On the Global Distribution of Persistent Organic Pollutants

ENVIRONMENTAL ANALYSIS 514 CHIMIA 2003, 57, No. 9

Chimia 57 (2003) 514–521 © Schweizerische Chemische Gesellschaft ISSN 0009–4293

Pilar Fernández* and Joan O. Grimalt

Abstract: The global distribution of persistent organic pollutants (POPs) has become one of the main environmental problems in the last decade. This article gives an overview of the main contributions to the knowledge of the atmospheric transport and accumulation mechanisms of POPs in remote areas, based on their analysis in selected environmental compartments from high altitude mountain regions of Europe. The studies indicated that transport and deposition of polycyclic aromatic hydrocarbons are mainly linked to atmospheric particles. Consequently, wet and dry deposition are the main removal processes of these compounds from the atmosphere, resulting in a significant influence of regional sources. In contrast, gas exchange seems to be the main input mechanism of organochlorine compounds (OCs) from the atmosphere to terrestrial and aquatic systems. For these compounds, an altitude dependence of their accumulation in fish muscle and sediments was detected, with a major retention of the less volatile compounds (vapor pressure ≤ 10–2.5 Pa) in the locations situated at higher altitude, those of lower annual average temperature, whereas no relation- ship was observed for more volatile OCs. The results represent a new aspect in the Global Distillation Effect theory as proposed for semivolatile persistent pollutants, indicating that this transport mechanism not only involves transfer from low to high latitudes, but also preferential accumulation of the less volatile compounds in high altitude regions of mid-latitude areas.

Keywords: Global distribution models · Organochlorine compounds · Persistent organic pollutants · Polycyclic aromatic hydrocarbons · Remote lakes

Introduction tation of international measures for the processes, which complicates even more control of their release into the environment the control of their emissions to the envi- POPs [1–3]. ronment. The list of anthropogenic com- Great concern has arisen during the last Most POPs are organochlorine compounds to be considered as potential POPs decade about the occurrence of the so- pounds (OCs) used for diverse applications, is not closed and different candidates are called persistent organic pollutants (POPs, both industrial and agricultural (Table). being evaluated for addition to the UN- Table) in the environment. Their semi- Their intentional use has been restricted or ECE POP Protocol [4]. volatile character and high environmental banned in many developed countries, but in half-lives result in long-range atmospheric some cases, e.g. 4,4’-DDT, their applica- Global Distribution Mechanisms transport and global planetary distribution, tion in developing countries is allowed or One peculiarity of the global POPs dis- which is especially relevant due to their unregulated. Other POPs like dioxins, fu- tribution is their accumulation in the envi- potential toxicity and strong tendency to rans or polycyclic aromatic hydrocarbons ronmental compartments situated at higher bioaccumulate in living organisms. All (PAH) are mainly produced in combustion latitude, resulting in an enrichment of the these factors have led to the implemen- Table. UNEP POP list adopted in the Stockholm Convention on persistent organic pollutants [3]. The compounds specifically analyzed in this study are underlined.

Aldrin Hexachlorobenzene Toxaphene Mirex DDTs Dioxines *Correspondence: Dr. P. Fernández PCBs Furans Environmental Chemistry Department Heptachlor Chlordane Institute of Chemical and Environmental Research of a Barcelona Dieldrin Chlordecone Jordi Girona, 18 Endrin Hexabromobiphenyla E-08034-Barcelona, Spain Polycyclic Aromatic Hydrocarbonsa Hexachlorocyclohexanesa Tel.: +34 93 400 6100 Fax: +34 93 204 5904 aChemicals included in the UN-ECE POP Protocol [1] E-Mail: [email protected] ENVIRONMENTAL ANALYSIS 515 CHIMIA 2003, 57, No. 9 concentrations of some POPs in polar ecosystems to levels that sometimes exceed Gas-Particle Partition human consumption guidelines [5]. A glo- Gas bal distribution model has been proposed to Air-soil or air-vegetation Dry Deposition explain this latitudinal gradient, referred to exchange as the Global Distillation Effect and Cold Wet Deposition Condensation [6][7]. This model is based on physico-chemical POP properties, their Photodegradation sources to the environment, and the Earth Air-water exchange climatic conditions. The atmosphere is the main transport Hydraulic transport media for the global distribution of POPs. Bioaccumulation Once in the environment and based on their Dissolved semivolatile character (Pv between 10–4 Phase and 10–11 atm at 25 oC), these compounds can be encountered in the gas phase, in as- Sedimentation sociation with atmospheric particles or distributed between these two phases [8–10] (Fig. 1). This distribution is important for Fig. 1. Main environmental processes during long-range atmospheric transport of POPs. their long-range transport, since preferential association with atmospheric particles increases their removal rate from the atmosphere by dry and wet deposition processes, which ultimately limits their T m = -2/-12 ºC travel distance from the sources. In addi- Grasshopper HIGH LATITUDES tion, during atmospheric transport, POPs Effect undergo a number of processes like degra- High volatility Moderate and high volatility (HCB, PCBs 1-4 Cl, HCHs), dation, deposition to soils, vegetation or (HCB, PCBs , HCHs, DDTs) Pv = 10-2 – 1 Pa water bodies, revolatization, sedimentation, and bioaccumulation (Fig. 1), which will determine their fate in the global envi- Moderate volatility ronment. The overall significance of all (DDT, PCBs 4-8 Cl), Pv = 10-4 –10-2 Pa these processes depends on the climatic HIGH ALTITUDE REGIONS conditions and physico-chemical properties Low volatility 35-60ºN of each compound. (PAH ring nº >4) Pv < 10-4 Pa T = -2/8 ºC As many physico-chemical properties m governing the environmental fate of POPs are temperature dependent, the theory of INTERMEDIATE the Global Distillation Effect predicts the LATITUDES transport of gas phase contaminants from 35-60ºN the warm regions of the planet, that is trop- T = 10 -20 ºC ical or temperate source areas, to colder, m higher latitude regions (Fig. 2). This temperature decrease will have an effect on the Fig. 2. Schematic representation of the Global Distillation Effect through the grasshopper mech- vapor pressure and Henry’s law constant of anism in temperate areas. Pv, vapor pressure of the subcooled liquid, Tm, mean air temperature in each region. these compounds, increasing their tendency to condense and accumulate in surfaces like atmospheric particles, soils, vegetation, and aquatic ecosystems, from where they can enough to trap them, an effect termed as the brominated diphenyl ethers (PBDE), used enter into the food chains. Depending on cold finger or cold trap [11]. as flame-retardants and not included in the their volatility, different POPs will con- A number of studies published in the POP list, have been found in high concen- dense at different ambient temperatures re- last decade reported global POP concentra- trations in Arctic ringed seals [20]. sulting in a fractionation of these chemicals tion patterns that are consistent with this Most of these studies have focused on in the Earth. distribution mechanism. For example, the polar high latitude regions. Less atten- The transfer from low to high latitudes hexachlorobenzene (HCB) levels in tree tion has been paid to the global distribution takes place in successive condensation/ bark exhibit a significant increase from the of these compounds in temperate areas volatization steps known as the grasshop- equator to northern regions [12][13]. Simi- where the main sources are located. In or- per effect by which these compounds are lar latitudinal gradients have also been der to avoid local pollution effects, the exchanged between air and terrestrial sur- described for polychlorinated biphenyls study of these areas must be focused on faces according to seasonal temperature (PCBs), mainly the more volatile con- remote sites. High mountain regions are changes at mid-latitudes (Fig. 2). Accord- geners, hexachlorocyclohexanes (HCHs), unique ecosystems for these purposes, and ing to this mechanism, most POPs would be and HCB in different environmental com- lakes located in these areas constitute stable ultimately accumulated in the polar regions partments such as air [14][15], sediments ecosystems where the influence of chroni- where the ambient temperature is low [16][17], and soils [18][19]. Recently, poly- cal inputs of atmospherically transported ENVIRONMENTAL ANALYSIS 516 CHIMIA 2003, 57, No. 9

POPs can be monitored. Thus, acid deposition and climatic change have been repor- 1. Arresjoen (20 m a.s.l.. Spitzbergen). S, F 1 2. Chibini (434 m. Russia). F Europa ted to have deleterious effects in some of 3. Ovre Neadalsvatn (728 m. Norway). S, F, W, A, D, Sn these ecosystems [21]. 4. Stavsvatn (1053 m. Norway). F On the other hand, high mountain re- 5. Lochnagar (785 m. Scotland). S, F 6. Lough Maam (436 m. Ireland). S gions also provide a temperature gradient 7. Zielowny Staw (1671 m. Poland). F 2 similar to that associated with latitude. In Ladove (2057 m. Slovakia). S, W, A, D, So Starolesnianske Pleso (2000 m. Slovakia). S, Sn this perspective, several research projects 8. Dlugi Staw (1783 m. Poland). S 3 funded by the European Union have been 9. Gossenköllesee (2417 m. Austria). S, F, W, A, D, Sn 4 Schwarsee ob Sölden (2799 m. Austria). S, F 5 focused on the study of POPs (those under- Oberer Plenderlesee (2344 m. Austria). F 6 lined in the Table) in high altitude European Mittlerer Plenderlesee (2317 m. Austria). F mountain lakes (Fig. 3). POPs levels in se- Lungo (2384 m. Italy). F Di Latte (2540 m. Italy). F 87 diments, lake water, fish, soils, atmospher- 10. Jörisee (2519 m. Switzerland). S, F, Sn 10 9 ic deposition, snow, and air have been ex- 11. Paione inferiore (2002 m. Italy). F 12 11 12. Noir (2750 m. France). S 13 amined in order to obtain an integrated pic- 15 14 13. Aube (2090 m. France). F 16 ture of the dynamics of these compounds in 14. Redó (2240 m. Spain). S, F, W, A, D, Sn, So 17 15. Cimera (2140 m.Spain). S, F these ecosystems. 16. Escura (1680 m. Portugal). S, F The lakes selected for study should be 17. La Caldera (3050 m. Spain). S 18 situated above the regional timberline, and 18. Teide* (2000-3100 m. Spain). A, D, So should be devoid of human disturbance Fig. 3. High mountain lakes network with indication of their altitude above sea level and the both in the lake or catchment area. In other environmental compartments analyzed in each site. S, sediments; F, fish; W, lake water; A, air; words, changes in their hydrology and eco- D, atmospheric deposition; Sn, snow; and So, soils. *Different altitudes in Mt. Teide (no lake logy should only respond to air pollution, present). climate and natural variability. All lakes selected for study are oligothrophic and co- vered with ice for a long period of the year Soils ered lake surface. The sampling device was [22]. With the exception of Lake Redó, all Soil cores were collected in an undis- a stand-alone pump combined with in situ these lakes are small shallow-water bodies, turbed area near the lakeshore or at differ- filtration and solid-phase extraction (Infil- with small catchment areas, constituted es- ent altitudes in Teide Mt. Dry samples were trex II, Axys Environmental Systems Ltd, sentially by bare rock with few mosses and Soxhlet extracted as described in [26]. Sidney, Canada). The materials retained in alpine meadows. As references, other Euro- Three clean-up procedure steps were per- the filters (GF/B, 1 µm nominal cutoff, pean remote zones have been included in formed before concentration and instru- Whatman) and the resins (XAD-2) were the study such as lake Arresjøen in the Arc- mental analysis. operationally defined as the particulate and tic, which is not a high mountain lake, but the dissolved phases, respectively. Analyti- it is situated far from any pollution source, Atmospheric Deposition cal procedures are described in [30][31], and a high mountain area located in the sub- and Snow briefly freeze-dried filter samples were ex- tropics, Teide Mt., Tenerife Island (Spain). Bulk and dry-wet only atmospheric tracted by sonication with dichlorome- This area does not contain lakes, but soils deposition samples were continuously col- thane/methanol 2:1, hydrolyzed overnight and air were analyzed for comparison. lected at high altitude sites for different pe- with 6 % KOH in methanol, and column riods, usually one year and a half. Detailed fractionated with 2 g of neutral alumina. description of the sampling procedure has The XAD-2 adsorbent column was eluted Material and Methods been reported elsewhere [27][28]. Briefly, with 200 ml of methanol followed by samples were filtered on-site through 200 ml of dichloromethane. Sediments preweighed glass fiber filters (Whatman, Samples were obtained by sediment GF/B, 45 mm diameter, 1 µm pore size), Air coring in the deepest point of the lake, di- and the filtrates were solid-phase extracted Atmospheric samples (approx. 100 m3, vided into sections of 0.5 cm in situ, and with C18 Empore disks (47 mm diameter, gas and particulate matter) were collected frozen until analysis. Wet samples were ex- 0.5 mm thickness). using a high-volume air sampler equipped tracted by sonication. Different clean-up Snow cores were taken at the time of with glass fiber filters and polyurethane steps by alkaline hydrolysis and column ad- maximum snow accumulation, left to melt foam plugs (PUFs) as described elsewhere sorption chromatography were applied un- and treated as wet deposition samples. [32][33]. Glass fiber filters were cut into til OCs and PAH fractions were obtained Freeze-dried glass fiber filters were ex- small pieces and extracted with dichloro- [23]. tracted by sonication with dichlorome- methane/methanol 2:1 in an ultrasonic bath thane/methanol 2:1. Compounds adsorbed (3 × 25 ml, 20 min each). PUFs were Soxh- Fish in the membrane extraction disks were elut- let-extracted with 400 ml of n-hexane for Samples were collected following stan- ed subsequently with methanol (5 ml), 24 h. Further clean-up by adsorption col- dard test-fishing procedures and dissection cyclohexane (5 ml) and dichloromethane umn chromatography was performed on as described in [24]. Muscle tissue was (5 ml). Both extracts were fractionated some samples before instrumental analysis. extracted by Soxhlet with hexane/dichlor- with aluminum oxide as described in [29]. omethane. Then, a clean-up step using con- Instrumental Analysis centrated sulphuric acid was repeated until Water POPs levels were determined by gas a colorless n-hexane layer was obtained Lake water samples (about 100 l) were chromatography with ECD (OCs) and gas [25]. Only OC compounds were deter- taken at several depths in different seasons chromatography coupled to mass spectro- mined in fish muscle. including periods of ice-free and ice-cov- metry in electron impact and selected - ENVIRONMENTAL ANALYSIS 517 CHIMIA 2003, 57, No. 9 ion monitoring modes (PAHs). Detailed the lakes showed similar low concentra- remote lakes is related directly to particle description of the chromatographic and tions (Fig. 4). This uniformity was also re- deposition through both dry and wet spectrometric conditions is given in flected in the qualitative distribution of the processes. Thus, PAHs should travel over [23][26][34][35]. OC identification was individual compounds, which was similar moderate distances and, therefore, their confirmed by gas chromatography coupled in all sites independent of their location or composition in remote sites should reflect to mass spectrometry in negative chemical pollution level [23]. influences from regional sources. ionization mode using ammonia as reagent In addition, analysis of PAHs in other In contrast, no common geographical gas [36]. Optionally, this technique was environmental compartments including air, trend was observed for the concentration of used for quantification when interferences snow, water, and soils, showed the same ge- OCs in sediments and fish of high altitude in GC-ECD do not allow OC determina- ographic distribution detected in sediments, mountain lakes, although the highest sedi- tion. indicating that lake sedimentary concentra- mentary levels also occur in the Tatra Mts tions reflect the input loads of these com- (Fig. 5). The different behavior of PAHs Quality Control and Assurance pounds from the atmosphere (Fig. 4). and OCs is evidenced further when consid- The analysis of trace pollutants in re- Moreover, detailed analysis on atmosphe- ering the environmental compartments mote areas currently involves POP determi- ric speciation of these compounds indicated mentioned above, since they do not show nation close to the instrumental detection that gas phase concentrations were similar any parallel trend for each specific location. limit. Thus, stringent precautions have to be at all sites, except in Eastern Europe, In the case of OCs, an altitude depend- taken in all methodological steps to avoid whereas seasonal and the above-mentioned ence for their accumulation in fish muscle sample contamination and careful calibra- geographical patterns were observed for and sediments (expressed as inventories) tion of the instrumental technique must be particle-associated PAH [32], pointing to a was observed, in that the less volatile com- performed. Specific description of the pre- higher influence of regional sources than in pounds (vapor pressure ≤ 10–2.5 Pa) were cautions taken is described in the above the gas phase. All these results suggest that retained to a major extent in the locations at reported literature referring to specific en- atmospheric particles are the main transport higher altitude, those of lower annual aver- vironmental compartments. In general, all media for these compounds [32][37] and age temperature. In contrast, no altitudinal materials were carefully cleaned and their that PAH deposition and accumulation in dependence was observed for the more purity was checked by vacuum concentration of 100 ml to 100 µl for gas chromatography analysis. A series of transport, labo- ratory and field blanks were processed to- 2,0 6 AIR PARTICLES 5 AIR GAS PHASE gether with the samples, which usually 1,5 -3 -3 4 involved 25% of the total samples ana- 1,0 3 ng m ng m lyzed. Method detection (MDL) and quan- 2 0,5 tification limits (MQL) were calculated for 1 each sample type, only compounds above 0,0 0 MQL were taken into account in the differ- Norway Pyrenees Alps Tatra Norway Pyrenees Alps Tatra ent studies. 7.9 Recoveries and reproducibility of the 4 4 analytical procedure were evaluated by ad- SNOW AIR TOTAL 3 3 -2 dition of surrogate standards before sample -3 extraction. Reported values were surrogate 2 2 ng m ng cm recovery and blank corrected. 1 1

0 0 Norway Pyrenees Alps Tatra Pyrenees Tatra Teide Results and Discussion 12100 1500 2000

Global Distribution of Persistent Total PAH WATER SOILS Organic Pollutants 1500

-1 1000 -1 The first studies on POP levels in high 1000 ng g mountain lakes were focused on the spatial pg l 500 and temporal trends of these long-range 500 x 10 0 atmospheric transported pollutants. Thus, 0 sediment cores and fish from diverse lake Norway Pyrenees Alps Tatra Pyrenees Tatra Teide sites were analyzed. Interestingly, all POPs 18100 investigated were found in all lakes, even in 1500 the one located in the Arctic area, and at SEDIMENT 1000 concentration levels that, in some cases, -1

cannot be considered low [23]. These first ng g studies also showed a differentiation be- 500 tween PAHs and OCs, since their spatial 0 distribution reflected distinct transport and Norway Pyrenees Alps Tatra accumulation mechanisms. PAH analysis in sediments evidenced Fig. 4. Total PAH levels (sum of 23 parent compounds from fluorene to coronene) in different high levels in Eastern Europe and a much environmental compartments from high altitude regions. Site identification based on Fig. 3 num- lesser extent in Norway, whereas the rest of bers: Norway 3, Pyrenees 14, Alps 9, Tatra 7, and Teide 18. ENVIRONMENTAL ANALYSIS 518 CHIMIA 2003, 57, No. 9

Fig. 5. HCB and PCBs (sum of congeners 28, PCBs HCB 52, 101, 118, 153, 138, and 180) in different environmental compartments from high altitude regions. Site identification as in Fig. 4. 100 AIR 200 AIR 150 -3 -3 50 100 pg m

pg m 50 0 0 Pyrenees Tatra Teide Norway Pyrenees Alps Tatra Teide

100 15 DEPOSITION DEPOSITION -1 -1 75 mo 10 mo -2

50 -2

ng m 25 5 ng m

0 0 Norway PyreneesAlps Tatra NorwayPyreneesAlps Tatra

120 10 WATER WATER 8 -1

80 -1 6 pg l

pg l 4 40 2 0 0 Norway Pyrenees Alps Tatra Norway PyreneesAlps Tatra 30 10 6 25 SEDIMENT SEDIMENT

-1 20 4 15 -1 ng g 10 2 5 ng g 0 0 Norway Pyrenees Alp Ta tra Norway Pyrenees Alps Tatra

4 2 SOILS SOILS 3 deposition may be subsequently transferred

-1 -1 to the atmosphere in the warm period 2 1 ng g ng g (grasshopper effect, Fig. 2). Only a fraction 1 of the less volatile compounds will be 0 retained in the lake in a proportion that is 0 Pyrenees Tatra Teide Pyrenees Tatra Teide defined by the local temperature. Further evidence of this accumulation mechanism can be obtained from the qualitative PCB distribution in atmospheric deposition, water and sediments from selected sites representing different ambient temperatures [29] (Fig. 8). PCB distributions in deposition samples are very similar be- volatile OCs (Fig. 6) [35]. This trend is ob- Analysis of OC levels in snow from tween sites dominated by the less chlorinat- served better for PCBs, since they include high altitude lakes [38] and soils collected ed, more volatile congeners. The resulting different congeners with a broad volatility at different altitudes in Teide Mt [26] compositions indicate a rather uniform range. Accordingly, less volatile congeners showed a well-defined altitude/temperature PCB deposition load to remote high moun- (PCB #153, #138 and #180; Fig. 6) showed dependence (Fig. 7) for all compounds, in- tain lakes that is independent of local con- altitudinal correlations (in fact, tempera- dependent of their volatility. In contrast to ditions. In contrast, large differences be- ture), whereas the more volatile congener fish and sediments, POPs in these two en- tween sites are observed in lake water, sed- PCB 28 did not. These different behaviors vironmental compartments reflect the bal- iment and/or fish (not shown), which are suggest the occurrence of a condensation ance between continuous inputs and losses enriched in less volatile congeners. This en- mechanism similar to that described in the from the atmosphere. Therefore, the more richment is more pronounced for the sites polar regions that drives the accumulation volatile compounds incorporated into these with the lowest average annual tempera- of these compounds in high altitude areas. high altitude regions through atmospheric ture. ENVIRONMENTAL ANALYSIS 519 CHIMIA 2003, 57, No. 9

HCB 4,4'-DDE4,4’-DDE PCB-28PCB-28

10 1000,0 10,0 y = 1.7E-04x - 0.71 y = 9.1E-04x - 0.91 ) y = -4.3E-05x - 0.34 R = 0,3087 1 100,0 R = 0,8363 R = 0,0985 10,0 1,0 ww 0,1 1,0 0,01 0,1 0,1 400 1000 1600 2200 2800 400 1000 1600 2200 2800 400 1000 1600 2200 2800

PCB-138PCB-138 PCB-153 PCB-153 PCB-180PCB-180

log (ng/g 100,0 100,0 y = 6.1E-04x - 0.84 10,0 y = 5.6E-04x - 0.81 y = 5.6E-04x - 0.94 R = 0,8524 10,0 R = 0,8959 10,0 R = 0,8312 1,0 1,0 1,0

0,1 0,1 0,1 400 1000 1600 2200 2800 400 1000 1600 2200 2800 400 1000 1600 2200 2800 HEIGHT [m] HEIGHT [m] HEIGHT [m]

Fig. 6. Linear regression between fish content and lake altitude for selected OCs.

The High Mountain Ecosystems As mentioned above, the composition accumulation in cold regions, such as re- in the Context of the Global POP of snow in the European sites reflects a tem- duced degradation rates due to lower tem- Distribution perature dependence of the less and the peratures or the presence of snow and ice Studies in the Canadian Rocky Moun- more volatile PCBs. Thus, in addition to for long periods. In this respect, there is a tains [39][40] also reported an altitudinal temperature effects, a matrix effect may al- lack of knowledge in the partitioning be- gradient of OC concentration measured in so partially account for the differences behavior of organic chemicals between air snow and conifer needles. In both cases, a tween Europe and Canada. Thus, the Euro- and snow and ice, and how these phases al- linear correlation of the more volatile con- pean samples reflect that all PCBs are re- ter the air exchange processes between geners with altitude was observed, whereas tained in proportion to the reciprocal of the these pollutants and the aquatic and terres- less volatile OCs were either unrelated or temperature in winter, e.g. snow, but only trial surfaces. inversely correlated. The differences in al- the less volatile congeners are retained at The understanding of the global distri- titude dependence observed between the summer temperatures, e.g. snow melting. bution mechanisms of persistent organic Canadian and European high mountain re- This interpretation is consistent with the pollutants is a key issue for the assessment gions can be explained in a first approach differences in PCB composition between of their true impact in the environment. by differences in air temperature ranges. atmospheric deposition, water and lake se- Transport and fate of POPs in the environ- Samples of snow from the Canadian Rocky diment (Fig. 8). ment result from a complex balance be- Mountains correspond to January tempera- tween inputs and losses, in which the inter- tures between –8 oC and –18 oC (air tem- action between all compartments, biotic peratures are not reported in the paper about Concluding Remarks and abiotic, has to be considered. Thus, the POPs levels in vegetation), while January significant role of oceanic biogeochemical temperatures at the European sites included PAHs are mainly transported in associ- processes in the global dynamics and fate of in this study range between –3 and –8 oC for ation with particles and their distribution in POPs, specifically phytoplankton uptake the highest lake. Thus, both observations remote areas, including high mountain re- and subsequent sink to deep waters, has are consistent with the Global Distillation gions essentially reflects regional contribu- been recently stated [41], but even in this Model proposed for POPs. As shown in Fig. tions. In contrast, OC concentrations in context, POP distribution is mainly gov- 2, more volatile compounds such as HCB or high altitude sites do not reflect nearby erned by their physico-chemical properties less chlorinated PCBs accumulate preferen- sources but are distributed as predicted by and temperature. tially in areas with mean temperatures in the global distillation model. That is, ac- o the range of –7 and –12 C, typically found cording to their physico-chemical proper- Acknowledgements in latitudes higher than 60 oN or mountain ties and air temperatures. Thus, high alti- Many people have contributed either direct- areas such as those of Canada, whereas less tude ecosystems accumulate POPs to the ly or indirectly to this study. In particular, we volatile compounds condense at mean tem- same extent as high latitude regions, which would like to thank R.M. Vilanova, L. Berdié, peratures between –3 oC and 5 oC, as mea- receive contaminants by long-range atmos- G. Carrera, B. van Drooge, and S. Ribes for the sured in the European lakes. However, these pheric transport. As a consequence, there is analysis of most of the samples described in this work. We are also grateful to H. Thies, U. less volatile compounds are mobilized at a net transfer of toxic and persistent chem- Nickus, and R. Psenner (Innsbruck University, o mean temperatures of 5–10 C or higher, icals from mid-latitude source areas to high Austria), M. Ventura, L. Camarero, and J. detected in low altitude sites of temperate altitude or latitude remote regions. Other Catalán (CEAM-CSIC, Spain), B. Rosseland and tropical latitudes. factors can also influence and enhance POP and L. Lien (NIVA, Norway), E. Stuchlik (Uni- ENVIRONMENTAL ANALYSIS 520 CHIMIA 2003, 57, No. 9

A PCB 28 PCB 52 PCB 101 1

- 1000 1000 1000 2 l R2 = 0,9374 R2 = 0,9374 R = 0,9844 100 100 100 pg 10 10 10

1900 2200 2500 1900 2200 2500 1900 2200 2500 HEIGHT [m] HEIGHT [m] HEIGHT [m]

PCB 118 PCB 153 PCB 138

1 1000 2 1000 2 1000 2 - R = 0,9803 R = 0,7835 R = 0,5538 l 100 100 100 pg 10 10 10

1900 2200 2500 1900 2200 2500 1900 2200 2500 HEIGHT [m] HEIGHT [m] HEIGHT [m]

Pentachlorobenzene Hexachlorobenzene 100,0 1000 R2 = 0.4194 R2 = 0.4173

10,0 100

1,0 10

0,1 1 0,0034 0,0035 0,0036 0,00340 0,0035 0,0036 PCB-70 PCB-123 PCB-153 100,0 1000,0 1000,00 2 2 R = 0.4308 R = 0.4493 R2 = 0.4618 100,0 Conc./TOC [ng/g] 100,0 10,0

10,0 10,0 1,0 1,0 1,0

0,1 0,1 0,1 0,0034 0,0035 0,0036 0,0034 0,0035 0,0036 0,0034 0,0035 0,0036 Temperaturere [1/ºK] Temperature [1/ºK] Temperature [1/ºK]

Fig. 7. Linear relation of (A) PCBs congeners in snow versus lake altitude, and (B) OCs in soils versus mean air temperature for high altitude sites. Concentration in soils related to organic carbon content (TOC). ENVIRONMENTAL ANALYSIS 521 CHIMIA 2003, 57, No. 9

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