2003 2001

1992

1982

1970

19631959



1998 Dieldrin

Figure 4. Pear Lake ( Sequoia National Park) sediment flux since 1879 for representative pesticides.

ng/cm2*yr*g(lipid)

0.0 2.0e+4 4.0e+4 6.0e+4 8.0e+4 1.0e+5 1.2e+5 1.4e+5

Dth

()

0

2

4

6

8

10

12


2003 2001

1992

1970 1963

1959



1998

1982

Endosulfans

ng/cm2*yr*g(lipid)

0 2e+4 4e+4 6e+4 8e+4 1e+5

0

2

4

6

8

10

12

14

2003 2001

1992

1982

1970

19631959



1998 Dieldrin

ng/cm2*yr*g(lipid)

0.0 2.0e+4 4.0e+4 6.0e+4 8.0e+4 1.0e+5 1.2e+5 1.4e+5

Dth

()

0

2

4

6

8

10

12


2003 2001

1992

1970 1963

1959



1998

1982

Endosulfans

ng/cm2*yr*g(lipid)

0.0 2.0e+4 4.0e+4 6.0e+4 8.0e+4 1.0e+5 1.2e+5 1.4e+5

Dth

()

0

2

4

6

8

10

12


2003 2001

1992

1970 1963

1959



1998

1982

Endosulfans

ng/cm2*yr*g(lipid)

0 2e+4 4e+4 6e+4 8e+4 1e+5

0

2

4

6

8

10

12

14

2003 2001

1992

1982

1970

19631959



1998 Dieldrin

ng/cm2*yr*g(lipid)

0 2e+4 4e+4 6e+4 8e+4 1e+5

0

2

4

6

8

10

12

14

2003 2001

1992

1982

1970

19631959



1998 Dieldrin

Figure 4. Pear Lake ( Sequoia National Park) sediment flux since 1879 for representative pesticides.


11

LONG-TERM STUDIES WITH SEMIPERMEABLE MEMBRANE DEVICES (SPMD) IN MOUNTANEOUS AREAS

Schramm K-W1,2, Levy W1, Henkelmann B1, Pfister G1, Bernhöft S1, Niklaus A1, Jakobi G1, R. Bassan3, C. Belis4, N. Kräuchi8, T. Magnani3, W. Moche9, P Schröder1, I. Sedivy8, P. Simončič10, P. Vannini4, U. Vilhar10, P. Weiss9 , Kirchner M1 1GSF-National Research Centre for Environment and Health, Ingolstädter Landstrasse 1, D-85764 Neuherberg, Germany, [email protected], 2TUM-Technische Universität München, Department für Biowissenschaftliche Grundlagen Weihenstephaner Steig 23, D-85350 Freising, Germany, [email protected], 3Regional Agency for Environmental Prevention and Protection of Veneto, 4Regional Agency for Environmental Protection of Lombardia, 7Austrian Ministry for Agriculture, Forestry, Environment and Water Resource, 8WSL-Swiss Federal Institute for Forest, Snow and Landscape Research, 9Federal Environment Agency Ltd. – Austria, 10Slovenian Forestry Institute Introduction

Semipermeable Membrane Devices (SPMD) were initially designed as passive samplers to operate in aquatic

environments but lately their use was extended as passive air samplers1. This device consists of a membrane in

this case composed of a low density polyethylene (LDPE) that encloses a lipophilic solvent: triolein. SPMDs

are integrative samplers, accumulating compounds during the exposure time until reaching equilibrium. The

device - air exchange of compounds obeys first order kinetics and can be divided into three stages a) linear

uptake where the uptake is proportional to the concentration of the compound in the device surroundings b)

curvilinear stage where the elimination of the absorbed compound achieves importance and c) equilibrium stage

where the uptake and release of the analyte in the device are equiparable3,4. When the device is operating in the

linear uptake stage, the sampler is called kinetic sampler. In the current work, SPMD were deployed at remote

mountain areas in different exposure periods. Organochlorine pesticides characterised by their different

properties were quantitatively analysed by means of HRGC-HRMS.

Materials and Methods

Analysis Membrane devices were cut into slices and spiked with 13C-Chloropesticides standards (Cambridge

Isotope Laboratories, USA), extracted for 24 hours with 100 ml cyclohexane, cleaned by mixed columns filled

with silica gel, Al2O3 and Na2SO4 and eluted with a mixture n-hexane/dichloromethane 1:1. and further eluted

through a C18 modified silica column with acetonitrile followed by separation with HRGC on a Rtx-Dioxin2

column (Restek, Germany) and detection with HRMS.

Results and Discussion

SPMD exposure in Period 1 finishes before winter, thus higher compound concentrations are expected and

period 2 finished in early summer. Analyzing the results obtained at the different altitudes for altitude profiles, a

very similar pattern is observed at the profile in the periods 1 and 2 for the compounds 2,4´DDT, 4,4´DDT,

cyclodiene pesticides cis-Chlordane, Dieldrin and α-Endosulfan and β-Endosulfan. It is also remarkable that the

sum of compounds accumulated in Period 1 and Period 2 assembles the amount of these chemicals accumulated

in the whole year (Period 3). We can infer for these compounds that the membrane devices are still working as


12

kinetic samplers due to the additivity of the Period 1 and 2 when comparing to Period 3. The accumulation of

these compounds is also characterized by a tendency to higher values at heights above 1400 m.a.s.l in the

altitude profile. As an example for this group, DDT isomers are plotted at the altitude profile (Figure 1). As the

passive sampler devices of the Period 3 are sampled together with the Period 2, the similarity in the pattern of

the height profile for periods 2 and 3 can be related to the stage of the uptake (curvilinear uptake or proximity

to the equilibrium) for DDE compounds in these passive samplers. Consequently, the results achieved after one

year exposure for 4,4´DDE tend to be similar to the last ½ year exposure (Period 2) in the whole height profile.

0

1000

2000

3000

4000

5000

6000

CH-01-2

CH-01-5

CH-01-7

CH-01-8

DE-21-1

DE-21-2

DE-21-3

DE-21-4

DE-21-5

DE-21-6

Altitude profiles

4,4´

DD

T (n

g kg

-1 tr

iole

in)

Period 1 Period 2Period 3 Sum of periods 1 + 2

0

500

1000

1500

2000

2500

3000

CH-01-2

CH-01-5

CH-01-7

CH-01-8

DE-21-1

DE-21-2

DE-21-3

DE-21-4

DE-21-5

DE-21-6

Altitude profiles

2,4´

DD

T (n

g kg

-1 tr

iole

in)

Period 1 Period 2Period 3 Sum of periods 1 + 2

Figure 1: a) 4,4´DDT and b) 2,4´DDT concentration at the altitude profiles for the periods 1, 2 and 3. The sum

of periods 1 and 2 is also depicted.

Regarding α-HCH and γ-HCH there is no similarity between patterns of the periods 1, 2 and 3. Period 2 present

a tendency to decrease for both isomers meanwhile the annual period (period 3) increases significantly at

altitudes above 1400 m.a.s.l. In summary, the compounds seem to be in different uptake stages regarding the

sampler device being very differently influenced by the period of exposure, inherent properties and height

profile.

Acknowledgements

MONARPOP is funded by the EU Interreg III B Alpine Space Programme (Alpine Space) and by the

participating national partners. Additionally, we would like to thank the Swiss Federal Office for the

Environment (FOEN - BAFU) for financial support.

References

1. Petty J, Huckins J, Zajicek J. Chemosphere 1993; 27:1609.

2. Opperhuizen A, van der Volde E W, Gobas F A P C, Liem D A K, van der Steen J M V. Chemosphere 1985;

14:1871.

3. Huckins J N, Manuweera G K, Petty J D, Mackay D, Lebo J A. Environ. Sci. Technol. 1993; 27:2489.

4. Bartkow M E, Booij K, Kennedy K E, Müller J F, Hawker D W. Chemosphere 2005; 60:170.

b) a)


13

Observation of Organochlorine Pesticides in Tibetan Plateau

Tong ZHUa, Feng WANGa, Jing LIa, Baiqing XUb, Xinghua QIUa, Weili LINa

aCollege of Environmental Sciences and Engineering, Peking University, Beijing 100871, China; bInstitute of Tibetan Plateau Research, CAS, Beijing 100085, China, [email protected]

Introduction: High mountains have been suggested to play an important role in the global transport of

persistent organic pollutants, as the highest and the largest plateau on the earth, Tibetan Plateau is affected by

Asian monsoons and westerly winds, which can transport the POPs to the plateau from the surrounding regions

where large amount of POPs has been used, yet research on POPs in Qinghai-Tibetan Plateau is limited. From

2002 to 2006, air, fresh-fallen snow, glacier melting water and ice cores were sampled to study the present and

historical levels of Organochlorine Pesticides (OCPs) in the Tibetan Plateau.

Method: In the summer of 2002, air samples were collected at Dingri with a height of 4400 meter above sea

level as well as Rongbuk Valley in Mt. Everest Region and analyzed with a LVI-GC-MS/MS. From 2004 to

2006, fresh-fallen snow and glacier melting water samples as well as and ice cores were collected in Tibetan

Plateau. Due to small volume of ice core and snow/water samples, the trace level of OCPs in these samples

were analyzed with the headspace solid phase microextraction (HS-SPME) and ion trap tandem mass spectrum.

Results and Discussion: The mean concentrations of organochlorine pesticides (OCPs) in the air samples were:

19.2, 11.2, 7.7, 8.9, 10.4, 27.6, 5.1, 5.1, and 3.7 pg m-3 for -HCH, -HCH, -HCH, HCB, heptachlor,

¬-Endosulfan, p,p’-DDE, o,p’-DDT, and p,p’-DDT, respectively. Backward trajectories were used to discuss

the association between source regions, transport paths, and observed OCPs concentrations. During the

sampling period, the o,p’-DDT/p,p’-DDT concentration ratios were observed between 1.23 to 1.41, much

higher than that of technical DDT, indicating the existing of a DDT source other than technical DDTs in the

source regions.

During a field campaign in April 2005, fresh-fallen snow samples were collected on the East Rongbuk Glacier

of the Mt. Qomolangma at four altitudes (6500 m, 6300 m, 6100 m and 5900 m), to study the role of Mt.

Qomolangma as “cold-traps” for Persistent Organic Pollutants. From these snow samples collected at the high

altitude, HCB p,p’-DDT and p,p’-DDD were detected, with the concentrations in the ranges of 44-72 pg L-1,

401-1560 pg L-1, and 20-80 pg L-1, respectively. The concentration of o,p’-DDT was around the method

detection limit. Analysis of backward trajectories showed that the detected compounds came from the North of

India, suggesting DDTs detected in the snow were possibly originated from new emissions in this area.

Relationships between the concentrations of OCPs in snow samples and the sampling altitudes were discussed.

The altitudes had no obvious effect on HCB concentrations in the fresh-fallen snow, while increases in the


14

concentrations of p,p’-DDT and p,p’-DDD with increasing altitude were found. Three factors likely resulted in

this trend: 1) the properties of the target compounds; 2) the low temperatures at high altitudes; 3) the location of

the mountain sampling sites relative to their sources.

-HCH and -HCH were detected in the Qomolangma ice core (Q-ice core) and Tanggula ice core (T-ice core),

while DDTs were found in only a few sections f the Q-ice core. From 1963to 2004, average concentrations of

HCHs were 1.84 4.05 ng L-1 (n 173) and 2.99 4.03 ng L-1 (n 88) in the Q-ice core and T-ice core,

respectively. The net deposition flux of HCHs in the Q-ice core (2.7×105 ng m-2) and T-ice core (2.9×105 ng

m-2) showed that the two ice cores contained samilar levels of HCHs concentrations. HCHs concentration had

a positive correlation (R2 0.49 n 51) with the -HCH/ -HCH ratio in the Q-ice core, yet no obvious

correlation was found in the T-ice core. A significant correlation (R2 0.79 n 38) was found between the

annual HCHs net deposition flux in the Q-ice core and the annual usage of Technical HCH in India, a lower

but also good correlation (R2 0.48 n 39) was found in the T-ice core. The cluster analysis of back trajectory

showed that the two areas where the ice cores were drilled were mainly affected by the Indian monsoons and

westerly wind. It suggested that the usage of technical HCH in India was probably the main source of the HCHs

detected in the Q-ice core and T-ice core, with the Q-ice core influenced more by the usage of technical DDT in

India.

Acknowledgement: This study was supported by the National Outstanding Young Scholar Fund (49925513)

and the project (40575061) of the Chinese Natural Science Foundation. The author also wishes to thank the

whole team of scientific expedition to Mt. Qomolangma in 2005.

References:

Wang F, Zhu T, Xu B Q, Kang S C (2007): Organochlorine pesticides in fresh-fallen snow on East Rongbuk Glacier of Mt. Qomolangma (Everest), Sci China Ser D-Earth Sci, 50: 1097-1102.

Li J, Zhu T, Wang F, Qiu, X H, Lin W L (2006): Observation of Organochlorine Pesticides in the Air in Mt. Everest Region, Ecotoxicology and Environmental Safety, 63: 33-41.


15

PHOTOCHEMICAL DEGRADATION OF PCBs IN SNOW

Klánová J,a Matykiewiczová N,a and Klán P b

a RECETOX, Masaryk University, Kamenice 126/3, 625 00 Brno, Czech Republic;

b Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno, Czech Republic.

Introduction The role of snow in distribution of organic contaminants 1-5 as well as in hosting their possible (photo)chemical

transformations in regions of high altitude and latitude 6, 7 has received growing attention. Many low-weight organic molecules, such as hydrocarbons or their halogenated derivatives, are present in snow at environmentally significant concentrations. 7 Recent laboratory studies of photochemical transformations of some organic compounds in frozen aqueous solutions 8-15 have raised the question whether compounds of anthropogenic origin, deposited in polar snowpacks or adsorbed on ice cloud crystals in the atmosphere, can afford products of a potentially high environmental risk and later be introduced into the environment via melting or evaporation processes. 6, 15, 16 These experiments utilized frozen solutions with relative high reactant concentrations (freezing the solution causes a considerable local concentration enhancement 17) and the phototransformations observed were very often intermolecular. In natural snow, concentrations are much lower; contaminants are deposited by scavenging processes, in which the concentration enhancement effect by freezing is absent.

In this work, artificial snow, containing approximately 100 ng L-1 concentration of PCB-7 or PCB-153, was photolyzed in

a cold chamber reactor, whilst the parent compounds and photoproducts mass distribution in snow and ambient air was followed. The main goal of the study was to estimate the scope of PCB photodegradation in natural snowpack. The work represents the first laboratory simulation of photochemical processes of organic contaminants in snow, occurring at relevant pollutant concentrations.

Results and Discussion Artificially prepared snow, containing ~100 ng L-1 concentration of either PCB-7 (2,4-dichloro-1,1'-biphenyl) or PCB-153

(2,2',4,4',5,5'-hexachlor-1,1'-bifenyl), in the absence or in the presence of H2O2, was photolyzed in a photochemical cold chamber at –25 °C. During the photolysis, the starting material and photoproducts fluxes from the snow sample were evaluated by measuring the total amount of compounds released into the air.

The dehalogenated derivatives (PCBs and biphenyl) were identified as the major products in all cases although traces of many chloroquaterphenyls and hydroxychlorobiphenyls were also detected based on the corresponding mass fragments observed by SIM analyses. Unfortunately, the initial nM and sub–nM PCB concentrations implied that those of the photoproducts, which must be several orders of magnitude lower, approach the detection limitations of analytical techniques. As a result, we were unable to accomplish the quantitative analysis of all trace compounds.

Dechlorination is the major photochemical process observed when PCBs are irradiated in inert media. 18 The mechanism

of the reductive dehalogenation is straightforward: following the excitation and usually efficient intersystem crossing (isc), the triplet state dissociates and the radicals formed may abstract hydrogen from neighboring hydrogen donors (HS) 18 or undergo radical aromatic substitution, in which the excessive hydrogen atom is simultaneously abstracted by another molecule. 10

When water as a nucleophile 19, or oxygen 20 are introduced, the corresponding hydroxy-substituted photoproducts are obtained. In contrast, photolysis of PCBs adsorbed on the surface of alumina and silica-alumina was found to produce radical cations as the major intermediates, which subsequently release the chlorine atoms. 21

As previously reported, irradiation of aromatic halogen compounds in frozen aqueous solutions (c >10-7 M) below –10 °C

afforded dehalogenation, coupling, or rearrangement reactions only; no photosolvolysis photoproducts, that is products from intermolecular reactions between organic and nucleophilic water molecules, were formed. 10, 11 PCBs in artificial snow were also reductively dehalogenated but other major photodegradation mechanisms were absent. Upon photolysis of PCBs in snow matrix, the formation of the biphenylyl radicals must precede hydrogen abstraction reaction from a hydrogen donor or minor arylation of a suitable aromatic reaction partner. 9-11 The coupling photoproducts (quaterphenyls derivatives) were identified in trace amounts but, with respect to their number and incomplete mass balance in all experiments, we believe that the radical arylation is a minor source of the hydrogen atom. However, this assumption cannot explain a predominant and extensive reductive dehalogenation observed.


16

Although water molecules cannot be a direct source of hydrogen (the O–H bond dissociation energy is too high), we still wanted to rule out any possible involvement of the water molecules in the reaction. The exhaustive photolysis of PCB-7 in deuterium oxide (97%) under the same conditions afforded no deuterated biphenyls, either formed within the solid matrix or released to the ambient air. Instead, a very similar product distribution of the same photoproducts was obtained. Therefore, the principle source of the hydrogen atom in our experiments remains unknown. We believe that trace amounts of various impurities, albeit undetected, originating from the air, entered the snow samples.

Hydroxylation reactions were obviously responsible for a more efficient PCB-7 degradation in the presence of H2O2 11

because traces of several hydroxylated photoproducts were identified. The presence of hydrogen peroxide enhanced the PCB-7 consumption by a factor of 4. In other experiments, such photoproducts (in significantly lower amounts) had to be produced only via addition of oxygen to form hydroperoxide/endoperoxide intermediates. 12

Natural snow is expected to release organic contaminants, such as PCBs. 2, 22 Therefore, we had to consider a partial

evaporation of the starting PCBs as well as the photoproducts from artificial snow samples during irradiation and it was found that the mass loss due to the photochemical transformations competed with that occurring by vapor flux to the ambient air. PCB-153 concentration decreased in dark cold chamber by volatilization from snow under the same conditions as used in the photolysis experiments; the curve had an exponential character and seemed to level off to a plateau at more than 50% concentration reduction (>12 days). This means that only less than 15% of the PCB-153 mass was released to the ambient air within the time required to accomplish a complete photochemical degradation in our experiments (2 days). Interestingly, only ~1% of the PCB-153 initial mass was detected in the air during the photochemical experiment but it is also possible that photodegradation of the parent molecule can still occur in the gas phase in a small extent. More volatile PCB-7 was found to be more susceptible to release; for example, ~3% of PCB-7 was found in air during 12-h Pyrex-filtered photolysis to a low conversion. This effect is well manifested in Figure 1, showing an increasing snow phase/air occurrence for 6 photoproducts upon irradiation of PCB-153 in artificial snow (the vapor pressure of least volatile PCB-101 and most volatile biphenyl is 1.6×10-3 and 104 Pa at 25 °C 23, respectively).

Freezing the aqueous solutions of organic molecules is known to be accompanied by their exclusion from the growing ice phase, resulting in increased local concentrations in a liquid layer covering ice crystals, which eventually freezes at low temperatures. 17, 24, 25 Very low concentrations of impurities may allow some species to be incorporated in the ice crystals; however, semi-volatile organic molecules of low polarity interact with ice through van der Waals interactions only and are not considered to dissolve in ice. 26, 27 The artificial snow production method utilized in this work (shock freezing in the liquid nitrogen) should provide a maximum distribution uniformity of the organic impurities within the crystals. Jacobi et al, however, observed that a large fraction of the inorganic nitrate is located close to the shock-frozen snow surface, enabling thus a quick mass exchange with the ambient air. 28 Since the volatilization of the starting compounds as well as products formed was considerable, it is highly possible that this sample preparation techniques produced ice crystals with hydrophobic organic impurities largely located on the surface, in the same way as they are located on ice crystals in natural snow.1 In order to find if premelting 29 can have any effect on enhancing the efficiency of coupling reactions, the aged snow samples were irradiated at the same conditions as fresh snow samples. Since both conversion and photoproduct distribution were found comparable, we can conclude that even if any changes in impurity distribution within the matrix occurred, it had no impact on the scope of the reaction.

Conclusions The PCB snow/air exchange is obviously a major competing process responsible for the pollutant loss from the snowpack

2, yet the question of the actual quantities of a chemical released back to the atmosphere is still open to debate. 2, 30 The snow quality and the location of pollutant molecules in the matrix is evidently the most important factor in evaluation, whether the pollutants reside there sufficiently long to undergo phototransformations. The properties of artificial snow samples used in this work were different than those of natural snow, which, nevertheless, can also vary significantly. 7 The release of PCBs from snow is strongly competing with its degradation upon irradiation with a solar simulator. However, the curve representing the volatilization loss levels off when the concentration is reduced below 50%, which possibly reflects a different location of organic molecules in snow matrix: those trapped within the crystals, unable to diffuse out, will have the greatest chance to react. In natural snowpacks, downward diffusion of desorbed vapors to deeper snow layers 2 will, furthermore, enhance the chance that photodegradation occurs if the molecules still reside in the photic layer. 31

Acknowledgments

The project was supported by the Czech Ministry of Education, Youth and Sport (MSM 0021622412) and by the Grant Agency of the Czech Republic (205/05/0819).


17

References

1. F. Wania, D. Mackay and J. T. Hoff, Environmental Science & Technology, 1999, 33, 195-197. 2. B. M. J. Herbert, C. J. Halsall, S. Villa, K. C. Jones and R. Kallenborn, Environmental Science & Technology, 2005, 39, 2998-3005. 3. B. M. J. Herbert, S. Villa and C. Halsall, Ecotoxicology and Environmental Safety, 2006, 63, 3-16. 4. R. W. MacDonald, L. A. Barrie, T. F. Bidleman, M. L. Diamond, D. J. Gregor, R. G. Semkin, W. M. J. Strachan, Y. F. Li, F. Wania, M. Alaee, L.

B. Alexeeva, S. M. Backus, R. Bailey, J. M. Bewers, C. Gobeil, C. J. Halsall, T. Harner, J. T. Hoff, L. M. M. Jantunen, W. L. Lockhart, D. Mackay, D. C. G. Muir, J. Pudykiewicz, K. J. Reimer, J. N. Smith, G. A. Stern, W. H. Schroeder, R. Wagemann and M. B. Yunker, Science of the Total Environment, 2000, 254, 93-234.

5. O. Gustafsson, P. Andersson, J. Axelman, T. D. Bucheli, P. Komp, M. S. McLachlan, A. Sobek and J. O. Thorngren, Science of the Total Environment, 2005, 342, 261-279.

6. P. Klan and I. Holoubek, Chemosphere, 2002, 46, 1201-1210. 7. A. M. Grannas, A. E. Jones, J. Dibb, M. Ammann, C. Anastasio, H. J. Beine, M. Bergin, J. Bottenheim, C. S. Boxe, G. Carver, G. Chen, J. H.

Crawford, F. Domine, M. M. Frey, M. I. Guzman, D. E. Heard, D. Helmig, M. R. Hoffmann, R. E. Honrath, L. G. Huey, M. Hutterli, H. W. Jacobi, P. Klan, B. Lefer, J. McConnell, J. Plane, R. Sander, J. Savarino, P. B. Shepson, W. R. Simpson, J. R. Sodeau, R. von Glasow, R. Weller, E. W. Wolff and T. Zhu, Atmos. Chem. Phys. Discuss., 2007, 7, 4165–4283.

8. P. Klan, J. Janosek and Z. Kriz, Journal of Photochemistry and Photobiology a-Chemistry, 2000, 134, 37-44. 9. P. Klan, D. Del Favero, A. Ansorgova, J. Klanova and I. Holoubek, Environmental Science and Pollution Research, 2001, 8, 195-200. 10. J. Klanova, P. Klan, J. Nosek and I. Holoubek, Environmental Science & Technology, 2003, 37, 1568-1574. 11. J. Klanova, P. Klan, D. Heger and I. Holoubek, Photochemical & Photobiological Sciences, 2003, 2, 1023-1031. 12. J. Dolinova, R. Ruzicka, R. Kurkova, J. Klanova and P. Klan, Environmental Science & Technology, 2006, 40, 7668-7674. 13. Y. Dubowski and M. R. Hoffmann, Geophysical Research Letters, 2000, 27, 3321-3324. 14. M. I. Guzman, A. I. Colussi and M. R. Hoffmann, Journal of Physical Chemistry A, 2006, 110, 3619-3626. 15. M. R. Hoffmann, in NATO ASI Series I, Editon edn., 1996, vol. 43, pp. 353-377. 16. L. Blaha, J. Klanova, P. Klan, J. Janosek, M. Skarek and R. Ruzicka, Environmental Science & Technology, 2004, 38, 2873-2878. 17. D. Heger, J. Jirkovsky and P. Klan, Journal of Physical Chemistry A, 2005, 109, 6702-6709. 18. N. J. Bunce, Chemosphere, 1982, 11, 701-714. 19. D. Dulin, H. Drossman and T. Mill, Environmental Science & Technology, 1986, 20, 72-77. 20. K. Hustert and F. Korte, Chemosphere, 1974, 3, 137-174. 21. Y. Mao and J. K. Thomas, Journal of the Chemical Society-Faraday Transactions, 1992, 88, 3079-3086. 22. K. M. Hansen, C. J. Halsall and J. H. Christensen, Environmental Science & Technology, 2006, 40, 2644-2652. 23. D. Mackay, W. Y. Shiu, M. K.-C. and S. C. Lee, Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals,

2nd edn., CRC Press, Boca Raton, 2006. 24. V. F. Petrenko and R. W. Whitworth, Physics of ice, Oxford University Press, Oxford, 1999. 25. S. R. Cohen, I. Weissbuch, R. PopovitzBiro, J. Majewski, H. P. Mauder, R. Lavi, L. Leiserowitz and M. Lahav, Israel Journal of Chemistry,

1996, 36, 97-110. 26. J. M. Blais, D. W. Schindler, D. C. G. Muir, L. E. Kimpe, D. B. Donald and B. Rosenberg, Nature, 1998, 395, 585-588. 27. G. L. Daly and F. Wania, Environmental Science & Technology, 2004, 38, 4176-4186. 28. H. W. Jacobi, T. Annor and E. Quansah, Journal of Photochemistry and Photobiology A-Chemistry, 2006, 179, 330-338. 29. J. G. Dash, H. Y. Fu and J. S. Wettlaufer, Reports on Progress in Physics, 1995, 58, 115-167. 30. F. Wania, J. T. Hoff, C. Q. Jia and D. Mackay, Environmental Pollution, 1998, 102, 25-41. 31. G. J. Phillips and W. R. Simpson, Journal of Geophysical Research-Atmospheres, 2005, 110.


18

The photolytic degradation of organophosphorus pesticides in simulated

ice and snow: implications for mountain environments Jan WEBERa, Romana KURKOVAb, Crispin HALSALLa, Jana KLANOVAb, Petr KLANc

aLancaster Environment Centre, Environmental Science Dept., Lancaster University, Lancaster LA1 4YQ, UK bRECETOX, Masaryk University, Kamenice 3/126, 625 00 Brno, Czech Republic cDepartment of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno, Czech Republic

Abstract. Two organophosphorus insecticides (methyl-parathion (MP) and fenitrothion (F)) were subject to light

irradiation in aqueous solutions as well as artificial ice and snow. Both these chemicals have been detected in

remote snowpacks and are susceptible to direct photolysis. Initial results indicate first order degradation kinetics

with different rates observed between water and ice. For example, half-lives (t1/2) in ice ranged between 2.6-5.2 hr,

whereas for water t1/2 was 1.4 h (FEN) and 22.9 h (MP), suggesting different degradation mechanisms between

water and ice, particularly for MP. Analysis of irradiated samples (MP) revealed the presence of

phototransformation products including 4-nitrophenol and methyl-paraoxon amongst others. Initial evidence would

suggest that the longevity of some of these photo-products is extended in the ice samples, due to the lack of liquid

water driving further degradation by hydrolysis, with possible toxicological implications for spring snowmelt.

Introduction. There is growing evidence that organophosphorus pesticides (OPPs), and other current-use

pesticides are subject to regional and long-range atmospheric transport with subsequent deposition and

accumulation in alpine and arctic environments (e.g. LeNoir et al. 1999; Muir et al. 2004). Notably, chemicals

such as chlorpyrifos, parathion and other phosphorothioate insecticides have been detected in snow and rain

samples collected in North American alpine regions (e.g. Hageman et al. 2006). Snow cores taken in the

Norwegian Arctic have revealed historical atmospheric accumulation of OPPs with concentrations ranging from

0.3-87 ng/L (meltwater), and 7.4 and 32.9 ng/L for FEN and MP respectively (Hermanson et al., 2005). Both FEN

and MP exhibited increasing concentrations towards the uppermost snow/ice layers, representing recent

accumulation during the late-1980s and 1990s, suggesting ongoing and possibly increasing loading to the remote

Arctic. The fate of these chemicals in these environments is poorly understood and yet photochemical degradation

may be an important process, particularly in surface snowpacks. This study examines comparative degradation

between water and snow/ice in an attempt to assess the fate of these chemicals in cold environments.

Methods. Buffered aqueous solutions of MP and FEN were prepared without co-solvents at concentrations ranging

from 2.8-3.8x10-5M. Photodegradation experiments were performed on aqueous solutions (pure water, pH buffered

5-9), ice (frozen aqueous samples) and snow respectively. Water and ice samples were placed into a merry-go-

round-apparatus and were irradiated in 13x100mm quartz- and Pyrex-glass tubes, sealed with septa. The quartz

tubes allowed for high UV light transmission (λ>254nm) in order to gain a high reaction yield, whereas the Pyrex


19

tubes transmit light at λ>300nm, broadly simulating environmental solar irradiation. Aqueous sample freezing (ice

samples) and subsequent irradiation (125W medium-pressure Hg lamp) was conducted in a circulatory type ultra-

cryostat at -15°C using ethanol as a coolant. The snow samples were prepared by spraying 4L of the standard

aqueous solution into an open polystyrene container, lined with Al-foil and filled with 10L of liquid nitrogen at -

178°C, with a stainless steel sprayer at 4bar pressure (nitrogen, 99%). A control sample was taken directly from the

sprayer in order to account for loss due to the spraying, with aqueous samples kept in the dark for to assess loss by

hydrolysis. Experiments were conducted over a period of 500 mins with samples analysed every 30 mins via

HPLC-DAD and phototransformation products qualified by GC-MS (EI)

Results. Both MP and FEN were found to degrade in water, ice and snow at differing rates, with degradation

illustrated in Figure 1 and the arise in phototransformation products (for MP) illustrated in Figure 2.

Figure 1. Photodegradation of FEN and MP in different aqueous media (water, ice, snow). Note the apparent

difference in rates between water and ice.

Figure 2. Chromatograms illustrating the degradation of MP in both water and ice. Note the presence of

phototransformation products prevailing in the ice.

References Hageman, K.J.; Simonich, S.L. et al. (2006) Environmental Scence &. Technology 40 3174-3180. Hermanson, M. H., Isaksson, E. H. et al. (2005). Environmental Science & Technology 39(21): 8163-8169. LeNoir, J. S., McConnell, L. L. et al. (1999). Environmental Toxicology and Chemistry 18(12): 2715-2722. Muir, D. C. G., Teixeira, C. et al. (2004). Environmental Toxicology and Chemistry 23(10): 2421-2432.

Water Water control Ice Ice control Snow Snow control

20

60

0

40

80

100

12

0 100 200 300 400 500 t/ min

% Fenitrothion 12

% Methyl Parathion

0 100 200 300 400 500 t/ min

0

40

80

100

60

20

t=0 mins t=15

t=30

t=60

t=120

t=360

methyl-parathion

4-nitrophenol

4.1

44

3.2

03

4.1

49

methyl-parathion

Intermediates including methyl-paraoxon

4-nitrophenol

WATER ICE


20

Concentration changes of organohalogen compounds along vertical mountain transects.

Biotic and abiotic processes

Joan O. Grimalt‡, Mireia Bartrons†‡, Eva Gallego‡, Jordi Catalan† and Pilar Fernandez‡

‡ Department of Environmental Chemistry. Institute of Chemical and Environmental Research (IIQAB-CSIC).Barcelona, Catalonia, Spain

† Limnology Unit (CSIC-UB). Centre for Advanced Studies of Blanes (CEAB-CSIC). Blanes, Catalonia, Spain.

The observation of altitudinal-temperature dependences for the accumulation of diverse organochlorine

compounds in mountain areas (1-3) called for studies of vertical gradients designed to minimize possible

geographical differences in emission rates (4) and biotic processes in the accumulation of these compounds (5).

One vertical gradient was already included in the first study showing these dependences in fish from

European high mountain lakes (1). Other gradients have also been examined in the Andes (6) and in Tenerife

(7). The present paper is devoted to get further insight into the European mountain gradients, including new

organohalogen compounds such as the polybromodiphenyl ethers (PBDEs). Analysis of these compounds in

fish from Pyrenean lakes distributed along an altitudinal transect shows higher concentrations at lower

temperatures, as predicted in the global distillation model. Conversely, no temperature-dependent distribution is

observed in a similar transect in the Tatra mountains (Central Europe) nor in fish from high mountain lakes

distributed throughout Europe (8). The fish concentrations of polychlorobiphenyls (PCBs) examined for

comparison showed significant temperature correlations in all these studied lakes. Cold trapping of both PCBs

and PBDEs concerned the less volatile congeners. In the Pyrenean lake transect the concentrations of PCBs and

PBDEs in fish were correlated despite the distinct use of these compounds and their 40 year time-lag of

emissions to the environment. Thus, temperature effects have overcome these anthropogenic differences

constituting at present the main process determining their distributions.

Figure 1. Concentrations of PCBs and PBDEs in fish from high altitude lakes in the Pyrenees and the Tatras.

PCB-101

R2 = 0.00820.01

0.1

1

0.00356 0.00362 0.00368

PCB-118

R2 = 0.69320.1

1

0.00356 0.00362 0.00368

PCB-138

R2 = 0.78931

10

0.00356 0.00362 0.00368

PCB-153

R2 = 0.72061

10

0.00356 0.00362 0.00368

PCB-180

R2 = 0.71120.1

1

10

0.00356 0.00362 0.00368

BDE-47

R2 = 0.49220.1

1

0.00356 0.00362 0.00368

BDE-99

R2 = 0.53360.1

1

0.00356 0.00362 0.00368

BDE-100

R2 = 0.87760.01

0.1

1

0.00356 0.00362 0.00368

BDE-153

R2 = 0.92170.01

0.1

1

0.00356 0.00362 0.00368

BDE-154

R2 = 0.99730.01

0.1

1

0.00356 0.00362 0.00368

PCB-101

R2 = 0.28320.1

1

10

0.00362 0.00368

PCB-118

R2 = 0.72761

10

0.00362 0.00368

PCB-138

R2 = 0.96521

10

0.00362 0.00368

PCB-153

R2 = 0.76281

10

0.00362 0.00368

PCB-180

R2 = 0.71811

10

0.00362 0.00368

BDE-47

R2 = 0.4031

0.1

1

0.00362 0.00368

BDE-99

R2 = 0.3428

0.1

1

0.00362 0.00368

BDE-100

R2 = 0.31030.01

0.1

0.00362 0.00368

BDE-153

R2 = 0.18830.01

0.1

0.00362 0.00368

BDE-154

R2 = 0.03730.01

0.1

0.00362 0.00368

281 276 272 281 276 272 281 276 272 281 276 272 281 276 272

281 276 272 281 276 272 281 276 272 281 276 272 281 276 272

276 272 276 272 276 272 276 272 276 272

276 272 276 272 276 272 276 272 276 272

Temperature (ºK)

Temperature (ºK)

PYRENEES

TATRAS


21

The role of insect larvae and pupae as sources of organohalogen compounds for high predators such as

fish has been evaluated. Trichoptera and diptera were taken as organisms of choice because they are common in

benthic aquatic habitats and accumulate substantial amounts of these compounds (9). The results have shown a

non-selective enrichment of OCs and PBDEs from larvae to pupae. This concentration increases may result

from the weight loss of pupae during metamorphosis mainly as consequence of protein carbon respiration and

lack of feeding. According to these results the intake of these compounds by trout are between two and five-

fold higher per calorie gained when predating on pupae than on larvae (Table 1). These intake differences have

implications for bioaccumulation through food web. Even though pupae have shorter duration of life stage (i.e.

degree-days required for development) and less energy content per individual (a difference that is more

remarkable in trichoptera), they usually have a larger contribution to diet than larvae because of the lower

predation effort required for their capture. Accordingly, since pollutant concentration, energy reward, predation

susceptibility and duration of life stage are largely different between larvae and pupae, these two metamorphic

stages are very distinct pollutant sources for higher trophic levels. Bioaccumulation food web models should

therefore distinguish between the two stages when modeling OCs and PBDEs intake.

Table 1. Estimation of the ΣPCBs and ΣPBDEs ingestion of a model trout feeding on larvae and pupae from the lakes considered for

study.

larvae pupae

Energy content trichoptera 130 51

(cal ind-1

) diptera 0.45 0.40

ΣΣΣΣPCBs trichoptera 1.5 ± 1.7 3 ± 1.8

(ng cal-1

) diptera 1.6 ± 0.8 5.4 ± 1.5

ΣΣΣΣPBDEs trichoptera 2.0 ± 2.5 5.2 ± 3.7

(ng cal-1

) diptera 0.24 ± 0.34 1.3 ± 0.3

Degree-day trichoptera 3135 ± 162 450 ± 127

(ºC) diptera 217 ± 57 22 ± 2

Trout diet contribution trichoptera 2.9 ± 0.12 37 ± 52

(% volume) diptera 21 ± 25 38 ± 48

References 1) Grimalt et al. Selective trapping of organochlorine compounds in mountain lakes of temperate areas. Environ. Sci. Technol. 35,

2690-2697 (2001)

2) I. Vives, J.O. Grimalt, J. Catalan, B.O. Rosseland and R.W. Battarbee. Influence of altitude and age in the accumulation of

organochlorine compounds in fish from high mountain lakes. Environ. Sci. Technol. 38, 690-698 (2004)

3) Blais et al. Accumulation of persistent organochlorine compounds in mountains of western Canada. Nature 395, 585-588 (1998)

4) G.L. Daly and F. Wania. Organic Contaminants in Mountains. Environ. Sci. Technol. 39, 385-398 (2005)

5) Blais et al. Concentrations of organochlorine pesticides and polychlorinated biphenyls in amphipods (Gammarus lacustris) along

an elevation gradient in mountain lakes of western Canada. Environ. Toxicol. Chem. 22, 2605-2613 (2003)

6) Grimalt et al. Temperature dependence of the distribution of organochlorine compounds in the mosses of the Andean mountains.

Environ. Sci. Technol. 38, 5386-5392 (2004)

7) A. Ribes, J.O. Grimalt, C.J. Torres Garcia and E. Cuevas. Temperature and organic matter dependence of the distribution of

organochlorine compounds in mountain soils from the subtropical Atlantic (Teide, Tenerife Island). Environ. Sci. Technol. 36,

1879-1885 (2002)

8) Vives et al. Polybromodiphenyl ether flame retardants in fish from lakes in European high mountains and Greenland. Environ. Sci.

Technol. 38, 2338-2344 (2004)

9) J. Catalan, M. Ventura, I. Vives and J.O. Grimalt. The roles of food and water in the bioaccumulation of organochlorine

compounds in high mountain lake fish. Environ. Sci. Technol. 38, 4269-4275 (2004)


22

Are POPs a threat to the aquatic alpine ecosystems?

Bizzotto E.C., Villa S., Vighi M.

Department of Environmental Sciences, University of Milano-Bicocca, Piazza della Scienza 1, 20126, Milano,

Italy

Abstract

Many international and national projects like IPCC (Intergovernmental Panel on Climate Change), AMAP

(Artic Monitoring Program), ACIA (Artic Climatic Impact Assessment) and RICLIC WARM (Regional Impact

of Climatic Change in Lombardy Water: Resources and Modelling) highlight the relevance of contaminant

effects in higher latitude/altitude systems.

To investigate fate and effect of persistent organic pollutants (POPs) accumulated in Alpine glaciers for the

cold condenser effect and released trough ice melting, the glacial-fed stream Frodolfo (Italian Alps) was

sampled during summer 2006, when ice and snow melting produces a significant increase of stream water flow.

The sampling was conducted monthly, from May to October, in four sites up to 2 km from the glacier lobe. In

the same geographic area, a non-glacial stream was sampled in order to evaluate possible differences in POP

concentrations as a function of water origin.

Water, sediment and biological (macro-invertebrates) samples were collected in both environments. In the

sampling station closest to the glacier, POP concentrations were investigated as a function of the daily

temperature cycle.

All abiotic and biotic samples, added with a suitable recovery standard and internal standard, were analyzed in

GC-MS in Single Ion Monitoring mode. The investigated molecules were 37 PCBs, DDTs (isomers and

metabolites), HCHs ( -, -, - isomers) and HCB. Prior to chemical analyses, macro-invertebrates were

taxonomically identified and grouped according to their trophic role.

Major objectives of the study are:

determining the contamination fingerprint in streams of different origin (glacial fed and non glacial fed) and

subject to different exposure patterns in Italian Alps;

evaluating the possible presence of a seasonal pattern in POP contamination, in order to assess the intensity

of the pollutants stress for aquatic ecosystem in a seasonal cycle;

analysing the relationship between distance from the glacier and POP contamination;

determining a relationship between daily temperature cycle and concentration of POPs in melting water;

assessing the potential transfer in the trophic chain and the level of risk for Alpine freshwater ecosystems

exposed to POPs.

The results for pesticides like DDT, HCH and HCB, in water and sediment, were in the range of literature data

for pristine areas (Villa et al., 2006, Blais et al., 2001a, 2001b; Lafrenière et. al, 2006). Concentration of

selected PCBs were higher than the literature data on comparable systems, but in the same order of magnitude

of data reported by Villa et al. (2001) for recent ice of Stelvio glacier, located in the same area of Frodolfo. In


23

both cases the fingerprint was those of the technical Aroclor mixture, supporting the hypothesis of a local recent

contamination.

POP contamination in glacial-fed stream during summer 2006 seems to be subject to two different inputs and

sources of pollutants; in early summer (May-June) contamination seems more affected by snow melting and

reflects the present atmospheric condition; in late summer (July - October) the contamination seems mainly due

to glacial ice melting and the fingerprint reflects old and long range transport.

In detail, at the beginning of the melting season (May), the preferential elution of HCHs (dominated by lindane)

was observed in the first snowmeltwater fractions. In this period, PCBs and HCB are retained in the snowpack.

This behaviour is reported also by Semkin (1996) for a small creek in the Amituk Lake region on Cornwallis

Island (Canadian High Arctic). This dynamic has been supported by modelling prediction (Wania et al., 1999)

and explained mainly by snow characteristics and the air-ice and air-water partition coefficients of the

chemical, which controls the timing of chemical release in the meltwater.

In the middle-late summer (late July to September) contamination is dominated by HCH (mainly the alfa

isomer) and p,p’-DDE.

Less evident are patterns during the daily cycle. POP concentrations show some variability, however, a regular

daily trend is not apparent, since the concentrations are not significantly correlated with water temperature.

Moreover, the distance from the glacier seems not to influence the POP content in the water; this is probably

due to the relative short distance between the glacier and the sampling sites.

In the macro-invertebrate community, evidences of bioaccumulation are measured. In non-predator macro-

invertebrates major patterns are bioconcentration processes, driven by physical chemical properties of the

molecules and environmental concentrations. On the contrary, data on predators macro-invertebrates seem to

suggest that a slight effect of biomagnification can occur, although the trophic chain analyzed is very short.

As pointed out by Wania (1999), the dynamics of contaminant release may be of crucial ecotoxicological

importance, because they determine the occurrence, timing and magnitude of a potential pulse exposure in

aquatic systems during early spring, a period when biological activity is starting and the life stages of some

organisms may be particularly vulnerable to contaminants.

References

Blais J. M., Schindler D. W., Muir D. C. G., Sharp M., Donald D., Lafrenière M., Braekevelt E., Strachan W.

M. J., 2001a. Ambio, 30, 410-415

Blais J. M., Schindler D. W., Sharp M., Braekevelt E., Lafrenière M., McDonald K., Muir D. C. G., Strachan

W. M. J., 2001b. Limnol. Oceanograph., 46, 2019-2031

Lafrenière M. J., Blais J. M, Sharp M. J., Schindler D. W., 2006. Environ. Sci. Technol, 40 (16), 4909-4915

Semkin RG.,1996. Synopsis of research conducted under the 1994-95 northern contaminants program., 73, 105-

118

Villa S., Negrelli C., Finizio A., Flora O., Vighi M., 2001. Contamin. Amb. XXX (9), 473-478

Villa S., Negrelli C., Finizio A., Flora O., Vighi M., 2006. Ecotox. Environ. Saf., 63(1), 84-90

Wania F., Semkin R., Hoff J.T., Mackay D., 1999. Hydrol. Processes, 13, 2245-2256


24

Chlorinated Paraffins in the Alpine Region

Iozza S a,b*, Müller CE a, Bogdal C a, Schmid P a, Oehme M b, Bassan R c, Belis C d, Jakobi G e, Kirchner M e,Schramm K-W e, Sedivy I f, Kräuchi N f, Uhl M g, Moche W g, Offenthaler I g, Weiss P g, Simon i P ha Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for Analytical Chemistry, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland; b University of Basel, Department of Chemistry, St. Johanns-Ring 19, CH-4056 Basel, Switzerland; c Regional Agency for Environmental Prevention and Protection of Veneto, Italy; d Regional Agency for Environmental Protection of Lombardia, Italy; e GSF-National Research Centre for Environment and Health, Germany; f Swiss Federal Institute for Forest, Snow and Landscape Research, Switzerland; g Federal Environment Agency Ltd., Austria; h Slovenian Forestry Institute, Slovenia * corresponding author: [email protected]

Introduction

Chlorinated paraffins (CPs) are polychlorinated straight-chain n-alkanes with a chlorination degree between 30

and 70%. They are produced since the 1930s and their global annual production is estimated to be about

300’000 t per year. 1 CPs are divided according to their carbon chain length into three main categories: short

chain (SCCPs, C10-13), medium chain (MCCPs, C14-17) and long chain CPs (LCCPs, C>17). They are used as

flame retardants and plasticisers, and as additives in metal working fluids, in sealants, paints, and coatings. CPs

are classified as persistent and their physical properties imply a high potential for bioaccumulation as well as

for global long-range atmospheric transport. Compared to other persistent organochlorine compounds like

PCBs or toxaphenes, limited information is available about environmental CP concentrations.

This study presents altitude profile of CP levels in humus layers and needle samples collected within the

MONARPOP project. Instrumental analysis was performed using a triple quadrupole in the EI-MS/MS mode. 2

This method allows the determination of total CP concentration (sum of SCCPs, MCCPs, and LCCPs) within

one fast measurement.

Materials and Methods

Chemicals, sample clean-up, instrumentation parameters, and glassware pre-treatment are published in detail

elsewhere. 3, 4

Needle and humus samples. Samples were taken within the MONARPOP project from seven altitude profiles,

which consisted up to five subplots to examine the vertical CP distribution.

Results and Discussion

CPs were detected in all analysed humus and needle samples. A frequency histogram of total CP levels of the

humus layers are shown in Figure 1. CP concentrations of the humus layers ranged between 7-199 ng/g dry

weight (dw) (mean 40 ng/g dw). The levels were approx ten times higher compared to reported total PCB

concentrations (sum of PCB 28, 52, 101, 138, 153 and 180) in this region (mean 4.5 g/kg dw).5


25

Most of the humus samples (n = 25) had a concentration between 10 and 50 ng/g dw as shown in Figure 1.

Similar concentrations are also observed in fresh needle samples.

Figure 2 shows the correlation between CP levels and altitude. Higher CP concentrations were determined at

low altitudes (700-900 m). A tendency of a Gaussian distribution was observed between 900 to 1900 m altitude

with a maximum between 1300 and 1500 m.

0

5

10

0-1010-2

020-3

030-4

040-5

050-6

060-7

070-8

080-9

0

90-100

100-110

190-200

concentration range [ng/g dw]

num

ber

of C

P co

ncen

trat

ions

Figure 1 Frequency histogram of total CP levels in humus layers from the Alps obtained by GC-EI-MS/MS.

0

30

60

90

701-900

901-110

0

1101-1

300

1301-1

500

1501-1

700

1701-1

900

altitude range [m]

CP

conc

entr

atio

n [n

g/g

dw]

~

Figure 2 Histogram of total CP levels in humus layers from the Alps related to altitude. Error bars indicate the standard deviations.

Acknowledgment

MONARPOP is funded by the EU Interreg III B Programme “Alpine Space” and by the participating national

partners (the listed institutions of the authors and, in particular, the Austrian Federal Ministry for Agriculture,

Forestry, Environment and Water Management, the Bavarian State Ministry of the Environment, Public Health

and Consumer Protection, the German Federal Environment Agency and the Swiss Federal Office for the

Environment). Furthermore, we like to thank the Swiss Federal Office for the Environment (FOEN - BAFU) for

financial support.

References

1. Muir DCG, Stern GA, Tomy G. In The Handbook of Environmental Chemistry, Paasivirta J (ed.), Springer, Berlin Heidelberg New York, 2000:203-236, ISBN 3-540-65838-6.

2. Zencak Z, Reth M, Oehme M, Analytical Chemistry 2004; 76:1957-1962. 3. Iozza S, Hüttig J, Reth M, Zencak Z, Oehme M, Organohalogen Compounds 2006; 68:2404-2407. 4. Iozza S, Schmid P, Oehme M, Bassan R, Magnani T, Belis C, Vannini P, Jakobi G, Kirchner M, Sedivy

I, Kräuchi N, Uhl M, Moche W, Offenthaler I, Weiss P, Simon i P, Organohalogen Compounds 2007;68:587-590.

5. Weiss P, Fohringer J, Hartl W, Thanner G, Simoncic P, Organohalogen Compounds 2003; 60:


26

POSSIBLE ROLE OF THE EXPOSURE TO THE SUN OF THE DIFFERENT

MOUNTAIN SIDES ON THE POP DISTRIBUTION

Paolo Tremolada1*

, Sara Villa2, Antonio Finizio

2, Elisa Bizzotto

2, Roberto Comolli

2 and Marco

Vighi2

1 Department of Biology, University of Milan, Via Celoria 26, Milan, I-20133 Italy.

2 Department of Environmental and Land Sciences (DISAT), University of Milan Bicocca, Piazza della Scienza 1,

Milan, I-20126 Italy.

INTRODUCTION

Given their special features, high mountains are important areas in which to study environmental

distribution of organic contaminants (Daly and Wania, 2005; Vighi, 2006). In a recent work of

Tremolada et al. (2007) two altitudinal series of soil samples (one in the Peruvian Andes, Cordillera

Blanca and the other in the Italian Alps, Mount Legnone) were analysed for several classes of

Persistent Organic Pollutants (PCBs, DDTs, HCHs, HCB and Chlordane). A concentration increase

in line with elevation were found only in the Italian altitudinal transect. A possible explanation of

this was done by the presence in Italy of an higher precipitation gradient parallel to the altitudinal

one (up to 2000 mm/year). As reported by other authors (Davidson et al., 2003) precipitations can

be considered a key factor, beside temperature, for contaminant deposition and retention at high

altitude. Precipitation can act in two ways: 1) by enhancing deposition through the well-known

scavenging process; 2) by reducing re-volatilisation because of high precipitations, especially in

summer, mean high soil humidity; humidity in soils allows high water evaporation with a

consequent cooling effect upon the soil; low soil temperature is expected to reduce hydrophobic

compound volatilization. By these considerations, two issues can be further explored: the role of

precipitation (intensity and seasonal distribution) and the soil temperature. The last one is linked to

precipitation (as explained above), and obviously to the altitude, but also, particularly, to the

exposition to the sun of the mountain side. The possible role of the exposure was also suggested by

some of the Mount Legnone results. Most of the samples were collected on the North face or in the

Eastern one, while only two samples in the upper part of the mountain (above 2400 m a.s.l.) were

collected near to the South face, because of the accessibility of the mountain. The contamination

levels of these two samples from the South-SW face on the top of the mountain (between 2400 and

2600 m a.s.l.) were lower than those of the other samples of similar altitude (between 2000 and

2200 m a.s.l.) but different exposure (East). Being Mount Legnone an isolated, not very high and

relatively sharp mountain, the precipitation intensity of the different sides, specially near to the top,

is presumably the same. Therefore, the possible role of the exposure to the sun of the different

mountain side is derived. This suggestion is based on a few experimental data and on a East/South

comparison, but it can be assumed as a reasonable preliminary hypothesis, waiting to more

appropriate experimentally-based analyses. This issue is currently under investigation by a specific

sampling campaign nearby, at the same altitude (2000 m a.s.l.) but considering two areas having the

opposite exposure faces (North vs. South).

MATERIALS AND METHODS

Sampling: Soil samples were taken from Mount Legnone, Italian Alps near Lake of Como in

August 2003. Details on the sampling modality and the pedological analyses are available in

Tremolada et al. (2007).

Chemical analysis: The following IUPAC congener numbers in elution order were screened: 30

(internal standard), 18, 31, 28, 52, 49, 104, 44, 64, 41, 40 (recovery standard), 95, 74, 70, 66, 90,

101, 99, 136, 97, 87, 110, 151, 149, 188, 118, 132, 153, 141 (internal standard), 105, 138, 187, 183,

128 (recovery standard), 174, 177, 156, 180, 201, 204 and 194. The extractions were performed


27

with n-hexane in a pre-cleaned Soxhlet apparatus (24 h) and the clean-up was performed by

sulphuric acid and Florisil column chromatography. Identification and quantification were done by

GC-MS technique. Details are reported in Tremolada et al. (2007).

RESULTS AND DISCUSSION

Total PCB concentrations and their congener composition (chlorination groups) in the East and

South-SW sides on Mount Legnone are shown in Figure 1.

Figure 1 – Comparison of the PCB concentrations from the East and South-SW side of Mount Legnone above 2000 m

a.s.l. and the relative composition of the different chlorination groups again for each exposition.

Observed differences between East and South-SW exposure are not high (below a factor 2) and

based on too few samples to allow any conclusion, but they are sufficiently interesting to suggest a

possible role of the mountain side, even more if we consider the possible comparison between the

North/South sides. This issue is related with summer POP re-volatilisation, as it seems to be

suggested also by the chlorination patterns of Figure 1. South exposure seems to reveal an higher

proportion of the less volatile congeners (highly chlorinated), while the East exposure seems to

retain more the more volatile ones (less chlorinated congeners).

REFERENCES Daly G.L. & Wania F. (2005) Organic contaminants in mountains. Environmental Science & Technology, 39, 385-398.

Davidson D.A., Wilkinson A.C., Blais J.M., Kimpe L.E., McDonald K.M. & Schindler D.W. (2003). Orographic cold-

trapping of persistent organic pollutants by vegetation in mountains of Western Canada. Environmental Science &

Technology, 37, 209-215.

Tremolada P., Villa S., Bazzarin P., Bizzotto E., Comolli R. and Vighi M. (2007). POPs in mountain soils from Alps

and Andes: suggestions for a ‘precipitation effect’ on altitudinal gradients. Accepted on Water, Air, & Soil

Pollution.

Vighi M. (2006). SETAC Europe Workshop Milan, Italy, 1-3 July 2004 Department of Environmental Sciences,

University of Milano-Bicocca ‘The role of high mountains in the global transport of persistent organic chemicals’.

Ecotoxicology and Environmental Safety, 63, 108-112.

East (2000-2200 m a.s.l.)

0

10

20

30

40

tri tetra penta hexa hepta octa % c

hlo

rin

atio

n g

rou

p

South-SW (2400-2600 m a.s.l.)

0

10

20

30

40

tri tetra penta hexa hepta octa

%ch

lori

nat

ion g

rou

p

Exposure

0

5

10

15

20

25

30

35

East South-SW

PC

B c

on

cen

trat

ion

(n

g/g

o.m

.)


28

Distribution of halogenated POPs across the Alps

Ivo Offenthaler1, , Rodolfo Bassan3,Claudio Belis4, Peter Futterknecht1, Saverio Iozza2, Gert Jakobi5, Manfred Kirchner5, Wilhelm Knoth8, Norbert Kräuchi6, Walkiria Levy-Lopez5,Wolfgang Moche1,Bernhard Schwarzl1, Gerhard Thanner1, Maria Uhl1, Karin Van Ommen1, Karl-Werner Schramm5, Isabella Sedivy6,

Primoz Simoncic7, Peter Weiss1

1Austrian Environment Agency; 2Eidgenössische Materialprüfungsanstalt, Switzerland; 3Regional Agency for Environmental Prevention and Protection of Veneto, Italy; 4Regional Agency for Environmental Protection of Lombardia, Italy; 5GSF-National Research Centre for Environment

and Health, Germany; 6WSL Swiss Federal Institute for Forest, Snow and Landscape Research; 7Slovenian Forestry Institute; 8Umweltbundesamt, Germany; ivo.offenthaler umweltbundesamt.at

1. Introduction

Part of the Interreg III B project MONARPOP was the investigation of POP loads in forest ecosystems of the

Alps, as indicated by pollutant contents in needles of Norway spruce (Picea abies [L.] Karst.), humus and

mineral soil. Among the numerous compounds included in the survey were polychlorinated dioxins and furans,

polychlorinated biphenyls and most of the pesticides belonging to the “Dirty dozen” of the Stockholm

Convention on Persistent Organic Pollutants. Norway spruce forests were selected for this project as the type of

woodland that forms a major part of the investigated area. Moreover, their rough canopy structure and the waxy

needle surface is a physical and chemical trap for airborne lipophilic compounds such as POPs. Forest humus at

these altitudes mineralises only slowly and remains undisturbed by soil cultivation. Similarly, biomass removal

is very limited so that humus and the topmost layer of mineral soil are likely to reflect POP input over the

previous years. Needles, in contrast, were chosen as ecologically relevant indicators of the current situation.

2. Material and Methods Samples were taken from Norway spruce stands at 1400 m a.s.l. which, by absence of obvious local traffic,

domestic, or industrial sources, qualified as “remote”. Shoots of the current year were harvested from two vital

adult spruce (2-3 branches from the top 7th whirl each). After collecting the entire humus layer from ten

regularly spaced 0.3×0.3 m pits, a soil core (0–10 cm mineral soil) was taken from each pit. Humus and mineral

soil samples were freeze-dried, ground (humus) under cool conditions, homogenised and sieved. PCDD/F, PCB

and OCP concentrations were determined with HRGC/HRMS.

3. Results and Discussion Humus generally showed the highest pollutant concentrations, followed by mineral soil and needles. This

pronounced difference is probably due to the enrichment of lipophilic, poorly degradable humus compounds in

coniferous stands which retain POP contamination from needle litter and throughfall.

Some compounds differed significantly between lati- or longitudinal zones (Figure 1): humus concentrations

and almost all needle concentrations were highest in one of the lateral groups. This suggests that the long-range

atmospheric transport of POPs is intercepted by the alpine range.


29

a b

south

central

north

2 4 6 8 10

sum PCDD/F

ng TEQWHO kg−1 d.m. Figure 1: a) Latitudinal grouping into northern (N), central (C) and southern (S) sites. b) Total PCDD/F concentrations in humus, expressed in TEQWHO. Ranking the sites by this criterium showed a highly significant1 imbalance between northern, central and southern scores.

Some classes of compounds, like PCDD/F and PCB, were strongly correlated (Figure 2). This suggests that

POP pollution in the Alps is an issue of multiple contamination with possibly synergistic amplification of

adverse effects.

0.1 0.2 0.3 0.4 0.5 0.6 0.7

0.5

1.0

1.5

2.0

2.5

3.0

Σ PCDD F [µg kg−1 d.m]

Σ PCBTE

[µg kg

−1 d.m.]

Figure 2: Highly significant2 correlation between total PCDD/F and content of twelve dioxinlike PCB.

Acknowledgements

The project MONARPOP was funded by the EU in the framework of the Interreg III B programme “Alpine space” and received

major contributions from the Austrian Ministry for Agriculture, Forestry, Environment and Water Ressources; several Austrian

provinces (Burgenland, Niederösterreich, Oberösterreich, Kärnten, Steiermark, Vorarlberg, Wien); the Bavarian State Ministry of the

Environment, Public Health and Consumer Protection; the Swiss Federal Office for the Environment; the Italian Fondo Rotazione;

together with substantial contributions in money or in kind from the following: Austrian Environment Agency (Umweltbundesamt),

German Federal Environment Agency, German National Research Center for Environment and Health (GSF), Italian ARPA

Lombardia and ARPA Veneto, Slowenian Forestry Institute, Swiss Federal Institute for Forest, Snow and Landscape Research.

1 Kruskal-Wallis, α ≤ 0.004, n=10/12/9 for northern/central/southern sites

2 rPearson=0.86, α ≤ 0.001


30

POPs in the Czech boarder mountains ecosystem – occurrence and long-term trends Ivan Holoubek, Jana Klanová, Jiří Jarkovský, Milan Sáňka, Jakub Hofman, Pavel Čupr

RECETOX, Masaryk university

Central and Eastern European POPs Centre National POPs Centre CR

Kamenice 126/3, 625 00 Brno, Czech Republic [email protected]

http://recetox.muni.cz

Persistent organic pollutants (POPs) are semi-volatile, mobile in the environment with the tendency to cummulation in abiotic part of environment and strong tendency to bioaccumulation. Soils play an important role in the global fate and distribution of POPs and have been identified as a sink for these toxic chemicals from where they can be released into water or air. Soils are natural sinks for persistent organic pollutants and represent rather a long-term archive for the atmospheric deposition than an indicator for the actual input of these compounds. A POPs study in different environmental compartments such as soils, sediments, water and snow in geographical areas with a continuous matter cycling flux could provide insights on the biogeochemical cycling of the pollutants within hydrographical basis according to their anthropogenic influence. Due to air and water transport, they are distributed widely across the globe, even in pristine regions, such as Antarctica. Recently, research has focused on altitudinal gradients where similar pollution patterns previously observed at latitudinal gradients are being observed in mountain areas, i. e. highland areas seems to be receiving a higher pollutant burden from nearby source areas. RECETOX project SOILS which is a part of long-term reaserch project INCHEMBIOL represents a scientific strategy uses the results from monitoring as one from the very useful experimental tools for the study of real environmental process. Project is based on the the following goals as a basic working hypothesis:

a) Summarised the levels of POPs (PAHs, OCPs, PCBs, PCDDs/Fs) in soils of the Czech Republic for the reference year 2001 and evaluated them;

b) Based on these experimental levels to calculate POPs soil burden in the CR; c) To measure laboratory volatilisation of basic POPs from various types of soils as a base

for the estimation of POPs emission fluxes; d) Based on the knowledge of real soil POPs burden and using of experimental soil emission

factors to calculate the contribution of POPs volatilisation from the soils in the CR to the actual levels of these substances in ambient air;

e) Estimation of risk potentials for human and wildlife of contaminated soils in the CR. f) Study of soil fate of POPs including high mountains regions.

As concerning to POPs contamination in the Czech high-mountain ecosystems, the first part were performed in the period 1994 - 1999. The goals of this part were the study of the contribution of long-range transport to the critical loading of environment, the distribution of selected POPs among air, needles and soils. The main part of sampling sites was located more than 1 000 m above the see level. This study continues in the years 2001, 2006 and 2007. The data from RECETOX reference year from high mountains sampling sites (n=9) are summarised in the following tables.


31

Table 1: Selected organic polutants [µg.kg-1]

Parameter Mean Median Minimum Maximum

HCB 1.572 1.410 0.500 2.920

α-HCH 0.382 0.350 0.120 0.940

β−HCH 0.094 0.030 0.030 0.390

γ.HCH 0.370 0.260 0.080 0.670

δ−HCH 0.010 0.010 0.010 0.010

Σ HCHs 0.857 0.650 0.260 1.660

Σ DDTs 315.219 69.160 8.810 1908.330

DDE 52.480 15.230 2.310 265.300

DDD 25.933 9.140 1.480 133.280

DDT 236.810 46.040 5.020 1509.760

Σ PAHs 3767.933 3713.200 1693.800 8187.500

PCB 153 6.086 5.700 1.950 10.110

Σ PCBs 22.759 22.640 7.900 36.180

DDT / DDTs 0.673 0.670 0.570 0.790

α−HCH/γ-HCH 1.061 0.940 0.620 1.720

Table 2: Levels of PCDDs/Fs

2378-PCDDs/Fs [ng.kg-1] TEQ 2378-TCDD [ng.kg-1]

Parameter Mean Median Minimum Maximum Mean Median Minimum Maximum

2378-TCDF 90.238 75.560 31.870 205.850 9.024 7.556 3.187 20.585

12378-PeCDF 32.682 26.300 9.810 78.010 1.634 1.315 0.491 3.901

23478-PeCDF 34.670 28.500 12.340 84.610 17.335 14.250 6.170 42.305

123478-HxCDF 51.017 40.230 16.760 142.810 5.102 4.023 1.676 14.281

123678-HxCDF 37.991 29.370 12.100 103.420 3.799 2.937 1.210 10.342

123789-HxCDF 32.377 25.110 11.780 84.510 3.238 2.511 1.178 8.451

234678-HxCDF 2.586 1.970 0.740 7.650 0.259 0.197 0.074 0.765

1234678-HpCDF 183.242 141.540 60.570 537.770 1.832 1.415 0.606 5.378

1234789-HpCDF 18.383 12.610 5.840 56.830 0.184 0.126 0.058 0.568

OCDF 273.694 197.770 91.730 954.400 0.027 0.020 0.009 0.095

Sum of 2378-PCDFs 756.880 575.880 253.930 2255.860 42.434 34.053 14.676 106.671

2378-TCDD 2.068 1.400 0.520 4.930 2.068 1.400 0.520 4.930

12378-PeCDD 8.422 7.040 2.480 19.900 8.422 7.040 2.480 19.900

123478-HxCDD 6.848 6.120 2.130 15.960 0.685 0.612 0.213 1.596

123678-HxCDD 11.504 10.480 3.570 25.510 1.150 1.048 0.357 2.551

123789-HxCDD 18.547 16.010 5.950 41.370 1.855 1.601 0.595 4.137

1234678-HpCDD 103.772 97.990 31.470 213.730 1.038 0.980 0.315 2.137

OCDD 410.642 385.180 125.730 816.510 0.041 0.039 0.013 0.082

Sum of 2378-PCDDs 561.803 523.910 171.850 1137.490 15.259 12.409 4.492 34.913

Sum of 2378-PCDDs/Fs 1318.683 1041.190 425.780 3393.350 57.692 46.086 19.168 141.584

The trends in POPs levels in the Czech mountains will be discussed. Acknowledgement: This project was/is supported by Ministry of Education of the Czech Republic, Project MSM 0021622412 INCHEMBIOL, and Ministry of Environment of the Czech Republic, Project SP/1b1/30/07.


32

Modelling the Orographic Cold-Trapping of Persistent Organic Pollutants

John N. WESTGATEa, Frank WANIA

b

a,bDepartment of Chemistry, University of Toronto Scarborough, 1265 Military Trail, Toronto, Ontario, Canada

M1C 1A4, [email protected],

[email protected],

bcorresponding author

Introduction Environmental fate and transport models, such as the multi-compartment fugacity-

based box model Globo-POP, have been widely used to help understand the distribution and

accumulation behaviour of Persistent Organic Pollutants (POPs) along latitudinal gradients on a

global scale (1). Recently a similar model, called Mountain-POP, has been developed to

elucidate the distribution and accumulation of POPs along altitudinal gradients in a variety of

mountain systems (2). Zonal and elevational gradients share many environmental characteristics

such as the change in surface cover and temperature. This suggests that similar mechanisms may

be responsible for the accumulation of POPs at the Earth’s poles and at high altitudes. However,

besides the widely different dimensions and distances involved, the global environment and

mountain regions also differ with respect to many other environmental factors that may impact

on the accumulation of POPs (e.g. precipitation gradients, water coverage). It is thus possible

that the mechanisms of accumulation are different, and in particular that a different suite of POPs

will accumulate in the two different environments.

Methods In its current form, the Mountain-POP model consists of five zones, or ‘boxes’, each

representing an elevational zone on the wind- or leeward side of a mountain range. The transport

of contaminant between the compartments (primarily air and soil) of each box and between the

boxes is treated dynamically as a function of time. A scenario of inputs of an organic

contaminant over time is supplied to the model, as well as a set of chemical partitioning

properties and degradation rates and their temperature dependence. By solving a series of mass

balance equations the concentrations of the contaminant as a function of time are computed for

all phases in each box. By systematically varying the partitioning properties of hypothetical, but

realistic, chemicals and computing their fates it is possible to determine which of the chemical

property combinations lead to accumulation in which environments. Furthermore, by

systematically varying the environmental parameters it is feasible that the mechanisms of

accumulation for one set of chemical properties be revealed.


33

Results and Discussion Preliminary results from this work show that there are differences in

the partitioning properties of theoretical, perfectly persistent chemicals which accumulate in the

high elevations of the mountain model versus those which indicate accumulation in the Arctic

zone of the global model. Work is ongoing to reveal what values of which environmental

parameters lead to those differences. Ultimately, the goal is to achieve a mechanistic and

quantitative understanding of the differences between orographic and global cold-trapping.

References

1. Wania, F., Mackay, D. A global distribution model for persistent organic chemicals. Sci.

Total Environ. 1995, 160/161, 211–232.

2. Daly, G.L., Lei, Y.D., Teixeira, C., Muir, D.C. G., Wania, F. Accumulation of current-

use pesticides in neotropical montane forests. Environ. Sci. Technol. 2007, 41, 1118-

1123.

Figure 1. A cartoon describing the general form of the MountainPOP model,

a simple level IV fugacity based box model, when used to describe a typical

generic mountain system.


34

A comparison of emissions vs. masses of semivolatile organic compounds

in the Alpine forests.

Belis C1, Bassan R2, Jakobi G3, Kirchner M3, Knoth W4, Kraeuchi N5, Moche W6, Nurmi-Legat J6, Raccanelli St7, Schramm K-W3, Sedivy I5, Simoncic P8, Uhl M6, Weiss P6

1Regional Agency for Environmental Protection of Lombardia, Italy; 2Regional Agency for Environmental Prevention and Protection of Veneto, Italy; 3GSF-National Research Centre for Environment and Health, Germany; 4German Environmental Agency; 5WSL Swiss Federal Institute for

Forest, Snow and Landscape Research; 6Umweltbundesamt Ltd. Austria; 7INCA Laboratory, Italy; 8Slovenian Forestry Institute

1. Introduction

Forest ecosystems represent the prevailing ecosystem type in the Alps. Approx. 7.5 Mio. ha (i.e. 50 % of the

area in the Alps) are covered with forests. In addition, forests are important sinks for semivolatile organic

compounds (SVOCs). The project MONARPOP analysed two important sink compartments, needles of

Norway spruce (Picea abies [L.] Karst.) and forest soil of remote Alpine forest sites in Austria, Germany, Italy,

Slovenia and Switzerland, for the concentrations of SVOCs.

The present contribution compares rough estimates of pollutant masses in the Alpine forests with emission and

use of these pollutants for the investigated countries.

2. Material and Methods The concentrations of several SVOCs (PCDD/F, PCB, PBDE, PAH, various chloropesticides) in 1/2-year old

needles, humus layer and mineral soil from 40 remote Norway spruce forest sites were used. For concentrations

below the detection limit zero was used. The sampling with defined volumes of the humus layer and the soil

cores allowed mass estimates of these compartments per hectare (ha). Forest areas were taken from the

investigated countries’ national forest inventories (NFIs). The green crown biomass of the forests was obtained

from the NFI (Switzerland) or estimated from results of various forest ecosystem studies. According to a

compilation of such studies the following figures were used: 17.5 tons (t) needle mass per ha for Norway spruce

forest and 3.5 t ha-1 needle and leave mass for all other tree species. The estimates were derived in two ways, i)

from country specific data and means and ii) from average data for the whole study area.

The emission data (PCDD/F, PAH) were taken from the national emission reports under the UN "Convention

on Long Range Transboundary Air Pollution". These figures were converted to per-capita emissions for

individual Alpine countries and on basis of these and the population figures for the Alps to emissions in the

Alpine region as a whole.

3. Results and Discussion Bearing in mind the various uncertainties of these estimates, both the pollutant masses in the forest ecosystems

and the emissions should be taken as a first rough estimate of scale. The uncertainties include, eg. the


35

generalisations from half-year old needles to all needle ages, Norway spruce forest to other forest ecosystems,

remote sites to all Alpine forest sites, but also the limited number of sites, or the variation of national emission

data which may be more representative for the whole country than for its Alpine regions. Given these

limitations and the methods used, pollutant masses in the forests will likely have been underestimated and

emissions in the Alpine region overestimated. Nevertheless, the total of the country specific estimates of

pollutant masses (approach i) does not deviate considerably from the estimate based on average values for the

whole study region (approach ii) despite the share of the Alpine area varies significantly among countries. This

indicates a rather robust estimate of scale.

The PCDD/F masses in the green crown biomass and soil of forests of the Austrian, German (Bavarian), Italian,

Slovenian and Swiss part of the Alpine region are 7 kg TEQ (“sum” estimate) or 12 kg TEQ (“mean” estimate).

These PCDD/F masses expressed in TEQ are three orders of magnitude higher than the estimated emissions in

this region in 2004. Forests cover approx. 50 % of the Alpine area. The difference between the actual emissions

and the masses bound in the forests is assumed to be caused by the accumulation of these compounds in the

studied compartments, higher emissions in previous years and, mainly, by an additional PCDD/F input from

regions outside the Alps. For PAH, estimated pollutant stocks in forests were one order of magnitude higher

than the corresponding emission estimates. For both groups of compounds the pollutant stocks in needles/leaves

are negligibly small (clearly below 1/1000) compared to forest soil.

Estimated masses of several chloro-pesticides and PCBs in Alpine forests amount to tons, despite their ban

since the 90ies of the last century (eg. sum PCB approx. 8 t, gamma-HCH approx. 2 t, Dieldrin and HCB

around 3 t each and still around 15 t of DDT isomers). Again, more than 99 % of the total pollutant masses are

bound in the forest soils, but the share in the forest crown is higher for HCH and HCB than for the PCDD/F and

PAH .

Acknowledgements

The project MONARPOP was funded by the EU in the framework of the Interreg III B programme “Alpine space” and received

major contributions from the Austrian Ministry for Agriculture, Forestry, Environment and Water Ressources; several Austrian

provinces (Burgenland, Niederösterreich, Oberösterreich, Kärnten, Steiermark, Vorarlberg, Wien); the Bavarian State Ministry of the

Environment, Public Health and Consumer Protection; the Swiss Federal Office for the Environment; the Italian Fondo Rotazione;

together with substantial contributions in money or in kind from the following: Austrian Environment Agency (Umweltbundesamt),

German Federal Environment Agency, German National Research Center for Environment and Health (GSF), Italian ARPA

Lombardia and ARPA Veneto, Slowenian Forestry Institute, Swiss Federal Institute for Forest, Snow and Landscape Research.


36

Origin of polluted air masses in the Alps August Kaiser, Central Institute for Meteorology and Geodynamics, Hohe Warte 38, 1190 Vienna,

Austria, [email protected]

Abstract

The Alps, situated in the centre of Europe, are surrounded by regions with high air pollutant

emissions: The main sources of NOx are located in the Po-Basin and in northwest Europe, main SO2

and PM sources are situated in northwest Europe, south Poland and north Czech Republic and some

strong point sources are in southeast Europe. Due to dilution processes, the concentrations of near

ground emitted primary air pollutants decrease with height in dependence of the life time of the

pollutant in the atmosphere – air pollutants with a longer life time showing weaker vertical gradients

e.g., CO) compared with air pollutants with shorter life time (e.g., NOx). On the other hand, some

secondary air pollutants (e.g., ozone) increase with height. Due to the increasing precipitation

amount, the wet deposition of air pollutants also increases with height. Thus, and due to the sensitive

alpine ecosystem, attention should be paid to air pollution in the Alps.

What are the transport processes, leading to high air pollutant concentration in the Alps? Thermal heating induces typical local and regional wind systems in mountain valleys (Fig.1 ). During

daytime, the slopes and the valley itself are warmed up by the solar radiation, causing up-slope and

up-valley winds (Fig. 1a). On the other hand, during nighttime, cold air descends form the slopes

(down-slope wind) and flows out of the valley (down-valley wind). These wind systems are most

pronounced in summer.

a) daytime b) nighttime Fig. 1: Thermally induced wind systems in mountain valleys.

The effects of the thermally induced wind systems on the air pollutant concentration is shown in

Fig. 2 for stations with different heights in the Achen Valley (Tyrol) and for Sonnblick (3105 m). At

valley floor the NOx concentration has its maximum in the early morning, when the emission is high

and the stratification of the valley atmosphere is stable. The NOx peak is connected with low ozone

concentration. With the onset of the up-slope wind, the air rich in NOx but poor in ozone is

transported to the higher situated stations. The higher the station, the later the station is reached by

the air rich in NOx but poor in ozone. At the highest station Sonnblick the daily variations of both

pollutants are very small.

In addition to the thermally induced local wind systems, air pollutants are transported with the large

scale synoptic flow. Fig 3 shows the NOx concentration at Sonnblick during 2006 (measured with a

molybdenum converter). The figure shows high concentration peaks especially during winter and

spring months. These concentration peaks are caused by the large scale air flow. Fig 4 shows the


37

dependence of the NOx concentration on the large scale air flow for Zugspitze and Jungfraujoch. For

each station, the air flow (trajectories) was calculated with the model FLEXTRA for each three hours

for the period from January 1999 to Dec. 2002 and weighted with the deviation of the measured NOx

concentration from a Gauss low pass filter (3-monthly running mean), so that air flows, connected

with high pollutant concentration get a positive (coloured red) and air flows with low concentration a

negative sign (blue). The method is described in Kaiser et al. (2007). The Figure and additional

simulations with dispersion models show that both stations are influenced from NOx sources in

northwest Europe; the western Alps (Jungfraujoch) are also influenced from sources in the Po Basin

and the east Alps (Sonnblick) is most exposed to sources in east Europe.

Mean daily variation for NOx (June-August)

0

50

100

150

200

250

300

350

400

00:30

03:00

05:30

08:00

10:30

13:00

15:30

18:00

20:30

23:00

10-1

ppb

0

5

10

15

20

25

30

35

40

Achental, 930 mAchental, 1280 mSonnblick, 3105 m

Mean daily variation for ozone (June-August)

0

10

20

30

40

50

60

70

00:3

0

02:3

0

04:3

0

06:3

0

08:3

0

10:3

0

12:3

0

14:3

0

16:3

0

18:3

0

20:3

0

22:3

0

ppb

Achental, 930 mAchental, 1280 mAchental, 1758 mSonnblick, 3105 m

a) NOx b) Ozone Fig. 2: Mean daily variation for NOx and ozone in different heights.

Fig 3: NOx (10-2 ppb) at Sonnblick, 2006: a) Zugspitze b) Jungfraujoch Fig. 4: Air flow regimes connected with high (red)

and low (blue) NOx concentration The contribution of ZAMG to MONARPOP A first air flow analysis for Sonnblick, Zugspitze and Weissfluhjoch confirm that Weissfluhjoch is also

influenced from the Po Basin, even though it is situated in the very east of Switzerland. Further

analyses are in progress.

References Kaiser, A. et al.: Transport of nitrogen oxides, carbon monoxide and ozone to the Alpine Global

Atmosphere Watch stations Jungfraujoch (Switzerland), Zugspitze and Hohenpeißenberg (Germany),

Sonnblick (Austria) and Mt. Krvavec (Slonenia). Atmospheric Environment (2007),

doi:10.1016/j.atmospenv.2007.09.027

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