Bioaccumulation and biomagnification of emerging and classical flame retardants in bird eggs of 14 species from Doñana Natural Space and surrounding areas (South-western Spain)

Abstract

The occurrence of classical (polybrominated diphenyl ethers, PBDEs) and emerging FRs (dechloranes, hexabromobenzene (HBB), pentabromoethyl benzene (PBEB) and decabromodiphenyl ethane (DBDPE)) in unborn eggs of 14 different species from Doñana Natural Space and surrounding areas was studied. PBDEs, Dec-602, Dec-603 and DP were detected in all the species, whereas HBB, PBEB, DBDPE and Dec-604 were not detected in any sample. ΣPBDE and ΣDechlorane levels ranged from 1.40 to 90.7, and from 0.77 to 260 ng/g lw, respectively. BDE-209 was the most abundant BDE congener in almost all the species, whereas Dec-602 was the predominant among dechloranes. In general, levels of PBDEs and dechloranes were similar and even higher for dechloranes, probably indicating the increasing use of dechloranes as a result of legal restrictions on PBDEs. In both cases, the most contaminated specie was the white stork. Using stable isotope characterization, differences among species and possible biomagnification processes were also evaluated. PBDE levels increased as the trophic position increased, showing biomagnification capacity. The same behavior was observed for Dec-602 and Dec-603; however, DP levels were not linearly correlated with trophic level. These results show that more attention should be given to emerging FRs such as dechloranes since they show similar environmental behavior as PBDEs.

Sources and environmental behaviors of Dechlorane Plus and related compounds — A review

“…Thereafter, different levels of DP were obtained in various biota samples including the human body (Barón et al, 2014a;Gauthier and Letcher, 2009;Guerra et al, 2011;Ren et al, 2009;Salamova and Hites, 2013;Sun et al, 2012;Wu et al, 2010), confirming bioavailability of DP in both the terrestrial and aquatic biotas. Chemicals were considered to be bioaccumulative if the bioaccumulation factor (BAF) was greater than 5000 (Kelly et al, 2007), corresponding to a logBAF of 3.70.…”

“…Similar situations were observed in the waterbirds from an e-waste recycling region in South China and in the unborn eggs of different species from Spain (Barón et al, 2014a), where no significant correlations were obtained between DP levels and trophic levels (p N 0.05), suggesting that the biomagnification of DP was not clear in waterbird and bird egg. By contrast, PBDEs were observed to be evidently biomagnified in waterbirds , bird eggs (Barón et al, 2014a) and the marine food web (Peng et al, 2014). This could be due to the lower logK OW values of PBDEs (6.0 for BDE-47 and 6.8 for PBDE-99) than those of DP (9.3), and therefore leading to high bioavailability of PBDEs in organisms (Peng et al, 2014).…”

“…The GC to mass spectrometry (MS) transfer line was generally held at the similar temperature as the injection port. Different GC-MS approaches, including electron capture negative ion (ECNI)-MS, negative chemical ionization (NCI)-MS, NCI-MS/MS and electron impact-high resolution mass spectrometry (EI-HRMS), were generally applied for DP analysis and quantification (Barón et al, 2012(Barón et al, , 2014a(Barón et al, , 2014bDe la Torre et al, 2010a;Hoh et al, 2006;Kang et al, 2010;Möller et al, 2010;Muñoz-Arnanz et al, 2011;Qiu and Hites, 2008;Xiao et al, 2012;Zeng et al, 2014). Molecular ion fragments at m/z 651.8/653.8 were generally selected for DP monitoring in ECNI-MS and NCI-MS, while the selected ion and transition at 654 N 35/ 654 N 37 were monitored in NCI-MS/MS (Barón et al, 2012).…”

“…The method detection limits (MDLs) for DP were reported at the level of pg m − 3 in air Möller et al, 2012a,b;Xiao et al, 2012), pg L −1 in water Na et al, 2015;Qi et al, 2010;Venier et al, 2014), pg g −1 dry weight (dw) in soil and sediment (Barón et al, 2012(Barón et al, , 2014aMa et al, 2011;Qi et al, 2010;Shen et al, 2011a,b;Wang et al, 2010a,b), and ng g −1 lipid weight (lw) in biota samples Peng et al, 2015;Salamova and Hites, 2013;Yan et al, 2012;Zhang et al, 2011aZhang et al, , 2015Zhu et al, 2014), respectively. Even lower MDL values were obtained in fish (pg g −1 lw) when using GC-NCI-MS/MS and GC-EI-HRMS (Barón et al, 2012;Shen et al, 2010Shen et al, , 2011a, which guaranteed the detection of DP with lower levels in the background areas.…”

“…In Great Lakes fish, the level of mirex could reach up to 4300 ng g − 1 lw (Shen et al, 2011a), while Dec 602, 603, 604 and CP could be detected to some extent with relatively lower concentrations (b LOD (limit of detection) -180 ng g − 1 lw) (Shen et al, , 2011a. Nevertheless, Dec 602 showed greater bioavailable or bioaccumulative than DP in many cases (Barón et al, 2014a(Barón et al, , 2015Guerra et al, 2011;Peng et al, 2014;Shen et al, 2010Shen et al, , 2011a, proposing new concern on its potential ecological risk. The reason might be due to its relatively low logK OW values (estimated logK OW : 8.1) and subsequent high bioavailability compared with DP (estimated value: 11.3) (Shen et al, 2011a).…”