Environ. Sci. Technol. 2007, 41, 2196-2202
Altitudinal Gradients of PBDEs and PCBs in Fish from European High Mountain Lakes EVA GALLEGO, JOAN O. GRIMALT,* MIREIA BARTRONS, AND JORDI F. LOPEZ Department of Environmental Chemistry (I.I.Q.A.B.-C.S.I.C.), Jordi Girona, 18, 08034 Barcelona, Catalonia, Spain LLUIS CAMARERO AND JORDI CATALAN Limnology Unit (CSIC-UB), Centre for Advanced Studies of Blanes (CEAB-CSIC), Acce´s Cala St. Francesc, 14, Blanes 17300, Catalonia. Spain EVZEN STUCHLIK Department of Hydrology, Charles University, Vinicna´ 7, 12044 Prague, Czech Republic RICK BATTARBEE Environmental Change Research Centre, University College London, 26, Bedford Way, London WC1H 0AP, United Kingdom
A first case of temperature-dependent distribution of polybromodiphenyl ethers (PBDEs) in remote areas is shown. 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 temperaturedependent distribution is observed in a similar transect in the Tatra mountains (Central Europe) nor in fish from high mountain lakes distributed throughout Europe. 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. These cases of distinct PBDEs and PCBs behavior in high mountains likely reflect early stages in the environmental distribution of the former since they have been under secondary redistribution processes over much shorter time than the latter.
Introduction Polychlorobiphenyls (PCBs) and polybromodiphenyl ethers (PBDEs) have common physical-chemical properties such as high stability, semivolatility, and hydrophobicity, which bring about their long-range transport and widespread distribution in the environment (1-4). Whereas the former * Corresponding author phone: 34934006122; fax: 34932045904; e-mail:
[email protected]. 2196
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started to be used in the 1930s (5), commercial distribution of the latter was not initiated until the 1970s (6) and increased considerably after the PCB ban. The introduction of these two groups of compounds into the environment has therefore a time lag of 40 years which provides an interesting case for comparison of the significance of secondary redistribution in the context of the “global distillation effect” (1, 7, 8). The distribution patterns of these compounds in remote sites may increase the knowledge of the processes involved in this theory. Thus, whereas there is a good level of understanding of the thermodynamic aspects of the model, e.g., temperature dependence and its relationship with the physicochemical constants of the compounds, virtually no information is available on the kinetic characteristics, e.g., the time span to reach steady-state distributions of concentrations. The time lag in the introduction of PCBs and PBDEs into the environment offers the possibility of obtaining useful information from this standpoint. Thus, several studies show latitudinal distributions of PCBs that are interpreted in relation to global distillation accumulation patterns (3, 9-11). In contrast, reports showing distributions of PBDEs that follow this model are not available to date. However, these compounds have been found in high concentrations in Arctic ringed seals (Phoca hispida; 12) and several studies indicate that their concentrations in remote sites are increasing (13-15). High mountains provide good examples for the study of processes involved in the “global distillation effect” since temperature is a major feature determining the distribution of organochlorinated compounds along altitudinal profiles (14-18). These studies have been performed in several types of environmental matrixes such as snow (16, 17), fish (18, 19), soils (20), and mosses (21). In the fish studies, examination of the lake average values in fish muscle or liver distributed throughout Europe and correlation with altitude or annual average air temperature at the sampling site provided statistically significant relationships for the PCBs with volatility lower than 10-5 Pa (p < 0.05 or 0.01), indicating that the highest sites, those most distant from potential pollution sources, were the most polluted (18, 19). These correlations were observed irrespectively of the geographic location of the lakes. In contrast, PBDEs in an equivalent series of fish samples from high mountain lakes did not show any significant correlation with either altitude or air temperature (22). The lack of correlation was attributed to the lack of steady-state conditions in the emission of these compounds (22). Regional differences in PBDEs emission to the environment may mask temperaturedriven accumulation trends. The study of fish from high altitude lakes distributed along altitudinal gradients from the same mountain region is a useful way to overcome this problem. In this way, two transects, located in the central southern Pyrenees and in the High Tatras, were selected to examine the altitudinal gradients of PCBs and PBDEs in fish (Figure 1). Five lakes were chosen in the Pyrenees, encompassing a difference in elevation between 1620 and 2688 m above sea level (a.s.l.) and a range of annual average air temperatures between 1.0 and 6.2 °C (Table 1). In the Tatras the four lakes selected encompassed altitudinal and temperature differences between 1395 and 1946 m a.s.l. and -0.7 and 2.4 °C, respectively (Table 1). In the absence of major pollution sources in the sampled areas, the lakes situated in each transect are assumed to be exposed to similar POP emissions from low altitudes. The two lake transects are located far away from human populated sites. None of them received water courses 10.1021/es062197m CCC: $37.00
2007 American Chemical Society Published on Web 03/06/2007
FIGURE 1. Map showing the location of the lakes chosen for study in the Pyrenees and the Tatras.
TABLE 1. Characteristics of the High Mountain Lakes and Fish Included in the Study
lake name
latitude (N)
1. Llebreta 2. Cavallers 3. Llong 4. Xic de Colomina 5. Vidal d’Amunt
42.55083 42.59257 42.57431 42.52149 42.53281
6. Morskie Oko 7. Zielony Staw 8. Czarny Staw 9. Vel’ke´ Hinc¸ ovo
49.19780 49.22890 49.20460 49.17970
longitude altitudea (E) (m) 0.89031 0.85779 0.95063 0.99564 0.99351 20.0722 20.0010 20.0277 20.0606
Tb (°C)
1620 1800 2000 2425 2688
6.2 5.5 4.1 2.5 1.0
1395 1672 1722 1946
2.4 0.8 0.6 -0.7
fish conditioning analyzed agec factord (no.) (year) (cg cm-3) Pyrenees 14 8.7c 14 5.5 13 10 12 7.6 12 6.3 Tatras 14 14 12 14
7.1 5.9 5.1 5.8
sex
lipid in muscle (%)
1.1c 1.2 1.2 1.1 1.2
1e-13f 4-10 5-8 1-11 3-9
1.4c 2.4 1.4 0.8 1.0
1.1 0.9 1.2 1.0
10-4 5-9 7-5 12-2
1.9 1.4 1.8 1.4
a Meters above sea level. b Annual average air temperatures. c Average values of the fish analyzed in each lake. (in cm3). e Male. f Female. g (standard deviation.
influenced by anthropogenic activity. The maximal planar projection distances between them are 13.8 and 7.0 km in the Pyrenees and Tatras, respectively (Figure 1). Thus, all lakes from the same transect must be under the same type of air-transported diffuse pollution. These transects provide two altitudinal series receiving air-transported pollutants from low altitude areas that are generally characteristic of urban sources (Pyrenees) and intensive industry (Tatras) (23).
Materials and Methods Information on the methods of calculation of annual average air temperatures, sample collection, chemicals, methods of PCBs and PBDEs analysis, and quality assurance are given in the on-line Supporting Information.
total PCBs (ng g-1)
total PBDEs (ng g-1)
3.8c ( 1.1g 0.74c ( 0.42g 4.6 ( 1.1 0.80 ( 0.31 8.3 ( 6.6 1.1 ( 0.69 7.2 ( 4.0 1.1 ( 0.58 9.4 ( 8.0 1.6 ( 0.83 7.3 ( 7.0 11 ( 3.4 16 ( 6.4 23 ( 14 d
0.71 ( 0.72 0.32 ( 0.13 0.79 ( 0.53 0.34 ( 0.16
Weight (in g) × 100/length3
Results Fish Population Characteristics. All studied lakes were oligotrophic and situated far from local pollution sources. About 12-14 fish were collected and analyzed per lake (Table 1). Only specimens between 20 and 30 cm long were caught. This sampling criterion was established to avoid fish younger than 3 years and to diminish the age effect when comparing the accumulation of compounds between different specimens (19, 24). Individual ages ranged between 3 and 10 years in the Pyrenees and 3 and 17 years in the Tatras. Average ages between lakes varied between 5.5 and 10.2 years in the Pyrenees and 5.1 and 7.1 years in the Tatras (Table 1). These lake average differences were not correlated to altitude. A higher number of females were analyzed in the Pyrenees (51/65) whereas male specimens dominated in the Tatras VOL. 41, NO. 7, 2007 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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FIGURE 2. Relative distributions of PCBs and PBDEs in fish muscle in the lakes included in the altitudinal transects of the Pyrenees and Tatras. Numbers refer to Table 1.
TABLE 2. Correlation Coeficients (r2), Slopes, and Enthalpies Calculated from the Log-Transformed Concentrations of PCBs and PBDEs in Fish Muscle Pyrenees altitude
Tatras temperature
compound
r2 a
slope
r2 a
slope
PCB101 PCB118 PCB138 PCB153 PCB180 BDE47 BDE99 BDE100 BDE153 BDE154
0.0162 0.7063** 0.7267* 0.6516* 0.6776* 0.4091 0.5775 0.8369* 0.9292** 0.9968**
0.0001 0.0001 0.0004 0.0004 0.0003 0.0002 0.0001 0.0005 0.0007 0.0006
0.0082 0.6932** 0.7893* 0.7206* 0.7112* 0.4922 0.5336 0.8776* 0.9217** 0.9973**
1160 2220 6730 6070 4780 2700 2210 8750 10440 8760
altitude ∆Hb 42 130 120 92 170 200 170
temperature
r2 a
slope
r2 a
slope
∆ Hb
0.2879 0.7495** 0.9550** 0.7800** 0.7384** 0.3859 0.3874 0.2864 0.1587 0.0284
0.0002 0.0004 0.0010 0.0008 0.0008
0.2832 0.7276** 0.9652** 0.7628** 0.7181** 0.4031 0.3428 0.3103 0.1883 0.0373
2480 5330 14670 10730 10450
100 280 210 200
theoreticalc ∆H 118 121 138 136 144 156 160 154 165 168
a *, p < 0.05; **, p < 0.01. b Calculated enthalpies (kJ‚mol-1) following the equation: ∆H ) SR ln(10), where S ) slope of the regression straight lines, R ) 8.314 J‚K-1 and ln(10) ) 2.303. c Summed condensation and solubilization theoretical enthalpies (30-32). Solubilization enthalpies for PBDE were estimated from (32).
(34/54). These distinct numbers reflect the population of fish captured for this study. No specific sex selection for analysis was done after sampling. The conditioning factors of the individual fish ranged between 0.7 and 1.3 cg cm-3 and 0.6 and 1.6 cg cm-3 in the Pyrenees and Tatras, respectively. Average lake conditioning factors were similar, encompassing 1.1-1.2 cg cm-3 and 0.91.2 cg cm-3 for the two regions, respectively (Table 1). The lipid content in muscle was 0.2-5.2% in the Pyrenees and 0.3-5.7% in the Tatras. Averaged fish lipid proportions per lake gave similar values, 0.8-2.4% in the Pyrenees and 1.41.9% in the Tatras (Table 1), that were not correlated to altitude. PCB and PBDE Concentrations. Nearly all lakes exhibited rather uniform PCB and PBDE distributions (Figure 2). PCB153 and PCB138 were the main congeners in all samples, varying between 21 and 40% and 18 and 35% of total PCBs, respectively. BDE47 was the most abundant PBDE congener 2198
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in all samples, followed by BDE99, which is consistent with previous studies (22). Their relative composition was 3249% and 20-35% of total PBDEs, respectively. BDE28 concentrations were below the limit of detection in all samples. These distributions in fish contrast with those observed in air where dominance of the more volatile congeners, e.g., BDE17, BDE28, and BDE47, is found (25). Specific analyses for BDE209 were performed and this very low volatility congener was not found in any of the samples. The mean lake fish concentrations of PCBs and PBDEs ranged between 4.2 and 24 ng g-1 and 0.32 and 1.6 ng g-1, respectively (Table 1). These concentrations were obtained after individual analysis of all specimens recovered in each lake. They are in the range of those previously reported in European high mountain lakes (18, 19, 22, 24). Fish from the Pyrenean transect exhibit lower average PCB concentrations (6.7 ( 2.4 ng g-1) than those from the Tatras (14 ( 6.8 ng g-1).
FIGURE 3. Lake-averaged muscle concentrations (n ) 12-14) of selected PCB and PBDE congeners vs reciprocal of annual mean air temperature. For simplicity the x-axis is annotated with the direct temperature values (°K). The variability bars indicate standard error. However, the former show higher PBDE concentrations (1.1 ( 0.34 ng g-1) than the latter (0.54 ( 0.24 ng g-1). Altitudinal Dependence. Both in the Pyrenean and the Tatra transects the log-transformed concentrations of PCB118, PCB138, PCB153, and PCB180 in fish muscle show significant correlations with altitude (p < 0.05 and 0.01, respectively) (Table 2). In both cases, the congeners correlated with altitude are those with vapor pressure lower than 10-3.0 Pa (26). These correlations are consistent with those found in previous studies on high mountain lakes (18, 19). Fish in the lakes at highest elevation are those having highest concentrations of low volatile PCB congeners. The log-transformed PBDE concentrations from the Pyrenean fish show statistically significant altitudinal correlations for the congeners BDE100 (p < 0.05), BDE153 (p < 0.01), and BDE154 (p < 0.01) (Table 2), that is, those with vapor pressure lower than 10-4.2 Pa (27). In contrast, no altitudinal dependence of PBDE is observed in the fish concentrations of the Tatra transect (Table 2).
Discussion Fish Characteristics and Concentrations of Organohalogen Compounds. Gender comparison of the average concentrations of PCBs and PBDEs show no significant statistical differences (p < 0.05) neither in the Pyrenees nor in the Tatras (Table S1, Supporting Information). The differences in the accumulation of PBDEs between these two mountain areas cannot therefore be attributed to the sex differences in their sampled fish populations (Table 1). Statistically significant age dependencies (p < 0.01) are only observed in Vidal d’Amunt (Table S2, Supporting Information) where the more hydrophobic congeners, e.g.,
PCB118, PCB138, PCB153, and PCB180, exhibit higher concentrations in older fish. These results are consistent with those observed in Lake Redon in which the association between age and concentrations was also observed for these more hydrophobic congeners (24). The concentrations of BDE47, BDE100, BDE153, and BDE154 also exhibit a significant age dependence (p < 0.01; Table S2, Supporting Information) in Vidal d’Amunt, which is expected in view of the similar properties of both compounds. Significant correlation coefficients between some PBDE congeners and age have also been observed in Llong (Table S2, Supporting Information). To the best of our knowledge, these results constitute the first report showing that PBDE accumulation in fish may be age-dependent. Nevertheless, having in mind the low number of lakes in which significant dependencies are observed and the lack of correlation between lake average fish age and altitude (Table 1), the distributions of lake average concentrations of both PCBs and PBDEs cannot be attributed to age. In Vidal d’Amunt, statistically significant correlations (p < 0.01) are observed between conditioning factor and the concentrations of PCB118, PCB138, PCB153, PCB180, BDE47, BDE100, BDE153, and BDE154 (Table S3, Supporting Information). That is, the same group of hydrophobic compounds exhibiting significant age dependence. This correlation is not surprising since older fish in high mountain lakes tend to have lower conditioning factors (24) as is the case in Vidal d’Amunt. Again, the low number of lakes in which these correlations are observed and the lack of association between lake altitude and average conditioning factor make it unlikely that this property could be relevant for the distributions of concentrations observed in these mountain transects. VOL. 41, NO. 7, 2007 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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FIGURE 4. Representation of the concentrations of summed BDE100, BDE153, and BDE154 vs summed PCB118, PCB138, PCB153, and PCB180 in fish muscle from the Pyrenean and Tatra high mountain lake transects. Fish lipid content is not correlated to concentration of organohalogen compounds in any of the lakes (Table S4, Supporting Information). Temperature Dependence. Compilation of the average annual air temperatures for each lake and correlation with the log-transformed lake-averaged fish concentrations shows similar coefficients as those observed with altitude. Thus, PCB118, PCB138, PCB153, and PCB180 exhibit significant correlations in the Pyrenean (p < 0.05) and Tatra (p < 0.01) transects (Table 2; Figure 3). This result is expected since the gradients of temperatures and altitudes in both mountain ranges are correlated (Figure S1, Supporting Information). The temperature correlations are in agreement with the predictions of the global distillation model and suggest that the observed altitudinal gradients result from condensation of compounds formerly present in the atmosphere. These temperature dependencies also require rather uniform vertical PCB distributions in the air masses arriving to each lake transect. PCB concentration differences of one to two were observed at 28° N when comparing the composition of the atmosphere near the surface, within the boundary layer, and in the free troposphere (altitudinal difference of 2400 m) (28). Smaller vertical atmospheric differences must be found in the Tatras and in the Pyrenees because the boundary layer in these sites may expand over the whole altitudinal range examined, particularly in the warm seasons. The specific temperature dependence of the less volatile compounds is consistent with previous observations on atmospheric deposition studies in high mountain lakes, showing that lakes located in temperate zones tend to retain less volatile PCB congeners whereas those that are more volatile are trapped in colder locations (29). In this respect, the higher concentrations of these compounds in the Tatra than in the Pyrenean transects (Table 2) are consistent with the lower average annual temperatures of the former. 2200
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In the present case, the compounds exhibiting significant correlations are those with volatilities lower than 10-3.0 (Table 2) whereas in previous studies the correlated compounds were those with vapor pressures lower than 10-2.5 (18, 19). The temperature range represented by the lakes included in these mountain transects, 5.2 and 3.1 °C, respectively, is smaller than the 10.15 °C temperature range of the lakes in previous studies (18, 19), which suggest a somewhat lower capacity for the observation of temperature effects in the present study. Furthermore, the minimum temperature is also a very relevant parameter for the efficient trapping of organohalogen compounds in mountain areas (21). In the Pyrenean and Tatra mountains these temperature values are 1.0 and -0.7 °C whereas in the studies of lakes distributed throughout Europe it was -1.45 °C. The concentrations of BDE100, BDE153, and BDE154 exhibit significant temperature dependencies in the Pyrenean but not in the Tatra transects (Table 2). As described above, PBDEs have been used and released into the environment much later than PCBs. In a previous study related to fish in high mountain lakes distributed throughout Europe the lack of temperature dependence of the concentrations of these compounds in trout muscle was attributed to lack of constant amounts of PBDEs arriving at these sites (22). This interpretation was in agreement with observations of increasing PBDE concentrations at remote sites (13-15). In the present study, the higher concentrations of PBDEs in the Pyrenean fish samples compared with those in the Tatra transects is in agreement with this lack of geographical temperature dependence in the European mountains. However, the observed temperature correlations in the Pyrenean transect indicate that, in this mountain region, at least the distribution of PBDEs is no longer dependent on local emissions and has already reached a temperature dependence indicating, as for the PCB case, that the sites situated at higher altitude are the ones more polluted by these compounds.
Phase-Change Enthalpies. Experimental phase change pseudo-enthalpies can be calculated from the slopes of the regression straight lines for the compounds exhibiting significant temperature dependencies, e.g., PCB118, PCB138, PCB153, PCB180, PBDE100, PBDE153, and PBDE154. In the Pyrenean transect, the observed values are in the range of 42-130 and 170-200 kJ‚mol-1 for PCB and PBDE, respectively (Table 2). In the Tatra Mountains, the enthalpy values are in the range of 100-280 kJ‚mol-1 for PCB (Table 2). Assuming that incorporation of these organohalogen compounds into high mountain lake fish occurs through vapor condensation and phase transfer from aquatic to organic media, the expected enthalpy values should result from the summed theoretical condensation (30, 31) and solubilization (32) enthalpies of these compounds. That is, 121-144 and 154168 kJ‚mol-1 for PCB and PBDE, respectively. The empirical enthalpies obtained from the Pyrenean and Tatra transects are tentative since they are calculated from a limited number of cases. Much higher values are observed in the Tatras than in the Pyrenees, the latter being closer to the theoretical estimates. The empirical PBDE enthalpies from the Pyrenean transect are not very different from the theoretical values. Higher experimental than theoretical enthalpy values must reflect some additional temperaturedependent mechanisms that enhance the accumulation of these compounds in fish (18, 19). The regional average annual air temperatures are lower in the Tatras than in the Pyrenees (0.8 and 3.9 °C, respectively). Lower temperatures imply lower fish metabolic activity and lower respiration rates. In addition, the higher solubility of oxygen at lower temperatures involves a reduced need of water circulation through the gills to obtain the same oxygen amount, thereby decreasing the exchange of compounds and limiting depuration by gills (33). Recent experiments in which perch (Perca flavescens) were dosed with PCB mixtures showed a strong temperature dependence in the rates of elimination of these compounds (34). Winter temperatures involved up to 7.5 times slower elimination rates than summer temperatures. Although these experiments were performed with different fish species and within a higher temperature range than in the high mountains, they illustrate a temperature-dependent kinetic effect that is consistent with the theoretical and experimental observations of our present study. Thus, the progressive accumulation of organohalogen compounds in fish muscle due to condensation effects must be higher at higher altitude lakes because they have lower annual average temperatures, involving lower metabolic and respiration rates by fish. Implications for the Global Distillation Model. Representation of the summed trout muscle concentrations of BDE100, BDE153, and BDE154 vs the summed concentrations of PCB118, PCB138, PCB153, and PCB180 shows significant positive correlations in the Pyrenees both at the level of individual values (r2 ) 0.5046, p < 0.05) or as lake averages (r2 ) 0.8347, p < 0.01) but not in the Tatras (Figure 4). PBDEs are still being produced and released whereas the use of PCBs ended 30 years ago. Thus, the correlation of these PCB and PBDE congeners of lower volatility in the Pyrenean transect indicate that despite the different sources and emission periods their environmental distribution is dominated by temperature effects. That is, secondary emission processes have largely redistributed the compounds arriving in these mountain environments. The lack of correlation between PCBs and PBDEs in the Tatras cannot be justified by lack of “trapping power” since the mean annual average temperatures of its constituent lakes is lower than those in the Pyrenean transect (Table 1). The overall results suggest latter use of PBDEs in the Tatra than in the Pyrenean regions. This interpretation is in agreement with the observation that PCBs are found at higher concentrations in the Tatra than in the Pyrenean fish (Table
1) as predicted by the global distillation model. In contrast, PBDEs are higher in the Pyrenean than in the Tatra lakes (Table 1) which is against model expectations. In summary, the data examined in the present study show that PBDEs follow the same trends as PCBs in some mountain ranges such as the Pyrenees. It is feasible, consequently, that the environmental distribution of PBDEs will fulfill the temperature dependencies of the global distillation model in the forthcoming decades.
Acknowledgments This work has been supported by the EU Project Euro-limpacs (GOCE-CT-2003-505540). Technical assistance in instrumental analysis by R. Chaler, D. Fanjul, and R. Mas and field work help by S. Jarque, M. Bacardi, and G. Mendoza is acknowledged. E.G. as student of the Universitat Autonoma de Barcelona acknowledges the support of this university.
Supporting Information Available Methods of calculation of annual average air temperatures, sample collection, chemicals, methods of PCBs and PBDEs analysis, and quality assurance. This material is available free of charge via the Internet at http://pubs.acs.org.
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Received for review September 14, 2006. Revised manuscript received January 13, 2007. Accepted January 19, 2007. ES062197M
