Bucle de ajuste de la frecuencia

In the carnivore species in this study, analytes from all the analysed compound classes were quantified except for brown bear and Eurasian lynx which were not analysed for PFCs (Appendix 5, 6, 7 and 9). In general, the HOC levels were higher in carnivores than in herbivores (Figure 2).

7.2.1. Levels and pattern of contaminants

0 1000 2000 3000 4000 5000 6000

Brown bear, Sarek, Sweden, 1998 Brown bear, Sarek, Sweden, 2008 Wolverine, Sarek, Sweden, 1998 Wolverine, Sarek, Sweden, 2008 Eurasian lynx, Sarek, Sweden, 1997 Eurasian lynx, Finnmark, 2007 Red fox, Varanger, coastal, 2006-07

Red fox, Varanger, inland, 2008

ng/g lw

p,p'-DDE Oxychlordane -HCH HCB PCB-28 PCB-118 PCB-138 PCB-153 PCB-180

0 1000 2000 3000 4000 5000 6000

Brown bear, Sarek, Sweden, 1998 Brown bear, Sarek, Sweden, 2008 Wolverine, Sarek, Sweden, 1998 Wolverine, Sarek, Sweden, 2008 Eurasian lynx, Sarek, Sweden, 1997 Eurasian lynx, Finnmark, 2007 Red fox, Varanger, coastal, 2006-07

Red fox, Varanger, inland, 2008

ng/g lw

p,p'-DDE Oxychlordane -HCH HCB PCB-28 PCB-118 PCB-138 PCB-153 PCB-180

Figure 6. Levels of p,p’-DDE, oxychlordane, -HCH, HCB, PCB-28, -118, -138, -153 and -180 (ng/g lw) in pooled serum/plasma samples of red fox from Varangerhalvøya (Varanger), Eurasian lynx from Sarek, Northern Sweden (1997) and Finnmark (2007), and wolverine and brown bear from Sarek, Northern Sweden.

0 50 100 150 200 250

Brown bear, Sarek, Sweden, 1998 Brown bear, Sarek, Sweden, 2008 Wolverine, Sarek, Sweden, 1998 Wolverine, Sarek, Sweden, 2008 Eurasian lynx, Sarek, Sweden, 1997 Eurasian lynx, Finnmark, 2007 Red fox, Varanger, coastal, 2006-07 Red fox, Varanger, inland, 2008

ng/g lw

BDE-28 BDE-47 BDE-99 BDE-100 BDE-153 BDE-206 BDE-207 BDE-208 BDE-209

Figure 7. Levels of BDE-28, -47, -99, -100, -153, -206, -207, -208 and -209 (ng/g lw) in pooled serum/plasma samples of red fox from Varangerhalvøya (Varanger), Eurasian lynx from Sarek, Northern Sweden (1997) and Finnmark (2007), and wolverine and brown bear from Sarek, Northern Sweden.

0 10 20 30 40 50 60 Wolverine, Sarek, Sweden, 1998

Wolverine, Sarek, Sweden, 2008 Red fox, Varanger, coastal, 2006-07 Red fox, Varanger, inland, 2008

ng/g ww

70

PFPeA PFOA PFNA PFDA PFUdA PFHxS PFOS

Figure 8. Levels of PFPeA, PFOA, PFNA, PFDA, PFUdA, PFHxS and PFOS (ng/g ww) in pooled serum/plasma samples of red fox from Varangerhalvøya (Varanger) and wolverine from Sarek, Northern Sweden.

Red fox

OCs: The coastal and inland red fox samples were analysed in parallels. The results were presented as mean of the two parallels. High concentrations of ∑CHLs (1520 ng/g lw; 2510 ng/g lw) and ∑7PCBs (3980 ng/g lw; 3030 ng/g lw) were measured in coastal and inland red fox from 2006-2007 and 2008, respectively (Appendix 6). p,p’-DDE, HCHs and HCB were found in lower concentrations (Figure 6). The OCs were ranked as ∑7PCBs > ∑CHLs > HCB > ∑HCHs > p,p’- DDE.

The most abundant PCB congeners were PCB-153 and PCB-180, contributing together >80% (>40% each) to ∑7PCBs (Figure 6). Lower chlorinated PCBs were measured at very low levels or below detection limits (LOD). Sim dominance of PCBs and CHLs was observed in Arctic fox studies from Svalbard (Fuglei et al., 2007) and from Canada and Alaska (Hoekstra et al., 2003a). It is known that species of the

Canidae family have the ability to degrade the otherwise highly persistent PCBs, such as PCB-

153 and PCB-180, of which even PCB-153 is degraded in larger degree. This can thus result in lower levels of PCB-153 than PCB-180 (Georgij et al., 1994). High ratios of PCB-180 to PCB- 153 in red foxes have also been observed in other studies of foxes (Hoekstra et al., 2003; Voorspoels et al., 2006). It is suggested that this unusual synthetic capability is caused by a cytochrome P-450 isoenzyme that can metabolize the 2,4,5-trichloro substituted biphenyls (Georgij et al., 1994).

The CHL and PCB levels in the studied red fox samples (collected in 2005-2006) were approximately two to three folds lower compared to the corresponding levels in adipose tissue of

ilar

Red fox. Photo by project ”Fjellrev i Finnmark”, University of Tromsø Red fox. Photo by project ”Fjellrev i Finnmark”, University of Tromsø

Svalbard Arctic fox that were collected in 1999 (Fuglei et al., 2007). However the PCB levels (ng/g lw) in the present red fox are just below PCB levels reported to influence the immune system in polar bears (Ursus maritimus) (Lie et al. 2004). Though, factors as species, age, gender, geography, feeding strategy, health and nutritional status should be taken into consideration when comparing and extrapolating results between red fox and Arctic fox and other species/studies.

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

Red fox, Varanger, coastal, 2006-07 Red fox, Varanger, inland, 2008

ng/g ww

PCB-28 PCB-118 PCB-138 PCB-153

PCB-180 4-OH-CB107 4-OH-CB146 3'-OH-CB138

4'-OH-CB159 3'-OH-CB180 4'-OH-CB172/OH-heptaCB 4-OH-CB187

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

Red fox, Varanger, coastal, 2006-07 Red fox, Varanger, inland, 2008

ng/g ww

PCB-28 PCB-118 PCB-138 PCB-153

PCB-180 4-OH-CB107 4-OH-CB146 3'-OH-CB138

4'-OH-CB159 3'-OH-CB180 4'-OH-CB172/OH-heptaCB 4-OH-CB187

Figure 9. Levels of PCBs and OH-PCBs (ng/g ww) in in pooled serum/plasma samples of red fox from Varangerhalvøya (Varanger), inland versus coastal.

Concentrations of OH-CB metabolites were detected in levels of 8.7 and 12.6 ng/g ww in coastal and inland foxes, respectively (Appendix 5). More than 50% of the analysed OH-CB metabolites were detected in fox from both areas. The main metabolite was 4-OH-CB187. The levels of the OH-PCBs are just above the levels of the PCBs (Figure 9). In polar bears, OH-PCBs are found to be about 1-2 times higher than the PCBs and to saturate the binding sites for thyroid hormone on its transport protein (Gutleb et al., submitted). PCP was detected in levels of 0.10 and 0.08 ng/g ww in coastal and inland fox, respectively (Appendix 5).

BFRs: Levels of ∑PBDEs and sum of only BDE-28, -47, -99, -100 and -153 (in parentheses) were 59 (15) and 141 (19) ng/g lw in coastal and inland fox, respectively (Appendix 7), and thus highest in inland fox (Figure 7). The sum of BDEs, excluding octa-, nona- and deca-BDE in the present foxes were lower than the geometric mean level of corresponding BDEs in subcutaneous adipose tissue of Arctic fox from Svalbard (32 ng/g lw) (Fuglei et al., 2007). However, these levels were about twenty times higher than the median level of corresponding BDEs in adipose tissue of red fox muscle from Belgium (1-44 ng/g lw) (Voorspoels et al., 2006). The OH-BDE metabolite 6-OH-BDE47 was the only metabolite that was detected only in the inland fox (Appendix 5). TBP was detected in levels of 0.15 and 0.05 ng/g ww in coastal and inland fox, respectively (Appendix 5).

PFCs: In red fox the ∑PFCs concentration was 22 and 28 ng/g ww, and PFOS was the dominant compound (12 and 16 ng/g ww) (Appendix 9; Figure 8). In contrast to reindeer, deer and moose, PFPeA and PFNA were much lower than PFOS. The levels of PFOS in red fox were lower than the levels found in Arctic fox from Arviat, in the Canadian Arctic (2001), of ∑PFOS 269 ng/g ww (Gamberg et al., 2005). The sum of the perfluorinated carboxylic acids (PFCAs; ∑PFCAs; sum of PFOA, PFNA, PFDA, PFDoA) in coastal and inland red fox were 3.4 and 6.1 ng/g ww respectively, and were also lower than the levels found in Arctic fox from Arviat (53 ng/g ww) (Gamberg et al., 2005).

Wolverine

OCs: The OCs that were found in highest levels in the wolverine samples were PCBs (Figure 6). The PCB levels were 647 and 320 ng/g lw in 1998 and 2008, respectively (Appendix 6). The OC ranking was: ∑7PCBs > HCB > ∑HCHs > ∑CHLs > p,p’-DDE. This was a different pattern compared to that found in wolverine liver from the Canadian Arctic (Hoekstra et al., 2003b) where CHLs were the second dominating OCs. PCB-153 was the most abundant PCB congener in the wolverines, followed by PCB-180. This pattern was also found in Canadian wolverines (Hoekstra et al., 2003b). However, the hepatic ∑PCB levels in the Canadian wolverine were about twice the levels in the Scandinavian wolverine (present study). In the Canadian study, the high ∑PCB levels in wolverines (1560 ng/g lw) were comparable to those in Canadian Arctic fox (1350 ng/g lw). This was explained by their habit of scavenging marine mammals (Hoekstra et al., 2003b). In the present study, ∑7PCBs levels in the wolverine from 2008 were about tenfold lower than ∑7PCBs in the red fox from 2008 (present study). The Scandinavian wolverines may therefore feed on preys with much lower PCB levels than the Canadian wolverines.

The OH-CB metabolites were detected at levels of 2.9 and 1.1 ng/g ww for the 1998 and 2008 samples, respectively (Appendix 5). The main metabolite was 4-OH-CB187. PCP was detected in levels of 0.11 and 0.07 ng/g ww in 1998 and 2008, respectively (Appendix 5).

BFRs: The ∑PBDEs in wolverines were 127 and 2.6 ng/g lw in 1998 and 2008 respectively (Appendix 7). In the 1998 sample, nona and deca-BDEs were the dominating BDEs (Figure 7). The BDE-209 contributed 81% to ∑PBDEs. In 2008, the only detectable PBDEs >MLOD were BDE-153 and -208. No OH-BDEs were found in the wolverine samples. TBP was detected in levels of 0.06 and 0.03 ng/g ww in 1998 and 2008, respectively (Appendix 5).

PCFs: The ∑PFCs in wolverine was 65 ng/g ww, and PFOS, PFPeA, and PFNA were the abundant PFCs (Appendix 9; Figure 8.). The PFC patterns were more comparable to the patterns found in the herbivores. It was not expected that PFPeA and PFNA would biomagnify in the food chain. No information on PFCs in wolverine is available in literature. The observed PFOS levels in wolverine (9.9 and 22 ng/g ww) are comparable to the levels found in Canadian Arctic mink (10 ng/g), but lower than in Arctic fox (269 ng/g ww).

Brown bear

OCs: The OC levels in the brown bear samples were very low (Appendix 6). The dominating OCs were PCBs followed by HCB and HCHs in the samples from 1998. However, the HCB level was higher than PCBs in the sample from 2001. Levels of p,p’-DDE were <LOD. The observed OC pattern was similar to that in Candian grizzly bears (2000-2001) (Christensen et al., 2005).

Brown bear. Photo by Jon M. Arnemo, Hedmark University College

Lynx. Photo by Jon M. Arnemo, Hedmark University College Lynx. Photo by Jon M. Arnemo, Hedmark University College Brown bear. Photo by Jon M. Arnemo, Hedmark University College The levels of ∑7PCBs, HCB and β-

HCH in the brown bears from 1998 were 25, 20 and 2.2 ng/g lw, respectively (present study). These were lower or comparable to the highest observed levels in the grizzly bears from 2000-2001 which were 43, 21 and 3.8 ng/g lw, respectively (Christensen et al., 2005). Lipid weight levels of PCB-153 in the present brown bear from 1998 were however more than ten times higher than PCB-153 levels in Japanese black bear (fat tissue) from 1991- 1993 (Hoshi et al., 1998). Christ grizzly bears that relied on terr the bears that lived on a higher (e.g. HCB and ∑HCHs) and PBDEs w in the salmon eating bears. Wh

not known.

The OH-CB metabolites were detected at le respectively (Appendix 5). 4'

metabolites. PCP was detected in levels of (Appendix 5).

BFRs: The ∑

respectively (Appendix 7). BDE-209 wa

∑PBDEs in 2008 (Figure 7). No OH-BDE metabolites were found in the bear samples. TBP was detected in levels of 0.03 and 0.02 ng/g ww in 1998 and 2008 respectively (Appendix 5).

Eurasian lynx

OCs: The OC levels in the Eurasian lynx were low to moderate (Appendix 6). PCBs were found in highest concentrations of 298 and 746 ng/g lw in 1997 and 2007, respectively (Figure 6). In the 1997 sample, the OCs were ranked as ∑7PCBs > HCB > p,p’-DDE > ∑HCHs.. In the 2007 sample the ranking was slightly different: ∑7PCBs > p,p’-DDE > HCB > ∑HCHs. CHLs were not detected in any lynx. The lynx from 1997 were males, captured in Sarek, Sweden, while the lynx from 2007 were

ensen et al. (2005) compared OC and PBDE levels between estrial food completely and those consuming salmon in autumn. In

proportion of terrestrial vegetation, higher levels of volatile OCs ere found. The levels of DDTs were in general lower than ether the bears in the present study include salmon in their diet is vels of 0.13 and 0.07 ng/g ww in 1998 and 2008, -OH-CB172/OH-heptaCB and 4-OH-CB187 were the main

0.02 and 0.01 ng/g ww in 1998 and 2008 respectively PBDEs were 0.5 and 7 ng/g lw in the bear samples from 1998 and 2008,

Lynx. Photo by Jon M. Arnemo, Hedmark University College Lynx. Photo by Jon M. Arnemo, Hedmark University College females, captured in Finnmark, Northern Norway. It is difficult to explain whether the different OC patterns were related to gender, spatial or temporal differences. In both samples, PCB-153 was the most abundant PCB congener, followed by PCB-180 (Figure 6). Compared to other carnivores, the ∑7PCB levels in the studied lynx were in the same range as ∑PCBs found in liver from Russian wolf (Canis lupus), calculated on lipid weight (AMAP, 2002). The OH-CB metabolites were detected at levels of 1.9 and 16 ng/g ww and 7/8 and 8/8 metabolites were detected in 1997 and 2007, respectively (Appendix 5). The most dominating metabolite was 4- OH-CB187. PCP was detected in levels of 1.1 and 0.22 ng/g ww 1997 and 2007 respectively (Appendix 5).

BFRs: The ∑PBDEs in lynx from 1997 and 2007 were 237 and 19 ng/g lw respectively (Appendix 7). In the 1997 sample, BDE-209 contributed 79% to ∑PBDEs (Figure 7). In the 2007 sample BDE-47 and BDE-153 dominated the PBDE pattern, contributing 28 and 41% to ∑PBDEs respectively. Mariussen et al. (2008) found hepatic median levels of ∑PBDEs in Norwegian lynx of 9.2, 7.5 and 13 ng/g lw in samples from 1995 (females), 2002 (females) and 2002 (males), respectively. Thus, somewhat lower level than in the serum from the lynx in 2007 (present study). Only in the 2007 sample PBDE metabolite 6-OH-BDE47 was detected (Appendix 5). TBP was detected in levels of 0.09 and 0.06 ng/g ww 1997 and 2007 respectively (Appendix 5).

7.2.2. Spatial trends

The ∑7PCB levels were higher in coastal foxes compared to inland foxes, whereas most levels of OH-PCBs were higher in inland fox compared to coastal fox (Figure 9). Also ∑PBDEs were highest in inland fox, mainly due to the higher level of BDE-209 (Figure 7). In this sample BDE- 209 contributed 83% to PBDEs compared to 69% in coastal foxes. A factor such as differences in feeding ecology between coastal and inland individuals would greatly influence the levels and patterns of red fox. For the wolverine and brown bear no spatial trend was available. For Eurasian lynx, large differences in levels and pattern were observed between samples from the Sarek lynx from 1997 and the Finnmark lynx from 2007 (Figure 6 and 7). It was however difficult to conclude if the differences in levels and patterns were a result mainly of living in different areas. 7.2.3. Temporal trends

No time trend was available for red fox. In wolverines most OCs levels decreased 40-51% in the time period 1998-2008 (Appendix 6; Figure 6). HCB levels decreased however only 9%. Levels of OH-PCBs and ∑PBDEs decreased 62 and 98% in the corresponding period, respectively (Table 6 and 8). In the 1998 wolverine sample, BDE-207 and BDE-209 constituted 8 and 82% of the ∑PBDEs. Both these congeners were absent in the 2008

sample. In contrast to the decreasing trend of most OCs, ∑CHLs increased 34% in the same time period (Appendix 6). The HOC levels in the brown bear were regarded too low for making any

speculations on a temporal trend. The levels of β-HCH, HCB and ∑PBDEs in Eurasian lynx decreased 34, 65 and 92% in the time period 1997-2007, respectively (Appendix 6 and 7). However, levels of p,p’-DDE, ∑7PCBs and ∑OH-PCBs increased 57, 60 and 88% in the same time period in this species (Appendix 5 and 6).

Because the use and production of many legacy HOCs have been banned or restricted since decades (e.g. DDTs, PCBs) it was expected to find decreasing temporal trends for certain HOCs. The observed increased levels of DDTs, CHLs and PCBs, could not be explained in the present report. However, it is expected that remobilisation and redistribution of HOCs in the ecosystem can take place as result of climate change.