Monitoraggio dei POPs sul territorio alpino Copyright 2007 - ARPA Lombardia ISBN 978-88-903167-0-8

Monitoraggio dei POPs sul territorio alpino Copyright 2007 - ARPA Lombardia ISBN 978-88-903167-0-8 33 Studio delle concentrazioni di POPs nell area dolomitica R. Bassan, C. Bellio, A. Cavinato, S. Ganz, R. Piol, C. Belis., D. Heublein., S. Iozza, T. Jakl, G. Jakobi, M. Kirchner, W. Knoth, N. Krauchi, W. Levy-Lopez, T. Magnani, W. Moche, M. Oehme, I. Offenthaler, R. Perthen-Palmisano, D. Schmid, K. W. Schramm, P. Schroder, H. Schrott, I. Sedivy, P. Simončič, M. Uhl, P. Vannini, U. Vilhar, P. Weiss Abstract In the context of the MONARPOP project a study on the POPs concentrations in the three sites of the Dolomites has been carried out. In the matrices needles, humus layer, mineral soil and semi permeable membrane devices (SPMD) different POPs groups have been investigated: OCP, PCB, PCDD/F, PBDE, CP and PAH and generally low or very concentrations arose, especially in the site Val Visdende, showing one of the best situation of the whole alpine area. Introduzione Nell ambito del progetto MONARPOP relativo alla presenza di inquinanti organici persistenti (POPs) in siti remoti dell arco alpino (Weiss, 2007), sono stati analizzati campioni provenienti da quattro matrici ambientali: aghi di Picea abies (L.) Karsten (Abete rosso), humus, suolo minerale e aria, quest ultima attraverso campionatori attivi e passivi. Lo studio qui presentato riguarderà in particolare le prime tre matrici più le membrane semipermeabili per il campionamento passivo dell aria (Schramm, 2007); per ognuna si analizzerà in dettaglio la situazione nel Veneto attraverso il profilo altimetrico della Val Visdende ed i siti della Val Prampera e del Monte Grappa. Materiali e Metodi La scelta dei siti di studio è stata condotta con lo scopo di coprire la montagna veneta tra 45 50 e 46 38 Nord, in modo tale da avere informazioni sia su aree remote affacciate sulle Alpi Austriache e l Europa, sia sulla pianura Padana. Con questi criteri informatori, a nord è stata scelta la Val Visdende con la contigua Val Frison, a sud il Massiccio del Grappa, alla testata della Val Stizzon affacciata sulla pianura trevigiana e vicentina; intermedia tra questi due siti è stata individuata la Val Prampera (Dolomiti Zoldane), inserita nel Parco Nazionale delle Dolomiti Bellunesi, come indicato in Figura 1. La Val Visdende è geograficamente collocata tra il mondo dolomitico a sud, caratterizzato da valli incise e forte energia del rilievo, e quello alpino a nord, con forme più dolci. La valle si presenta particolarmente ampia per la confluenza di due rami guidati dalla tettonica e modellati dalle forme glaciali e fluvio-lacustri; risulta protetta verso meridione dall orografia e viene a trovarsi relativamente aperta alle correnti

34 Monitoraggio dei POPs sul territorio alpino Figura 1. Mappa dei punti veneti di campionamento. Tratta da Google earth 2007 e modificata. provenienti dal nord delle Alpi. E un area di pregio naturalistico caratterizzata da pochi insediamenti, popolati quasi esclusivamente nel periodo estivo, dall assenza di attività artigianali e industriali, e dalla presenza di viabilità esclusivamente silvo pastorale con valenza turistica nella buona stagione. Per queste motivazioni la valle è stata scelta per la realizzazione del profilo altimetrico tra 1123 e 1656 m s.l.m. e per il posizionamento delle capannine contenenti i campionatori passivi (SPMD). Nella valle sono stati anche eseguiti campionamenti di aghi di abete, humus e suolo minerale. La Val Prampera costituisce una valle remota di accesso al Parco Nazionale delle Dolomiti Bellunesi dalla valle di Zoldo. Collocata al centro delle Dolomiti Bellunesi tra i Gruppi del Talvena, S. Sebastiano e Cime di Mezzodì, la valle presenta orografia e morfologia particolarmente aspre; è caratterizzata da una notevole energia del rilievo che la rende isolata dai contigui territori antropizzati. La Val Prampera è contraddistinta dall assenza di insediamenti stabili, dalla presenza di viabilità esclusivamente silvo pastorale con valenza turistica prevalentemente estiva. Per il campionamento è stato scelto un sito a quota 1486 m. Il Monte Grappa è un massiccio montuoso che raggiunge i 1775 m. Appartiene alle Prealpi Venete e risulta diviso tra le province di Vicenza, Treviso e Belluno. Nell ambito dei siti di progetto costituisce la finestra sulla pianura padano-veneta. Il punto di campionamento è stato scelto a 1345 m in una zona sub pianeggiante ubicata alla testata della bellunese Val Stizzon, caratterizzata anch essa da scarsissima antropiz-

Studio delle concentrazioni di POPs nell area dolomitica 35 zazione. Il campionamento di aghi di abete rosso, strato di humus e suolo minerale, così come la conservazione ed il trasporto dei campioni, sono avvenuti secondo metodologie standardizzate e condivise da tutti i partners di progetto, definite nell ambito di numerosi incontri tecnici. Le analisi chimiche per la ricerca degli inquinanti organici persistenti sono state quindi svolte presso i laboratori selezionati. Le elaborazioni dei dati analitici svolte presso il Dipartimento Provinciale ARPAV di Belluno, rivolte allo studio della situazione locale, sono state effettuate mediante l impiego del software statistico Kyplot e fogli di calcolo. Risultati e discussione Le elaborazioni effettuate verranno di seguito riportate per singola matrice d indagine. Si considereranno sia i siti standard che i profili altimetrici e nei confronti e calcoli delle variabili statistiche saranno trattati indistintamente. Eventuali valutazioni saranno effettuate nel dettaglio solo per i tre siti veneti, ove presenti i dati. Nella Figura 2 sono rappresentati i valori minimi, massimi e medi per le famiglie di inquinanti indagate nei siti del Veneto e del resto dell arco alpino, divisi per matrice. Aghi di abete. Gli aghi delle piante di abete sono stati sottoposti all analisi di quattro famiglie di POPs: pesticidi organoclorurati (OCP), policlorobifenili (PCB), diossine e furani (PCDD/F) e idrocarburi policiclici aromatici (PAH) (Schroder et al., 2007). Nel profilo altimetrico della Val Visdende per tutti gli OCP i valori di concentrazione più alti si sono osservati a quota 1553 m, in corrispondenza del terzo punto del profilo, con concentrazioni in quota o in fondo valle sempre inferiori (Kirchner, 2007). Sebbene tutte le concentrazioni siano comprese nell intervallo (µ 2σ) <x<(µ+2σ), il punto sopraccitato spesso presenta concentrazioni che si discostano di molto da quelle degli altri punti, in particolare per DDT e Dieldrina. Nel caso di PCB, diossine e furani in Val Visdende si sono sempre riscontrate le concentrazioni più basse dell intero arco alpino; in Val Prampera la situazione si è dimostrata lievemente peggiore per i PCB, con concentrazioni comunque nella media, mentre diossine e furani hanno presentato basse concentrazioni. Per il sito del Monte Grappa, invece, le concentrazioni di PCB e PCDD/F rilevate sono apparse nettamente superiori a quelle degli altri siti provinciali, probabilmente a causa dell influenza della vicina pianura veneta (Offenthaler et al., 2007; Offenthaler, 2007). Concludendo con l analisi dei PAH (Bassan & Ganz, 2007; Belis et al., 2007), in Val Visdende si sono riscontrate concentrazioni molto basse alle quote inferiori del profilo verticale (rispettivamente 1123, 1305 e 1553 m). Il quarto punto del profilo, a 1656 m, ha presentato invece concentrazioni decisamente elevate rispetto alla media dell arco alpino, superiori anche alle concentrazioni dei punti campionati in Val Prampera e sul Monte Grappa. Strato di humus. La matrice del suolo più superficiale e di natura organica nota come humus è stata analizzata ricercando OCP, PCB, PCDD/F, difenileteri polibromurati (PBDE), cloroparaffine (CP) e PAH. A rappresentare la situazione veneta è disponibile

36 Monitoraggio dei POPs sul territorio alpino Figura 2. Valori minimi, massimi e medi per inquinanti nei siti veneti e nel resto delle Alpi, per matrice d indagine.

Studio delle concentrazioni di POPs nell area dolomitica 37 come unico sito quello della Val Visdende. Qui le concentrazioni maggiori di OCP si sono registrate nel punto di fondovalle (1123 m), mentre salendo di quota la situazione ha registrato significativi miglioramenti, fino a raggiungere le concentrazioni più basse di tutto l arco alpino. Per PCB, diossine e furani si è ripresentato un andamento con un massimo a quota 1553 m, terzo punto del profilo; nel caso dei PCB spesso il valore massimo è risultato notevolmente superiore alle concentrazioni di fondovalle e in quota, mentre minori differenze si sono riscontrate per diossine e furani. I PBDE hanno mostrato andamenti simili ai precedenti composti, ma con concentrazioni molto basse, prossime ai valori minimi dell intero campione (Knoth et al., 2007a, Knoth et al., 2007b). La concentrazione di cloroparaffine hanno invece presentato un trend di crescita da valle a monte, con il raggiungimento alle quote più alte (1656 m) di valori molto elevati (Iozza, 2007). Infine i PAH (Bassan & Ganz, 2007; Belis et al., 2007), presenti in concentrazioni sempre inferiori alla media, hanno di contro evidenziato un profilo decrescente con la quota, dove a 1656 m si è presentato il minimo assoluto dell intero campione alpino. Suolo minerale. Per la matrice suolo minerale i dati attualmente disponibili sono quelli relativi ai soli idrocarburi policiclici aromatici. L unico campione veneto, relativo alla Val Visdende, ha presentato concentrazioni molto basse vicine ai minimi assoluti. SPMD. I Semi Permeable Membrane Devices (SPMD) sono campionatori passivi dell aria, posizionati all interno di colonnine di legno (Levy-Lopez et al., 2007). Anche per questa matrice le analisi disponibili sono quelle relative ai PAH, con campioni provenienti dalla Val Visdende con concentrazioni mediamente basse, al di sotto della media dell arco alpino. Conclusioni Dalle analisi effettuate nei siti remoti della provincia di Belluno scelti per il monitoraggio degli inquinanti organici persistenti emerge che la situazione rispetto al quadro generale è fra le migliori. Le concentrazioni sono risultate generalmente basse, spesso inferiori alla media dell arco alpino, con valori che a volte rappresentano i minimi assoluti dell intero campione di dati. Il sito meno contaminato è risultato la Val Visdende; a seguire, nell ordine, la Val Prampera e il Monte Grappa, suggerendo così un gradiente nord-sud tra i tre siti dell area dolomitica. Interessante è risultato infine l andamento dei profili verticali in Val Visdende: per OCP negli aghi di abete e PCB, PCDD/F e PBDE nello strato di humus i massimi di concentrazione si sono verificati alla quota intermedia (1553 m), probabilmente a causa delle dinamiche dello strato mescolato nella valle. In altri casi, come ad esempio PAH e OCP nell humus, i profili sono risultati decrescenti con l altezza, con valori di concentrazione in quota pari ai minimi assoluti del campione; viceversa profili con massimi di concentrazione in quota, molto alti anche rispetto agli altri campioni dell arco alpino, si sono verificati nel caso, seppur unico, delle cloroparaffine nell humus.

38 Monitoraggio dei POPs sul territorio alpino Bibliografia Bassan R. & S. Ganz, 2007. PAHs presence in the investigated matrixes: comparison end evaluation. Presenza degli inquinanti organici persistenti nelle valli alpine. Venezia, 5/10/2007. Belis C., R. Bassan, D. Heublein, S. Iozza, T. Jakl, G. Jakob, M. Kirchner, W. Knoth, N. Krauchi, W. Levy-Lopez, T. Magnani, W. Moche, M. Oehme, I. Offenthaler, R. Perthen- Palmisano, K.W. Schramm, H. Schrott, I. Sedivy, P. Simoncic, M. Uhl, U. Vilhar, P. Weis, 2007. PAHs in needles and humus in alpine ecosystem (MONARPOP). Organohalogen Compounds (in press). Iozza S., P. Schmid, P. Oehme, R. Bassan, C. Belis, G. Jacobi, M. Kirchner, I. Sedivy, N. Krauchi, W. Moche, Offenthaler, I. Simoncic, M. Uhl, P. Weiss., 2007. Chlorinated paraffins in humus layers from the Alps (MONARPOP). Tokyo Dioxin 2007. Kirchner M., G. Jakobi, B. Henkelmann, S. Bernhöft, R. Bassan, C. Belis, N. Kräuchi, W. Moche, I. Offenthaler, P. Simončič, P. Weiss, K. W. Schramm, 2007. Pesticides in soil and spruce in the Alps. Presenza degli inquinanti organici persistenti nelle valli alpine. Venezia, 5/10/2007. Knoth W., R. Bassan, C. Belis, D. Heublein, S. Iozza, T. Jakl, G. Jakobi, M. Kirchner, N. Krauchi, W. Levy-Lopez, W. Moche, M. Oehme, I. Offenthaler, R. Perthen-Palmisano, D. Schmid, K. Schramm, H. Schrott, P. Schroder, I. Sedivy, P. Simoncic, M. Uhl, P. Weiss, 2007a. Results from the Monitoring Network in the Alpine Region for POPs-MONARPOP. Polybrominated diphenyl ether (PBDE) in humus layers in remote forests. International Workshop on Brominated Flame Retardants BFR 2007 Amsterdam. Knoth W., R. Bassan, C. Belis, G. Jacobi, M. Kirchner, N. Krauchi, W. Mann, R. Meyer, W. Moche, J. Nebhuth, I. Offenthaler, I. Sedivy, P. Simoncic, M. Uhl, U. Vilhar, P. Weiss, 2007b. Poster: PBDE in humus layers in remote forests. 4th International Workshop on Brominated Flame Retardants Amsterdam. Levy-Lopez W., B. Henkelmann, G. Pfister, S. Bernhoft, A. Niklauss, M. Kirchner, G. Jakobi, R. Bassan, C. Belis, T. Jakl, N. Krauchi, T. Magnani, W. Moche, I. Offenthaler, R. Perthen- Palmisano, P. Schroder, H. Schrott, I. Sedivy, P. Simoncic, M. Uhl, P. Vannini, U. Vilhar, P. Weiss, K. W. Schramm, 2007. Semipermeables membrane devices (SPMD) as passive samplers: data interpretation regarding exposure time. Tokyo Dioxin 2007. Offenthaler I., 2007. Dioxinlike and other halogenated pollutants in forest ecosystems of the Alps. Presenza degli inquinanti organici persistenti nelle valli alpine. Venezia, 5/10/2007. Offenthaler I., W. Moche, G. Thanner, M. Uhl, K. Van Ommen, R. Bassan, C. Belis, G. Jakobi, M. Kirchner, N. Krauchi, K. W. Schramm, W. Levy-Lopez, I. Sedivy, P. Simoncic, U. Vilhar, P. Weiss, 2007. Dioxin and dioxin-like pollutants in alpine forests. Tokyo Dioxin 2007. Schramm K. W., 2007. Novel diagnostic tools for POPs in alpine area. Presenza degli inquinanti organici persistenti nelle valli alpine. Venezia, 5/10/2007. Schroder P., R. Bassan, C. Belis., D. Heublein., S. Iozza, T. Jakl, G. Jakobi, M. Kirchner, W. Knoth, N. Krauchi, W. Levy-Lopez, T. Magnani, W. Moche, M. Oehme, I. Offenthaler, R. Perthen-Palmisano, D. Schmid, K. W. Schramm, H. Schrott, I. Sedivy, P. Simoncic, M. Uhl, P. Vannini, U. Vilhar, P. Weiss, 2007. Detoxification of organic pollutants by glutathione S transferas in spruce needles alpine forests - Results from a Monitoring in the Alpine Region for POPs (MONARPOP). Chicago Americal Society for Plants Biologists (ASPB). Weiss P., 2007. MONARPOP: starting point, plan and goals of the project. Presenza degli inquinanti organici persistenti nelle valli alpine. Venezia, 5/10/2007.

Monitoraggio dei POPs sul territorio alpino Copyright 2007 - ARPA Lombardia ISBN 978-88-903167-0-8 39 Results from the Monitoring Network in the Alpine Region for POPs MONARPOP POLYBROMINATED DIPHENYL ETHER (PBDE) IN HUMUS LAYERS IN REMOTE FORESTS Knoth W 1, Bassan R 2, Belis C 3, Jakobi G 4, Kirchner M 4, Kräuchi N 5, Mann W 1, Meyer R 1, Moche W 6, Nebhuth J 1, Offenthaler I 6, Sedivy I 5, Simončič P 7, Uhl M 6,Vilhar U 7, Weiss P 6 1 Federal Environment Agency Germany 2 Regional Agency for Environmental Prevention and Protection of Veneto 3 Regional Agency for Environmental Protection of Lombardia 4 GSF National Research Center for Environment and Health Germany 5 WSL Swiss Federal Institute for Forest, Snow and Landscape Research 6 Federal Environment Agency Ltd. Austria 7 Slovenian Forestry Institute Riassunto I bifenili etere polibromurati (PBDE) sono una famiglia di composti molto utilizzati come ritardanti di fiamma nella produzione di sostanze plastiche e di tessuti. Nel presente lavoro vengono presentate le concentrazioni di PBDE nell humus dei congeneri più significativi tra cui la miscela PentaBDE ( BDE 28+47+99+100+ 153+154), l OctaBDE (BDE 183) e il DecaBDE (BDE 209). Introduction Polybrominated diphenyl ether (PBDE) are heavily used as flame retardants in plastics and textiles and have therefore become ubiquitous (de Wit 2002, Letscher & Behnisch 2003). There exist three technical products: Pentabromodiphenylether (PentaBDE) mix, octabromodiphenylether (OctaBDE) mix and decabromodiphenylether (DecaBDE). Because of exponentially increasing levels of the congeners of PentaBDE and OctaBDE mix in human blood and milk (Hites 2004), these two products were banned in many countries (BSEF, EU 2003, NCEL) and industry voluntarily ceased production (Tullo 2003). Decabromodiphenylether was not included in these bans because it is believed to have low bioaccumulation (EU 2004) and low long-range air transport potential (Wania & Dugani 2003). About 8000 t DecaBDE were used in EU countries in 2004 (EBFRIP 2005). Industry tries to reduce existing emissions throughout the live-cycle and sponsors a deca-monitoring programme (BSEF). Plant surfaces were already used for sampling of PBDE from air. (Hassanin 2005, Mariussen 2005, Ohta 2002, Okazawa 2004, Schlabach & Gjerstad 2006, Schütz 2004, Zhu & Hites 2006). Especially the rough canopy of coniferous forests combs the bypassing air for pollutants and conifer needles efficiently trap lipophilic organic compounds due to their highly absorbing epicuticular wax. The topsoil humus layers

40 Monitoraggio dei POPs sul territorio alpino in forests with their high organic carbon content accumulate POPs from deposition and fall of needles over a long period (Weiss 2002). For this study humus samples from remote Norway spruce (Picea abies) forests were analysed for PBDE. This paper presents results from the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP, Bassan 2005). Its main goal is to investigate the actual contamination of the Alps and to understand the role of high mountains in the global atmospheric transport of POPs (Daly & Wania 2005, Vighi 2006). Materials and Methods Humus Sampling 56 humus samples from remote Norway Spruce forest sites in the Alps were sampled for PBDE analysis. This was done by collecting the entire humus layer within a 30 x 30 cm metal frame. Ten pits along a 5 x 30 m rectangular grid were collected systematically and mixed to one sample. This yielded up to 60 l of humus per sampling plot. Analytical Method In indoor dust high concentrations of PBDE were detected (Knoth 2003, 2006). Therefore, a clean laboratory environment is essential for the analysis of PBDE, in particular for the analysis of DecaBDE. Polymer material (e.g. red rubber septa) was tested before use. Silica, sodium sulfate and glass wool were extracted with dichloromethane. After evaporation of the solvent, silica and sodium sulfate and all laboratory glassware used for the clean-up procedure were baken out for 16 hours at 450 C. Glass fibre extraction thimbles and filters, Pasteur pipettes and glass wool, which became brittle if heated so long, were immediately cooled down after heating up. After cooling down the glassware was immediately capped with aluminium foil or stored in metal boxes until usage. Sodium hydroxide water solution for the preparation of SiO 2 -NaOH was extracted three times with dichloromethane. To avoid cross contamination the vapour tubes of the rotary evaporators were changed after each sample. 20 g freeze-dried and homogenized humus sample was spiked with the 13 C 12 -BDE standard mixture (1 ng BDE 28, 47, 99; 2 ng BDE 153, 154, 183 and 5 ng BDE 209) and extracted by Soxhlet extraction (Knöfler-Böhm hot extractor). Residual water (0-11%) was simultaneously distillated with Dean-Stark water separator with toluene. The extract was cleaned by a four column clean-up (1. Multi-layer SiO 2 -H 2 SO 4, NaOH. 2. Macro alumina. 3. GPC bio-beads S-X3. 4. Mini alumina), spiked with the injection standard (1 ng 13 C 12 -BDE 138) and reduced to 50 µl. 1 µl was injected on-column (guard column 2 m x 0.32 mm, uncoated, deactivated) and analysed by GC-SIM(EI+)HRMS (TRACE GC-MS MAT 95 XP, ThermoFinnigan, Bremen) using a DB-5MS (15 m x 0.25 mm, 0.1 µm). The two most intense masses of the bromine cluster (Tri- and TeBDE: M +. Te- to DeBDE: M + -2Br) were measured for each homologue group. The identification of PBDE was based on retention time and correct isotope ratio for both fragments recorded. Quantification was performed by means of the 13 C 12 -labeled internal standards. All congeners except BDE 100 were quantified based on their corresponding 13 C 12 -labeled analogues used as internal

Polybrominated diphenyl ether (pbde) in humus layers in remote forests 41 standards. BDE 100 was quantified using the 13 C 12 -BDE 99 internal standard. PBDE concentrations were recalculated with conversion factors to reduce freeze-dried to oven dry (at 105 C) humus mass. All samples were analysed at the German Federal Environment Agency. The laboratory took part in the BSEF/QUASIMEME interlaboratory study on brominated flame retardants December 2001 to March 2002 and the interlab trial for ISO/DIS 22032 November 2004 to February 2005. Method blanks were spiked on a plug of glasswool in a Soxhlet extraction thimble and extracted and clean-up processed every four samples. Blank concentrations were calculated on a fictive mean sample weight of 18.3 g d.m.. The method detection limit (MDL) was determined as the mean concentration in the blank plus 3 times the standard deviation of 19 measurements (Table 1). Table 1. Concentrations of PBDE in humus layers in Norway spruce forests in the Alpine region Results and Discussion PBDE were detected in all humus samples. The total concentration of six significant congeners of the technical PentaBDE mix ( BDE 28+47+99+100+ 153+154) ranges from 190 to 1500 (median 490) and the significant congener of the technical OctaBDE mix (BDE 183) from 14 to 3000 (median 140) ng kg -1 d.m.. Although four multimedia models predicted for DecaBDE (BDE 209) a very low potential to reach remote areas (Wania & Dugani 2003) levels from 610 to 85000 (median 1400) ng kg -1 d.m. were observed. (Table 1 and Fig. 1-3). A contribution of local but until now unknown sources is probable for two very high BDE 209 concentrations (29000 and 85000 ng kg -1 d.m.) (Fig. 3). The dominating congeners in the humus samples are BDE 209 (51-97%), BDE 183 (0.7-31%), BDE 47 and BDE 153 (both 0.2-18%) and BDE 99 (0.1-13%). The contribution of the other congeners is of minor importance (BDE 100 0.03-3, BDE 154 0.1-1.5 and BDE 28 0.01-0.4%). BDE 183 is a minor congener in many environmental samples. Its higher percental contribution in humus layers may be due to revolatilisation of the congeners with less than seven bromine from humus to air (Fig. 4).

5% 2 97 52 14 12 6 207 23 674 10% 3 104 56 15 16 7 220 28 823 25% 4 141 70 19 28 10 313 65 1064 50% 5 252 124 35 39 16 485 139 1414 42 75% 7 320 197 55 74 31 Monitoraggio 795 dei 297POPs sul 2550 territorio alpino 90% 10 504 326 82 174 49 1028 789 7483 MDL 1 49 16 4 2 1 73 4 133 6 BDE = BDE 28+47+99+100+153+154 12 25 number of 6 BDE concentrations 10 8 6 4 2 number of BDE 183 concentrations 20 15 10 5 0 0 // 0-100 100-200 200-300 300-400 400-500 500-600 600-700 700-800 800-900 900-1000 1000-1100 1100-1200 1200-1300 1300-1400 1400-1500 0-100 100-200 200-300 300-400 400-500 500-600 600-700 700-800 800-900 900-1000 1000-1100 1100-1200 3000-3100 concentration ranges [ng kg -1 d.m.] concentration ranges [ng kg -1 d.m.] 30 100% number of BDE 209 concentrations 25 20 15 10 5 0 // // 80% 60% 40% 20% BDE 209 BDE 183 BDE 154 BDE 153 BDE 100 BDE 99 BDE 47 BDE 28 0-1000 1000-2000 2000-3000 3000-4000 4000-5000 5000-6000 6000-7000 7000-8000 8000-9000 9000-10000 10000-11000 11000-12000 28000-29000 84000-85000 0% 1 6 11 16 21 26 31 36 41 46 51 56 concentration ranges [ng kg -1 d.m.] sample no. Fig. 1-3. Frequency histogram of 6 BDE (BDE 28+47+99+100+153+154), BDE 183 and BDE 209 Fig. concentrations 1-3. Frequency in humus histogram layers in of Norway Σ 6 BDE spruce (BDE forests 28+47+99+100+153+154), in the Alpine region. BDE 183 and BDE 209 concentrations in humus layers in Norway spruce forests in the Alpine region. Fig. 4. PBDE congener profiles in humus layers in Norway spruce forests in the Alpine region. Fig. 4. PBDE congener profiles in humus layers in Norway spruce forests in the Alpine region. Acknowledgement MONARPOP is funded by the EU Interreg III B Alpine Space Programme (Alpine Space) and by the Austrian Federal Ministry of Agriculture, Forestry, Environment and Water Management (lead partner of MONARPOP), by the Bavarian State Ministry for Environment, Health and Consumer Protection and by the Swiss Federal Office for the Environment (together with the institutions listed above). References Alpine Space. INTERREG III B Alpine Space Programme. <http://www.alpinespace.org/ (January 17, 2007) Bassan R, Belis C, Heublein D, Iozza S, Jakl T, Jakobi G, Kirchner M, Knoth W, Kräuchi N, Levy-Lopez W, Luchetta A, Magnani T, Moche W, Oehme M, Offenthaler I, Perthen- Palmisano B, Schmid D, Schramm K-W, Schrott H, Schröder P, Sedivy I, Simoncic P, Uhl M, Weiss P. Monitoring network in the Alpine region for persistent and other organic pollutants: A multinational approach to investigate the contamination of the Alps with organic compounds. Organohalogen Comp 2005;67:1839. BSEF. Bromine Science and Environmental Forum. <http://www.bsef.com/ (January 17, 2007) Daly GL, Wania F. Organic contaminants in mountains. Environ Sci Technol 2005;39,385.

Polybrominated diphenyl ether (pbde) in humus layers in remote forests 43 de Wit CA. An overview of brominated flame retardants in the environment. Chemosphere 2002;46:583. EBFRIP. European brominated flame retardant industry panel. Decabromodiphenyl ether (Deca-BDE) usage in EU countries in 2004 in metric tons. 27 May 2005, 1 p. EU 2003. Directive 2003/11/EC of the European Parliament and of the Council of 6 February 2003 amending for the 24th time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (pentabromodiphenyl ether, octabromodiphenyl ether). Official Journal of the European Union 2003;L42:45. EU 2004. Update of the risk assessment of bis(pentabromophenyl)ether (decabromodiphenyl ether). Final environmental draft of May 2004. CAS No. 1163-19-5, EINECS No. 214-604-9, 114pp. Hassanin A, Johnston AE, Thomas GO, Jones KC. Time trend of atmospheric PBDEs inferred from archived U.K. herbage. Environ Sci Technol 2005;39:2436. Hites RA. Polybrominated diphenyl ethers in the environment and in people: A meta-analysis of concentrations. Environ Sci Technol 2004;38:945. Knoth W, Mann W, Meyer R, Nebhuth J. Brominated diphenyl ether in indoor dust. Organohalogen Comp 2003;61:207. Knoth W, Mann W, Meyer R, Nebhuth J. Humus from coniferous forests a reservoir for PBDE from air and deposition analysis and quality control. Organohalogen Comp 2006;68:1163 Letcher RJ, Behnisch PA, Ed.. The state-of-the science and trend of BFRs in the environment. Environment international 2003;29:663. Mariussen E, Steinnes E, Gundersen H, Borgen A, Schlabach M. Analysis of polybrominated diphenyl ethers in moss (Hylocomium splendens) from the Norwegian environment. Organohalogen Comp 2005;67:591. MONARPOP. Monitoring network in the Alpine Region for persistent and other organic pollutants. <http://www.monarpop.at/ (January 17, 2007)> NCEL. National Caucus of Environmental Legislators. Bulletins March 4 and May 31, 2005. <http://www.ncel.net/base.cgim?template=bulletins_archive (January 17, 2007)> Ohta S, Ishizuka D, Nishimura H, Nakao T, Aozasa O, Shimidzu Y, Ochiai F, Kida T, Nishi M, Miyata H. Comparison of polybrominated diphenyl ethers in fish, vegetables and meats and levels in human milk of nursing women in Japan. Chemosphere 2002;46:689. Okazawa T, Hanari N, Guruge K, Wzykowska B, Orlikowska A, Yamashita N, Falandysz J. Congener-spezific data of PBDEs in pine needles. Organohalogen Comp 2004;66:3725. Schlabach M, Gjerstad KI. Deposition of airborne BFR around the city of Ålesund, Norway. Organohalogen Comp 2006;68:73 Schütz A. Bestimmung polybromierter Diphenylether (PBDE) in Umweltproben unter besonderer Berücksichtigung des DecaBDE. Diplomarbeit, Universität Ulm, Abteilung Analytische Chemie und Umweltchemie 2004;146 pp.

44 Monitoraggio dei POPs sul territorio alpino Tullo A. Flame-retardant phase out. Chemical & Engineering News November 10, 2003:13. Vighi M, Ed.. The role of high mountains in the global transport of persistent organic pollutants. Ecotoxicology and Environmental Safety 2006;63:1. Wania F, Dugani CB. Assessing the long-range transport potential of polybrominated diphenyl ethers: A comparison of four multimedia models. Environ Toxicol Chem 2003;22:1252. Weiss P. Organische Schadstoffe an entlegenen Waldstandorten Sloweniens und Kärntens. Berichte BE-195. Umweltbundesamt GmbH, Wien, September 2002. ISBN 3-85457- 616-1. 121 S. Zhu L, Hites RA. Brominated flame retardants in tree bark from North America. Environ Sci Technol 2006;40:3711.

Monitoraggio dei POPs sul territorio alpino Copyright 2007 - ARPA Lombardia ISBN 978-88-903167-0-8 45 Distribution of dioxins, polychlorinated biphenyls and chlorinated pesticides in the alpine environment Ivo Offenthaler 1,*, Rodolfo Bassan 2, Claudio Belis 3, Gert Jakobi 4, Manfred Kirchner 4, Norbert Kräuchi 5, Walkiria Levy Lopez 4, Teresa Magnani 3, Wolfgang Moche 1, Karl Werner Schramm 4, Isabella Sedivy 5, Primož Simončič 6, Maria Uhl 1, Peter Weiss 1 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; * ivo.offenthaler@umweltbundesamt.at Riassunto Le concentrazioni di diossine e furani policlorurati, di bifenili policlorurati e di pesticidi organoclorurati sono misurabili negli ecosistemi forestali ancora anni dopo che il rilascio di queste sostanze è stato bandito. Le concentrazioni sono in generale più elevate nell humus seguite dallo strato minerale del suolo e dagli aghi. Nessuno dei composti è presente su tutta l area di studio e le concentrazioni presentano differenze longitudinali o latitudinali significative. Le informazioni ricavate da humus e aghi non sempre risultano congruenti. Con poche eccezioni le concentrazioni di inquinanti sono risultate più elevate nelle aree periferiche delle Alpi e si ritiene siano associate alla deposizione di composti legati al materiale particolato. In genere le correlazioni tra diversi inquinanti sono deboli con la sola eccezione delle diossine/furani e i PCB in una delle matrici studiate. Abstract Polychlorinated dioxins and furans (PCDD/F), polychlorinated biphenyls (PCB) and organochloropesticides (OCP) were detectable in forest ecosystems of the Alps even at remote sites and years after the banned release of some of these substances. Pollutant concentrations were generally highest in humus, followed by mineral soil and needles. Neither of the compounds was spread evenly across the investigated region, and concentrations frequently showed significant longi- or latitudinal differences. Screening humus and needles, either with its particular history of exposure, did not always lead to congruent pollution maps. With few exceptions, however, needle and

46 Monitoraggio dei POPs sul territorio alpino humus pollution was higher in the peripheral regions of the alpine range. Pollutant patterns suggested wash- and fallout of particlebound compounds at the fringes of the study area. While in a given matrix there were numerous high correlations between PCDD/F and PCB congeners and/or totals, the majority of investigated pesticides was only weakly associated with the two earlier pollutant classes. 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. Material and Methods Criteria for site selection and extent of the sampling network are described elsewhere in this volume 1-2. Shoots of the current year were harvested from two vital adult Norway spruce (2-3 branches from the top 7th whirl each), transferred in airtight vessels, defoliated in liquid nitrogen and distributed to the laboratories in airtight vials. All manipulations between opening of the transport jars and redistributions were conducted in inert N 2 atmosphere. 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. Results and Discussion Humus generally showed the highest pollutant concentrations, followed by mineral soil and needles [Figure 1]. This pronounced difference is probably due to the enrich- 1 Weiss P., R. Bassan, C. Belis, G. Jakobi, M. Kirchner, N. Kräuchi, W. Levy Lopez, W. Moche, I. Offenthaler, K.-W. Schramm, I. Sedivy, P. Simončič, M. Uhl, 2007. Synthesis of the findings of the project MONARPOP. This volume. 2 supplemenal information at: http://www.monarpop.at

d Discussion ly showed the highest pollutant concentrations, followed by mineral soil and needles is pronounced Distribution difference is probably due topesticides the enrichment of lipophilic, poorly of dioxins, PCB and chlorinated in the alpine environment mus compounds in coniferous stands which retain POP contamination from needle ghfall. 47 8 10 6 4 2 0 µg kg 1 d.m. sum HCH isomers humus soil needles Figure 1: Comparison of HCH concentrations (sum of alpha epsilon-hch) in humus, mineral soil and 0.5 year old Norway spruce needles at 18 remote alpine sites. of lipophilic, poorly degradable humus compounds coniferous parison of HCHment concentrations (sum of alpha epsilon-hch) in humus,inmineral soil stands which retain POP contamination from needle litter and throughfall. d Norway spruce needles at 18 remote alpine sites. After forming longi- or latitudinal groups of comparable site count [Figure 2a], significant concentration differences site werecount found [Figure for a number of compounds [Figure longi- or latitudinal groups of comparable 2a], significant 2b]. Humus andof almost all needle[figure concentrations were highest in one differences were found concentrations for a number compounds 2b]. Humus and almost all needle concentrations were highest in one of the lateral groups. This he long-range atmospheric transport of POPs is intercepted by the alpine range. san, C. Belis, G. Jakobi, M. Kirchner, N. Kräuchi, W. Levy Lopez, W. Moche, I. Offenthaler, K.-W. vy, P. Simonþiþ, M. Uhl, 2007. Synthesis of the findings of the project MONARPOP. This volume. ormation at: http://www.monarpop.at a: Latitudinal grouping into northern (N), central (C) and southern (S) sites. Figure 2 a: Latitudinal grouping into northern (N), central (C) and southern (S) sites. sum PCDD/F north central south 2 4 6 ng TEQWHO kg 8 1 10 d.m. Figure 2 b: Total PCDD/F concentrations in humus, expressed in TEQWHO. Ranking the sites by this criterium showed a highly significant* imbalance between northern, central and southern scores. * Kruskal-Wallis, α 0.004, n=10/12/9 for northern/ central/southern sites b: Total PCDD/F concentrations in humus, expressed in TEQWHO. Ranking the sites by this showed a highly significant3 imbalance between northern, central and southern scores. and PCB congener profiles differed regionally, and there were continguous zones of ongener patterns [Figure 3]. For instance, humus from the south did not only have a higher

ng TEQWHO kg 1 d.m. Monitoraggio dei POPs sul territorio alpino 48 tal PCDD/F concentrations in humus, expressed in TEQWHO. Ranking the sites by this 3 wed a highly significant imbalance between northern, central and southern scores. 6 congener 8 10 profiles differed regionally, and there were continguous zones of PCB 1 ner patterns [Figure 3]. For instance, humus from the south did not only have a higher QWHO kg d.m. ans but among these the heavier particlebound congeners dominated [Figure 3]. Note different congener pattern correspond approximately to the latitudinal bands depicted s, expressed in TEQ. Ranking the sites by this Different deposition WHO regimen (temperature, precipitation, windspeed) and atmospheric etween northern, central and southern scores. ely cause for the geographical segregation between sites of similar pollutant pattern. 1 0.25 0.20 0.15 0.10 0.05 TCDF PeCDF HxCDF HpCDF OCDF TCDF PeCDF HxCDF HpCDF OCDF OCDD HxCDD HpCDD PeCDD 0.00 TCDD gionally, and there were continguous zones of humus from the south did not only have a higher ticlebound congeners dominated [Figure 3]. Note d approximately to the latitudinal bands depicted rature, precipitation, windspeed) and atmospheric ation between sites of similar pollutant pattern. 4 1 0.25 0.20 0.20 0.15 0.15 0.10 0.10 0.05 0.05 OCDD HxCDD HpCDD PeCDD OCDF HpCDF HxCDF PeCDF TCDF OCDD HpCDD HxCDD TCDD PeCDD TCDD 0.00 0.00 4 Figure 3: Sites of the same number (1 4) have similar PCDD/F congener patterns in humus. The aver0.20 age congener pattern of clusters 1 (north) and 4 (south) is shown on the right. OCDF HpCDF HxCDF PeCDF TCDF OCDD HpCDD HxCDD TCDD PeCDD 0.15 α 0.004, n=10/12/9 for northern/central/southern sites of0.10the lateral groups. This suggests that the long-range atmospheric transport of POPs is0.05intercepted thesimilar alpine PCDD/F range. congener patterns in humus. The of the same number (1 4) by have 0.00 PCCD/F and PCB congener differed and there were continguous ner pattern of clusters 1 (north) and 4 (south)profiles is shown on theregionally, right. zones of similar congener patterns [Figure 3]. For instance, humus from the south did not only have a higher furans among these the heavier particlecb pollution were associated as shown byfraction several of strong andbut significant correlations ers of the two pollutant classes [Figure 4]. Σ PCBTE [µg kg 1 d.m.] outhern sites 3.0 2.5 2.0 1.5 1.0 0.5 0.1 0.2 0.3 0.4 0.5 Σ PCDD F [µg kg 0.6 1 d.m] 0.7 Figure 4: Highly significant correlation between total PCDD/F and content of 12 dioxinlike PCB (rpearson=0.86, α 0.001) y significant correlation between total PCDD/F and content of 12 dioxinlike PCB α 0.001) ns

Distribution of dioxins, PCB and chlorinated pesticides in the alpine environment 49 bound congeners dominated [Figure 3]. Note that zones of different congener pattern correspond approximately to the latitudinal bands depicted in Figure 2a. Different deposition regimen (temperature, precipitation, windspeed) and atmospheric loads are a likely cause for the geographical segregation between sites of similar pollutant pattern. PCDD/F and PCB pollution were associated as shown by several strong and significant correlations between members of the two pollutant classes [Figure 4]. Conclusions Dioxinlike compounds and chlorinated pesticides are traceable even in remote forest sites of the alps. The detection of the highly toxic chemicals in needles shows that these substances are still around despite rigorous emission control in large parts of Europe and the US (in the case of PCB already since the 1970ies). The degree of pollution and the chemical patterns found in environmental samples changes across the investigated area in a way which indicates that the Alps form a climatical and orographical barrier for atmospheric POP transport. As a corollary, mountainous forests can be expected to receive increased inputs of airborne POPs. Even within the narrow range of substances described here, chemicals of different source and properties were closely associated. This demonstrates how POP pollution is an issue of multiple contamination with possibly synergistic amplification of adverse effects. 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.