Preservation of brevetoxins in Southwest Florida coastal sediments.

Florida red tide is a natural phenomenon caused by the dinoflagellate, Karenia brevis. Karenia brevis blooms produce potent toxins (brevetoxins) that can cause neurotoxic and respiratory illness in humans and marine life. Red tides were recorded by Spanish explorers as early as the 17th century, however published red tide studies before 1940 are unavailable. Recent studies have suggested that red tide events may be becoming more frequent, intense, and longer lasting, which may be linked to modern land development and changing water quality. While the scientific record of modern red tides is relatively short, the distributions and concentrations of chemical biomarkers (e.g., brevetoxins produced by K. brevis) in coastal-marine sediments can potentially be used to study historic red tides. This study aims to quantify the concentration and vertical distribution of brevetoxins in coastal Southwest Florida (SWFL) sediment cores in order to determine if downcore brevetoxins may potentially be used to reconstruct historic red tide events. Sediment samples were radiometrically dated using 210Pb and subsamples were analyzed utilizing liquid chromatography/triple quadrupole mass spectrometry (LC-MS/MS) for brevetoxin congeners, namely, PbTx-1, PbTx-2, PbTx-3, and PbTx-5. The 210Pb-dated sediment cores represent ∼60-80 years of brevetoxin accumulation and total brevetoxin (ΣPbTx) concentrations in sediment cores varied from below detection limits to 25.3 ng g - 1 of dry sediments. Highest concentrations were found in surficial sediments (top 0-3 cm) and may indicate brevetoxin preservation from the 2017-2019 red-tide event. The down-core preservation and variability of brevetoxin indicate its potential use as a chemical biomarker to assess long-term red tide intensities and frequencies. This research is a first step towards reconstructing historic red tide events from sedimentary chemical biomarkers and may allow for future assessment of the human impacts on red tide frequency, intensity and duration.

Scavenging of select radionuclides and trace elements by pelagic Sargassum in the Caribbean Sea.

In recent years, the North Atlantic and the Caribbean Sea have experienced unusual and unprecedented pelagic Sargassum blooms, which may adversely affect coastal ecosystems and productive ocean. Sargassum has the potential to scavenge trace elements and radionuclides from seawater, and when bioaccumulated and thus concentrated, can pose a potential threat to higher trophic organisms, including humans that consume impacted seafood. In this study, trace elements and naturally-occurring U/Th-series radionuclides were measured in Sargassum that were collected in the coastal waters of the Caribbean Sea (Antigua/Barbuda, Belize, and Barbados) to better define baseline concentrations and activities, and to assess the scavenging potential for these trace elements and radionuclides. The mean concentration of trace elements observed in Sargassum collected across these three Caribbean Sea are ranked accordingly to the following descending order: Sr > As>Fe > Mn > Zn > Ni > V > C > Cd > Se > Co > Cr > Pb > Ag > Hg. 210-Po and 210Pb activities in Sargassum were observed to be more elevated than previously reported values.

Correction: Coupled effects of oil spill and hurricane on saltmarsh terrestrial arthropods.

[This corrects the article DOI: 10.1371/journal.pone.0194941.].

Coupled effects of oil spill and hurricane on saltmarsh terrestrial arthropods.

Terrestrial arthropods play an important role in saltmarsh ecosystems, mainly affecting the saltmarsh's primary production as the main consumers of terrestrial primary production and decomposition. Some of these arthropods, including selected insects and spiders, can be used as ecological indicators of overall marsh environmental health, as they are differentially sensitive to ecological stressors, such as land loss, erosion, oil spills, and tropical storms. In the present study, we used terrestrial arthropods collected from seven (three lightly-oiled, four heavily-oiled) sites in Barataria Bay and from three unoiled reference sites in Delacroix, Louisiana, to determine the impacts of the distribution and re-distribution of Deepwater Horizon (DWH) oil on these saltmarsh ecosystems. A total of 9,476 and 12,256 insects were collected in 2013 and 2014, respectively. The results show that the terrestrial arthropods were negatively affected by the re-distribution of DWH oil by Hurricane Isaac in 2012, although the level of impacts varied among the arthropod groups. Moreover, the mean diversity index was higher (>1.5) in 2014 than in 2013 (<1.5) for all sites, suggesting a recovery trajectory of the saltmarsh arthropod population. The higher taxonomic richness observed in the reference sites compared to the oiled sites for both years also indicated long-term impacts of DWH oil to the saltmarsh arthropod community. Whereas a slow recovery of certain terrestrial arthropods was observed, long-term monitoring of arthropod communities would help better understand the recovery and succession of the marsh ecosystems.

Application of enhanced gas chromatography/triple quadrupole mass spectrometry for monitoring petroleum weathering and forensic source fingerprinting in samples impacted by the Deepwater Horizon oil spill.

Accurate characterization of petroleum hydrocarbons in complex and weathered oil residues is analytically challenging. This is primarily due to chemical compositional complexity of both the oil residues and environmental matrices, and the lack of instrumental selectivity due to co-elution of interferences with the target analytes. To overcome these analytical selectivity issues, we used an enhanced resolution gas chromatography coupled with triple quadrupole mass spectrometry in Multiple Reaction Monitoring (MRM) mode (GC/MS/MS-MRM) to eliminate interferences within the ion chromatograms of target analytes found in environmental samples. This new GC/MS/MS-MRM method was developed and used for forensic fingerprinting of deep-water and marsh sediment samples containing oily residues from the Deepwater Horizon oil spill. The results showed that the GC/MS/MS-MRM method increases selectivity, eliminates interferences, and provides more accurate quantitation and characterization of trace levels of alkyl-PAHs and biomarker compounds, from weathered oil residues in complex sample matrices. The higher selectivity of the new method, even at low detection limits, provides greater insights on isomer and homolog compositional patterns and the extent of oil weathering under various environmental conditions. The method also provides flat chromatographic baselines for accurate and unambiguous calculation of petroleum forensic biomarker compound ratios. Thus, this GC/MS/MS-MRM method can be a reliable analytical strategy for more accurate and selective trace level analyses in petroleum forensic studies, and for tacking continuous weathering of oil residues.

(234)Th as a tracer of vertical transport of polycyclic aromatic hydrocarbons in the northern Gulf of Mexico.

Particle-mediated vertical flux of polycyclic aromatic hydrocarbons (PAHs) plays an important role in their removal from upper oceans and sets a limit on the amount delivered to the deep-sea sediments. In this study, we applied a one-dimensional steady-state (234)Th scavenging model to estimate vertical flux of PAHs in the northern Gulf of Mexico and compared them with sediment trap based flux estimates. The (234)Th-based ∑PAH43 fluxes were 6.7±1.0µgm(-2)d(-1) and 3.7±0.6µgm(-2)d(-1) while sediment trap-based fluxes were 4.0±0.6µgm(-2)d(-1) and 4.5±0.7µgm(-2)d(-1) at 150m and 250m, respectively. Alkylated homologues contributed to 80% of the total PAH fluxes which is in contrary to other regions where combustion derived parent PAHs dominate the fluxes. The results indicate that the (238)U-(234)Th disequilibria can be an effective tracer of particulate PAH fluxes in upper mesopelagic zones and can provide flux estimates with high spatial coverage needed to quantify their long term fate and transport in the marine systems.

Distributions and accumulation rates of polycyclic aromatic hydrocarbons in the northern Gulf of Mexico sediments.

Sediment samples collected from shelf, slope and interior basin of the northern Gulf of Mexico during 2011-2013, 1-3 years after the Deepwater Horizon (DWH) oil spill, were utilized to characterize PAH pollution history, in this region. Results indicate that the concentrations of surface ΣPAH43 and their accumulation rates vary between 44 and 160 ng g(-1) and 6-55 ng cm(-2) y(-1), respectively. ΣPAH43 concentration profiles, accumulation rates and Δ(14)C values are significantly altered only for the sediments in the immediate vicinity of the DWH wellhead. This shows that the impact of DWH oil input on deep-sea sediments was generally limited to the area close to the spill site. Further, the PAHs source diagnostic analyses suggest a noticeable change in PAHs composition from higher to lower molecular weight dominance which reflects a change in source of PAHs in the past three years, back to the background composition. Results indicate low to moderate levels of PAH pollution in this region at present, which are unlikely to cause adverse effects on benthic communities.