Trends of legacy and emerging organic contaminants in a sediment core from Cienfuegos Bay, Cuba, from 1990 to 2015.

Legacy and emerging organic pollutants pose an ever-expanding challenge for the marine environment. This study analysed a dated sediment core from Cienfuegos Bay, Cuba, to assess the occurrence of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), alternative halogenated flame retardants (aHFRs), organophosphate esters (OPEs), and phthalates (PAEs) from 1990 to 2015. The results evidence the continuing presence of historical regulated contaminants (PCBs, OCPs, and PBDEs) in the southern basin of Cienfuegos Bay. PCB contamination declined since 2007, likely in response to the gradual global phasing out of PCB containing materials. There have been relatively consistent low accumulation rates for OCPs and PBDEs at this location (in 2015 approximately 1.9 and 0.26ng/cm2/year, respectively, with 2.8ng/cm2/year for Σ6PCBs), with indications of recent local DDT use in response to public health emergencies. In contrast, sharp increases are observed between 2012 and 2015 for the contaminants of emerging concern (PAEs, OPEs, and aHFRs), and in the case of two PAEs (DEHP and DnBP) the concentrations were above the established environmental effect limits for sediment dwelling organisms. These increasing trends reflect the growing global usage of both alternative flame retardants and plasticizer additives. Local drivers for these trends include nearby industrial sources such as a plastic recycling plant, multiple urban waste outfalls, and a cement factory. The limited capacity for solid waste management may also contribute to the high concentrations of emerging contaminants, especially plastic additives. For the most recent year (2015), the accumulation rates for Σ17aHFRs, Σ19PAEs, and Σ17OPEs into sediment at this location were estimated to be 10, 46 000, and 750ng/cm2/year, respectively. This data provides an initial survey of emerging organic contaminants within this understudied region of the world. The increasing temporal trends observed for aHFRs, OPEs, and PAEs highlights the need for further research concerning the rapid influx of these emerging contaminants.

A First Comprehensive Baseline of Hydrocarbon Pollution in Gulf of Mexico Fishes.

Despite over seven decades of production and hundreds of oil spills per year, there were no comprehensive baselines for petroleum contamination in the Gulf of Mexico (GoM) prior to this study. Subsequent to the 2010 Deepwater Horizon (DWH) spill, we implemented Gulf-wide fish surveys extending over seven years (2011-2018). A total of 2,503 fishes, comprised of 91 species, were sampled from 359 locations and evaluated for biliary polycyclic aromatic hydrocarbon (PAH) concentrations. The northern GoM had significantly higher total biliary PAH concentrations than the West Florida Shelf, and coastal regions off Mexico and Cuba. The highest concentrations of biliary PAH metabolites occurred in Yellowfin Tuna (Thunnus albacares), Golden Tilefish (Lopholatilus chamaeleonticeps), and Red Drum (Sciaenops ocellatus). Conversely, biliary PAH concentrations were relatively low for most other species including economically important snappers and groupers. While oil contamination in most demersal species in the north central GoM declined in the first few years following DWH, more recent increases in exposure to PAHs in some species suggest a complex interaction between multiple input sources and possible re-suspension or bioturbation of oil-contaminated sediments. This study provides the most comprehensive baselines of PAH exposure in fishes ever conducted for a large marine ecosystem.

Chronic PAH exposures and associated declines in fish health indices observed for ten grouper species in the Gulf of Mexico.

Ten grouper species grouper (n = 584) were collected throughout the Gulf of Mexico (GoM) from 2011 through 2017 to provide information on hepatobiliary polycyclic aromatic hydrocarbon (PAH) concentrations in the aftermath of the Deepwater Horizon (DWH) oil spill. Liver and bile samples were analyzed for PAHs and their metabolites using triple quadrupole mass spectrometry (GC/MS/MS) and high-performance liquid chromatography with fluorescence detection (HPLC-F), respectively. Data were compared among species and sub-regions of the GoM to understand spatiotemporal exposure dynamics in these economically and ecologically important species. Significant differences in the composition and concentrations of PAHs were detected spatially, over time and by species. The West Florida Shelf, Cuba coast and the Yucatan Shelf had a greater proportion of the pyrogenic PAHs in their livers than the other regions likely due to non-oil industry related sources (e.g., marine vessel traffic) in the regional composition profiles. Mean liver PAH concentrations were highest in the north central region of the GoM where DWH occurred. Biliary PAH concentrations and health indicator biometrics initially decrease during the first three years following the DWH oil spill but significantly increased thereafter. Increased exposures are likely explained by the resuspension of residual DWH oil as well as continued inputs from natural (e.g., seeps) sources and other anthropogenically derived sources (e.g., riverine runoff, other oil spills, and leaking oil and gas infrastructure). The increasing trend in PAH concentrations in the bile and liver of grouper species in the north central region of the GoM post-DWH suggest continued chronic exposures, however the critical stage at which permanent, irreparable damage may occur is unknown. Long-term monitoring of PAH levels and associated fish health biomarkers is necessary to evaluate impacts of chronic exposures, particularly in regions subject to intensive oil extraction activities.

Decadal Assessment of Polycyclic Aromatic Hydrocarbons in Mesopelagic Fishes from the Gulf of Mexico Reveals Exposure to Oil-Derived Sources.

This study characterizes a decadal assessment of polycyclic aromatic hydrocarbons (PAHs) in the muscle tissues of mesopelagic fish species as indicators of the environmental health of the Gulf of Mexico (GoM) deep-pelagic ecosystem. Mesopelagic fishes were collected prior to the Deepwater Horizon (DWH) oil spill (2007), immediately post-spill (2010), 1 year after the spill (2011), and 5-6 years post-spill (2015-2016) to assess if the mesopelagic ecosystem was exposed to, and retained, PAH compounds from the DWH spill. Results indicated that a 7- to 10-fold increase in PAHs in fish muscle tissues occurred in 2010-2011 (4972 ± 1477 ng/g) compared to 2007 (630 ± 236 ng/g). In 2015-2016, PAH concentrations decreased close to the levels measured in 2007 samples (827 ± 138 ng/g); however, the composition of PAHs still resembles a petrogenic source similar to samples collected in 2010-2011. PAH composition in muscle samples indicated that natural sources (e.g., Mississippi River and natural seeps) or spatial variability within the GoM do not explain the temporal variability of PAHs observed from 2007 to 2016. Furthermore, analysis of different fish tissues indicated the dietary intake and maternal transfer of PAHs as the primary mechanisms for bioaccumulation in 2015-2016, explaining the elevated levels and composition of PAHs in ovarian eggs.