Spatial distribution and mass transport of Perfluoroalkyl Substances (PFAS) in surface water: A statewide evaluation of PFAS occurrence and fate in Alabama.

Per- and polyfluoroalkyl substances (PFAS) have been previously detected near suspected sources in Alabama, but the overall extent of contamination across the state is unknown. This study evaluated the spatial distribution of 17 PFAS within the ten major river basins in Alabama and provided insights into their transport and fate through a mass flux analysis. Six PFAS were identified in 65 out of the 74 riverine samples, with mean ∑6PFAS levels of 35.2 ng L-1. The highest ∑6PFAS concentration of 237 ng L-1 was detected in the Coosa River, a transboundary river that receives discharges from multiple sources in Alabama and Georgia. PFAS distribution was not observed to be uniform across the state: while the Coosa, Alabama, and Chattahoochee rivers presented relatively high mean ∑6PFAS concentrations of 191, 100 and 28.8 ng L-1, respectively, PFAS were not detected in the Conecuh, Escatawpa, and Yellow rivers. Remaining river systems presented mean ∑6PFAS concentrations between 7.94 and 24.7 ng L-1. Although the short-chain perfluoropentanoic acid (PFPeA) was the most detected analyte (88%), perfluorobutanesulfonic acid (PFBS) was the substance with the highest individual concentration of 79.4 ng L-1. Consistent increases in the mass fluxes of PFAS were observed as the rivers flowed through Alabama, reaching up to 63.3 mg s-1, indicating the presence of numerous sources across the state. Most of the mass inputs would not have been captured if only aqueous concentrations were evaluated, since concentration is usually heavily impacted by environmental conditions. Results of this study demonstrate that mass flux is a simple and powerful complementary approach that can be used to broadly understand trends in the transport and fate of PFAS in large river systems.

Enhanced effectiveness of oil dispersants in destabilizing water-in-oil emulsions.

Oil impacting the northern Gulf of Mexico shoreline from the 2010 Deepwater Horizon accident was predominantly in the form of water-in-oil emulsions (WOE), a chemically weathered, highly viscous, neutrally buoyant material. Once formed, WOE are extremely difficult to destabilize. Commercially-available oil dispersants are largely ineffective de-emulsifiers as a result of the inability of dispersant surfactants to displace asphaltenes stabilizing the oil-water interface. This study investigated the effectiveness of the commercially-available dispersant Corexit 9500A, modified to enhance its polar fraction, in destabilizing WOE. Results suggest that Corexit modified to include between 20-60% fractional amount of either polar additive (1-octanol or hexylamine) will produce a modest increase in WOE instability, with a Corexit to hexylamine ratio of approximately 80/20 providing the most effective enhanced destabilization. Results support the hypothesis that modifying the fraction of polar constituents in commercial dispersants will increase asphaltene solubility, decrease oil-water interface stability, and enhance WOE instability.

A rapid UHPLC-MS/MS method for quantitation of phytoestrogens and the distribution of enterolactone in an Alabama estuary.

Endocrine disrupting chemicals (EDCs) are natural or synthetic compounds that can interfere with the endocrine systems of humans and wildlife. EDCs can pass through wastewater treatment systems, or run off from urban areas or agricultural operations, into natural water bodies, exposing resident and migratory organisms to complex EDC mixtures. Some phytoestrogenic polyphenolics (PEPP) are known or suspected EDCs; however, their contribution to total EDC burden in natural surface water systems is largely unknown. We describe a rapid, sensitive, and reproducible quantitative method for analysis of 15 PEPP in estuarine sediment and water, using ultra-high performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS). The method provides excellent peak resolution, peak separation, and rapid run times (method separation/total run time: 8/12.5 min). With two exceptions, spiking experiments demonstrated that the percent recoveries for target PEPP in sediment and water samples were within acceptable analytical validation limits. LOD and LOQ values ranged from 0.004 to 0.010 ng/injection and 0.013-0.032 ng/injection, respectively. The validated method was used for PEPP analysis of sediment and water samples collected from 11 locations within the Perdido Bay estuary in coastal Alabama. No PEPP above the LOD were detected in sediment samples. The mammalian-derived lignin enterolactone was observed at low concentrations in water throughout the estuary, and significantly, at elevated concentrations at two locations associated with small-scale septic systems (3.66 ±â€¯0.27 ng L-1 and 4.01 ±â€¯0.33 ng L-1) and a large wastewater treatment system (4.56 ±â€¯0.24 ng L-1 and 5.69 ±â€¯0.43 ng L-1).

A rapid UHPLC-MS/MS method for simultaneous quantitation of 23 perfluoroalkyl substances (PFAS) in estuarine water.

Per- and polyfluoroalkyl substances (PFAS) represent a large group of synthetic organic compounds which, as a result of their unique chemical properties, render them extremely recalcitrant to environmental degradation. Research concerning the environmental, ecological, and human health effects of PFAS has focused on long aliphatic chain (> C7) compounds having no ether bonds. For new, less studied, or previously unknown PFAS (≤ C7 with ether bonds), there is little to no information about their environmental behavior, transport, fate, exposure, and toxicological effects. LC-MS/MS has proven effective for detection and quantitation of some PFAS, however, straightforward analytical methods for simultaneous trace quantitation of broad mixtures of PFAS in varied complex environmental media, available to a wide range of researchers and also suitable for routine monitoring, remain critical needs. Here we describe a simple, rapid, sensitive, and reproducible quantitative analytical method for trace analysis and monitoring of 23 PFAS in estuarine water, using ultra-high performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS). The developed MRM method allows simultaneous trace quantitation of a broad mixture of PFAS, including 13 perfluoroalkyl carboxylic acids, 8 perfluoroalkyl sulfonates, and 2 short-chain perfluoroethers. The method provides better peak resolution and peak separation, and shorter run times (method separation/total run time: 6/8 min) compared to those of existing analytical methods. Percent recoveries for the validated method ranged from 78.54 to 112.61. LOD and LOQ values ranged from 0.48 to 1.68 pg/injection and 1.71 to 5.40 pg/injection, respectively. The validated method was used for quantitative PFAS analysis of estuarine water samples collected from 16 locations within the Perdido Bay estuary in coastal Alabama.

An ultrahigh-performance chromatography/tandem mass spectrometry quantitative method for trace analysis of potential endocrine disrupting steroid hormones in estuarine sediments.

RATIONALE: Estuaries are dynamic ecosystems, providing vital habitat for unique organisms of great ecological and commercial importance. The influx of natural and synthetic steroid hormones into estuaries poses risks to these organisms and to broader ecosystem health. However, detecting these trace level pollutants in estuarine water and sediment requires improved analytical techniques. METHODS: We describe an optimized ultrahigh-performance chromatography/tandem mass spectrometry (UHPLC/MS/MS) method for simultaneous quantitation of four classes of steroid hormones (estrogens, glucocorticoids, androgens and progestins) in sediment samples collected from an Alabama estuary. Sediment samples were homogenized using Hydromatrix (HM) sorbent and extracted with methanol and water (70%, v/v). Centrifuged extracts were purified using an Agilent Bond Elut QuEChERS dispersive-SPE kit to eliminate interfering substances that could negatively influence the ionization process. Chromatographic separation was achieved on a Poroshell 120 Phenyl-Hexyl column using an Agilent 1290 Infinity II UHPLC pump. Quantitation was carried out using an Agilent triple quadrupole mass spectrometer equipped with a JetStream/ESI source in dual mode. RESULTS: Chromatographic separation and better peak resolution were accomplished on an Agilent Poroshell 120 Phenyl-Hexyl column using a binary gradient method with a mobile phase consisting of 1 mM ammonium fluoride in water and a mixture of methanol/acetonitrile. A dynamic multiple reaction monitoring (MRM) method was developed by optimizing various MS parameters. The method was used to analyze target steroid hormones in estuarine sediments. A total of ten steroid hormones were detected at trace amounts in estuarine sediments. CONCLUSIONS: The optimized analytical method described here involves reasonably simple sample preparation and simultaneous trace level quantitation of four classes (estrogens, glucocorticoids, androgens and progestins) of steroid hormones in a single experimental run. Copyright © 2016 John Wiley & Sons, Ltd.

Correction: a tale of two recent spills-comparison of 2014 Galveston Bay and 2010 Deepwater Horizon Oil Spill Residues.

[This corrects the article DOI: 10.1371/journal.pone.0118098.].

A tale of two recent spills--comparison of 2014 Galveston Bay and 2010 Deepwater Horizon oil spill residues.

Managing oil spill residues washing onto sandy beaches is a common worldwide environmental problem. In this study, we have analyzed the first-arrival oil spill residues collected from two Gulf of Mexico (GOM) beach systems following two recent oil spills: the 2014 Galveston Bay (GB) oil spill, and the 2010 Deepwater Horizon (DWH) oil spill. This is the first study to provide field observations and chemical characterization data for the 2014 GB oil spill. Here we compare the physical and chemical characteristics of GB oil spill samples with DWH oil spill samples and present their similarities and differences. Our field observations indicate that both oil spills had similar shoreline deposition patterns; however, their physical and chemical characteristics differed considerably. We highlight these differences, discuss their implications, and interpret GB data in light of lessons learned from previously published DWH oil spill studies. These analyses are further used to assess the long-term fate of GB oil spill residues and their potential environmental impacts.

Long-term monitoring data to describe the fate of polycyclic aromatic hydrocarbons in Deepwater Horizon oil submerged off Alabama's beaches.

The 2010 Deepwater Horizon (DWH) catastrophe had considerable impact on the ∼ 50 km long sandy beach system located along the Alabama shoreline. We present a four-year dataset to characterize the temporal evolution of various polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologs trapped in the residual oil buried along the shoreline. Field samples analyzed include the first arrival oil collected from Perdido Bay, Alabama in June 2010, and multiple oil spill samples collected until August 2014. Our field data show that, as of August 2014, DWH oil is still trapped along Alabama's beaches as submerged oil, predominately in the form of surface residual oil balls (SRBs). Chemical characterization data show that various PAHs present in the spilled oil (MC252 crude) weathered by about 45% to 100% when the oil was floating over the open ocean system in the Gulf of Mexico. Light PAHs, such as naphthalenes, were fully depleted, whereas heavy PAHs, such as chrysenes, were only partially depleted by about 45%. However, the rate of PAH weathering appears to have decreased significantly once the oil was buried within the partially-closed SRB environment. Concentration levels of several heavy PAHs have almost remained constant over the past 4 years. Our data also show that evaporation was most likely the primary weathering mechanism for PAH removal when the oil was floating over the ocean, although photo-degradation and other physico-chemical processes could have contributed to some additional weathering. Chemical data presented in this study indicate that submerged oil containing various heavy PAHs (for example, parent and alkylated chrysenes) is likely to remain in the beach system for several years. It is also likely that the organisms living in these beach environments would have an increased risk of exposure to heavy PAHs trapped in the non-recoverable form of buried DWH oil spill residues.

Fate of Deepwater Horizon oil in Alabama's beach system: understanding physical evolution processes based on observational data.

The impact of MC252 oil on northern Gulf of Mexico (GOM) beaches from the 2010 Deepwater Horizon (DWH) catastrophe was extensive along Alabama's beaches. While considerable amount of cleanup has occurred along these beaches, as of August 2014, DWH oil spill residues continue to be found as surface residual balls (SRBs), and also occasionally as submerged oil mats (SOMs). Four years of field observations informing the fate and transport of DWH SRBs in Alabama's beach system are presented here, along with a conceptual framework for describing their physical evolution processes. The observation data show that SRBs containing MC252 residues currently remain in Alabama's beach system, although their relationship to SOMs is not fully known. Based on our field observations we conclude that small DWH SRBs are likely to persist for several years along the Alabama shoreline.

Evaluation of differential cytotoxic effects of the oil spill dispersant Corexit 9500.

AIMS: The British Petroleum (BP) oil spill has raised several ecological and health concerns. As the first response, BP used a chemical dispersant, Corexit-9500, to disperse the crude oil in the Gulf of Mexico to limit shoreline contamination problems. Nevertheless, portions of this oil/Corexit mixture reached the shoreline and still remain in various Gulf shore environments. The use of Corexit itself has become a significant concern since its impacts on human health and environment is unclear. MAIN METHODS: In this study, in vitro cytotoxic effects of Corexit were evaluated using different mammalian cells. KEY FINDINGS: Under serum free conditions, the LC50 value for Corexit in BL16/BL6 cell was 16 ppm, in 1321N1 cell was 33 ppm, in H19-7 cell was 70 ppm, in HEK293 was 93 ppm, and in HK-2 cell was 95 ppm. With regard to the mechanisms of cytotoxicity, we hypothesize that Corexit can possibly induce cytotoxicity in mammalian cells by altering the intracellular oxidative balance and inhibiting mitochondrial functions. Corexit induced increased reactive oxygen species and lipid peroxide levels; also, it depleted glutathione content and altered catalase activity in H19-7 cells. In addition, there was mitochondrial complex-I inhibition and increase in the pro-apoptotic factors including caspase-3 and BAX expression. SIGNIFICANCE: The experimental results show changes in intracellular oxidative radicals leading to mitochondrial dysfunctions and apoptosis in Corexit treatments, possibly contributing to cell death. Our findings raise concerns about using large volumes of Corexit, a potential environmental toxin, in sensitive ocean environments.

Provenance of Corexit-related chemical constituents found in nearshore and inland Gulf Coast waters.

The dispersants Corexit 9527 and Corexit 9500 were extensively used during the response to the Deepwater Horizon accident in 2010. In addition to the monitoring programs established by federal and state governments, local communities also conducted studies to determine if chemical constituents from these dispersants impacted nearshore and inland waters. One community (the City of Orange Beach, Alabama) collected water samples between September, 2010 and January, 2011, and found the dispersant-related chemicals propylene glycol, 2-butoxyethanol, and dioctyl sodium sulfosuccinate at nearshore and inland water sampling sites. In this paper, we examine their dataset in an attempt to discern the origin of these chemicals. Our assessment indicates that these compounds are unlikely to be present as a result of the use of Corexit dispersants; rather, they are likely related to point and non-point source stormwater discharge.