Abstract

PBDEs, HBCD, novel DBDPE, PBEB and HBB, dechloranes, OPFRs and natural MeO-PBDEs were monitored in muscle of striped dolphins (Stenella coeruleoalba) from the Mediterranean Sea collected in three time periods (1990, 2004–2009 and 2014–2018). PBDEs levels decreased about 60% in under three decades, from 5067 ± 2210 to 2068 ± 2642ngg−1 lw, evidencing the success of their ban. Most PBDEs were found in all the samples, with BDE-47, -99, -154, -100 and -153 as the main contributors. Found in 71.4% of the samples, α-HBCD was stable through time and usually <LOQ. DBDPE concentrations decreased by 89% from 1990 to 2004–2009 and have remained stable since. HBB occurred rarely and decreased by 94% to a current few ngg−1 lw. Dec 602 was the main dechlorane with stable concentrations around 1200 ngg−1 lw, but a declining trend might have started in the last years. OPFRs concentrations were stable and showed the highest concentrations of all FRs in 2014–2018: 6253 ± 11,293ngg−1 lw. TBOEP and TNBP contributed to most of the OPFR concentration, the former with decreasing levels by 96%. MeO-PBDEs showed mean concentrations between 600 and 700ngg−1 lw in all periods. Non-targeted analysis allowed the identification and semi-quantification of additional chlorinated pollutants, such as polychlorinated terphenyls (PCTs) (levels decreasing by 81% to a current 770 ngg−1 lw mean) and polychlorinated diphenyl ethers (PCDEs) (decreasing by 83% to a current 3200ngg−1 lw) in Mediterranean marine mammals for the first time.

Highlights

  • Concentrations of flame retardants (FRs) in muscle of striped dolphins are summarized in Table 2 (see Supporting Information for results of compound groups and individual compounds in each sample (Tables: S2, groups, S3, legacy FRs; S4, emerging halogenated flame retardants (HFRs); S5, organophosphorus flame retardants (OPFRs), and S6, MeO-polybrominated diphenyl ethers (PBDEs)))

  • Due to the intrinsic variability of results from individuals that could differ in even a couple of decades of age, the standard deviation within a period is comparable to the contamination level

  • The result showed a highly decreasing of trend of PBDE concentrations of about 60% from 1990 to 2018. (R = 708, p > 0.001) (Fig. 1) and it is reasonable to think that the trend continues

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Summary

Materials and methods

Nowadays there is an obvious concern about the human impact on the environment, including marine pollution Regulation such as the Stockholm Convention on Persistent Organic Pollutants (POPs) and European directives have restricted or banned the use of some contaminants of concern. Hexabromocyclododecane (HBCD) is another FR than can leach out of the materials and is toxic to aquatic organisms, albeit less than PBDEs (Alaee et al, 2003; SC, 2008; Lu et al, 2018) It has been detected in environmental and biotic samples (Eljarrat et al, 2004a; Eljarrat et al, 2009) and included in the REACH regulation and the Stockholm Convention.

Sampling
Standards and reagents
Sample preparation
Instrumental analysis
Quality assurance
Non-targeted analysis
Statistical analysis
Results and discussion
Legacy BFRs
Emerging HFRs
MeO-PBDEs
Non-targeted compounds
Conclusions
Full Text
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