Hot and Cold: Photochemical Weathering Mediates Oil Properties and Fate Differently Depending on Seawater Temperature.

Photochemical weathering transforms petroleum oil and changes its bulk physical properties, as well as its partitioning into seawater. This transformation process is likely to occur in a cold water marine oil spill, but little is known about the behavior of photochemically weathered oil in cold water. We quantified the effect of photochemical weathering on oil properties and partitioning across temperatures. Compared to weathering in the dark, photochemical weathering increases oil viscosity and water-soluble content, decreases oil-seawater interfacial tension, and slightly increases density. Many of these photochemical changes are much larger than changes caused by evaporative weathering. Further, the viscosity and water-soluble content of photochemically weathered oil are more temperature-sensitive compared to evaporatively weathered oil, which changes the importance of key fate processes in warm versus cold environments. Compared to at 30 °C, photochemically weathered oil at 5 °C would have a 16× higher viscosity and a 7× lower water-soluble content, resulting in lower entrainment and dissolution. Collectively, the physical properties and thus fate of photochemically weathered oil in a cold water spill may be substantially different from those in a warm water spill. These differences could affect the choice of oil spill response options in cold, high-light environments.

Recommendations for advancing test protocols examining the photo-induced toxicity of petroleum and polycyclic aromatic compounds.

Photo-induced toxicity of petroleum products and polycyclic aromatic compounds (PACs) is the enhanced toxicity caused by their interaction with ultraviolet radiation and occurs by two distinct mechanisms: photosensitization and photomodification. Laboratory approaches for designing, conducting, and reporting of photo-induced toxicity studies are reviewed and recommended to enhance the original Chemical Response to Oil Spills: Ecological Research Forum (CROSERF) protocols which did not address photo-induced toxicity. Guidance is provided on conducting photo-induced toxicity tests, including test species, endpoints, experimental design and dosing, light sources, irradiance measurement, chemical characterization, and data reporting. Because of distinct mechanisms, aspects of photosensitization (change in compound energy state) and photomodification (change in compound structure) are addressed separately, and practical applications in laboratory and field studies and advances in predictive modeling are discussed. One goal for developing standardized testing protocols is to support lab-to-field extrapolations, which in the case of petroleum substances often requires a modeling framework to account for differential physicochemical properties of the constituents. Recommendations are provided to promote greater standardization of laboratory studies on photo-induced toxicity, thus facilitating comparisons across studies and generating data needed to improve models used in oil spill science.

Nematostella vectensis exhibits an enhanced molecular stress response upon co-exposure to highly weathered oil and surface UV radiation.

Crude oil released into the environment undergoes weathering processes that gradually change its composition and toxicity. Co-exposure to petroleum mixtures and other stressors, including ultraviolet (UV) radiation, may lead to synergistic effects and increased toxicity. Laboratory studies should consider these factors when testing the effects of oil exposure on aquatic organisms. Here, we study transcriptomic responses of the estuarine sea anemone Nematostella vectensis to naturally weathered oil, with or without co-exposure to environmental levels of UV radiation. We find that co-exposure greatly enhances the response. We use bioinformatic analyses to identify molecular pathways implicated in this response, which suggest phototoxicity and oxidative damage as mechanisms for the enhanced stress response. Nematostella's stress response shares similarities with the vertebrate oxidative stress response, implying deep conservation of certain stress pathways in animals. We show that exposure to weathered oil along with surface-level UV exposure has substantial physiological consequences in a model cnidarian.

How the 2010 Deepwater Horizon spill reshaped our understanding of crude oil photochemical weathering at sea: a past, present, and future perspective.

The weathering of crude oil at sea has been researched for nearly half a century. However, there have been relatively few opportunities to validate laboratory-based predictions about the rates, relative importance, and controls of oil weathering processes (e.g., evaporation, photo-oxidation, and emulsification) under natural field conditions. The 2010 Deepwater Horizon (DWH) spill in the Gulf of Mexico provided the oil spill science community with a unique opportunity to evaluate our laboratory-based predictions in nature. With a focus on photochemical weathering, we review what we knew prior to the DWH spill, what we learned from the DWH spill, and what priority gaps in knowledge remain. Three key findings from the DWH spill are discussed. First, the rate and extent of photochemical weathering was much greater for the floating surface oil than expected based on early conceptual models of oil weathering. Second, indirect photochemical processes played a major role in the partial oxidation of the floating surface oil. Third, the extensive and rapid changes to the physical and chemical properties of oil by sunlight may influence oil fate, transport, and the selection of response tools. This review also highlights findings and predictions about photochemical weathering of oil from several decades ago that appear to have escaped the broader scientific narrative and ultimately proved true for the DWH spill. By focusing on these early predictions and synthesizing the numerous findings from the DWH spill, we expect this review will better prepare the oil spill science community to respond to the next big spill in the ocean.

How Persistent and Bioavailable Are Oxygenated Deepwater Horizon Oil Transformation Products?

About half of the surface oil floating on the Gulf of Mexico in the aftermath of the 2010 Deepwater Horizon spill was transformed into oxygenated hydrocarbons (OxHC) within days to weeks. These OxHC persist for years in oil/sand aggregates in nearshore and beach environments, and there is concern that these aggregates might represent a long-term source of toxic compounds. However, because this OxHC fraction is a continuum of transformation products that are not well chemically characterized, it is not included in current oil spill fate and effect models. This challenges an accurate environmental risk assessment of weathered oil. Here, we used molecular and bulk analytical techniques to constrain the chemical composition and environmental fate of weathered oil samples collected on the sea surface and beaches of the Gulf of Mexico. We found that approximately 50% of the weathering-related disappearance of saturated and aromatic compounds in these samples was compensated by an increase in OxHC. Furthermore, we identified and quantified a suite of oxygenated aliphatic compounds that are more water-soluble and less hydrophobic than its presumed precursors, but only represent <1% of the oil residues' mass. Lastly, dissolution experiments showed that compounds in the OxHC fraction can leach into the water; however, the mass loss of this process is small. Overall, this study shows that the OxHC fraction is prevalent and persistent in weathered oil/sand aggregates, which can act as a long-term source of dissolved oil-derived compounds.

Antegrade transverse or sigmoid colonic enema through a percutaneous endoscopic gastrostomy tube is an option in the treatment of colorectal dysfunction.

BACKGROUND: Antegrade colonic enemas are used in patients with colorectal dysfunction resistant to conservative therapy. A number of different operative techniques are applied, but their effectiveness is by and large unknown. We therefore evaluated the long-term usefulness of the left-sided percutaneous endoscopic gastrostomy (PEG) tube method in adult patients. METHODS: Twenty-one patients with colorectal dysfunction underwent insertion of a PEG tube colostomy by laparotomy between 1997 and 2006. In 2014, we evaluated how many of the patients had the tube still in place, how the patients coped with the tube, and what the reasons for the removal were. RESULTS: The main indications were severe constipation or fecal incontinence mainly related to neurological diseases. In 2014, 5 out of 21 patients had the tube still in use (median follow-up 14 years, range 11-17 years) and 4 out of 5 deceased patients had had the tube in use until their death, unrelated to this treatment (median follow-up 7 years, range 0-8 years). Four out of the 5 living patients considered the benefit of the tube to be good or excellent. Tubes were removed in 11 (52%) patients for various reasons, local skin irritation being the most common. CONCLUSIONS: A left-sided PEG tube colostomy was removed in over half of the patients, but despite that, it still seems to be a viable long-term option in the treatment of individual patients with colorectal dysfunction, when conservative methods are ineffective.

Immunomodulatory properties of frondoside A, a major triterpene glycoside from the North Atlantic commercially harvested sea cucumber Cucumaria frondosa.

Frondoside A, a major triterpene glycoside from North Atlantic commercially harvested sea cucumber Cucumaria frondosa, possesses strong immunomodulatory properties in subtoxic doses. Frondoside A stimulates lysosomal activity of mouse macrophages in vivo at a maximal effective stimulatory dose of 0.2 microg per mouse and is maintained over 10 days. This glycoside also shows a 30% stimulation of lysosomal activity in mouse macrophages in vitro at concentrations of 0.1-0.38 microg/mL. Frondoside A enhances macrophage phagocytosis of the bacterium Staphylococcus aureus in vitro at a maximal effective concentration of 0.001 microg/mL. Frondoside A stimulates reactive oxygen species formation in macrophages in vitro at a maximal effective concentration of 0.001 microg/mL. Frondoside A stimulates an increase in the number of antibody plaque-forming cells (normally B-cells in spleen) in vivo with a maximal stimulatory effect at a concentration of 0.2 microg per mouse (stimulatory index, 1.86). Frondoside A has a weak effect upon immunoglobulin (Ig) M production after immunization with sheep erythrocytes in mice. Frondoside A does not stimulate Ig production in mice and does not significantly enhance the ovalbumin-stimulated IgM and IgG antibody levels in ovalbumin-immunized mice. Hence frondoside A is an immunostimulant of cell-based immunity including phagocytosis without a significant effect on amplification of humoral immune activity or adjuvant properties. Therefore, frondoside A may provide curative and/or preventive treatment options against diseases wherein a depleted immune status contributes to the pathological processes.

[Effects of keto-analogs of essential amino acids with or without associated protein restriction on the phospho-calcium metabolism of hemodialysed patients: a randomized prospective crossover study]. / Effets des céto-analogues des acides aminés essentiels avec ou sans restriction protidique associée sur le métabolisme phospho-calcique des patients hémodialysés: étude prospective randomisée en essai croisé.

The short term effects of a low (RP: 0.4 g/kg/day) and a normal (RN: 1 g/kg/day) protein diet supplemented by calcium salts of keto-analogs (CA) (200 mg/kg/day) were observed in a crossover study of phosphocalcic metabolism in 15 chronic dialysed patients during 15 days using a crossover device. CA were well tolerated but CA.RP was accompanied by a caloric diminution of 12% (p = 0.001) and albumin reduction of 5% (p = 0.004). Blood urea nitrogen was reduced by 32% (p = 0.001) with CA.RP. Blood creatinine was not modified by CA.RP or CA. RN. Blood phosphorus (P) and parathormone (PTH) levels were respectively reduced by 29% (p = 0.001) and 27% (p = 0.008) with CA.RP; and by 15% (p = 0.03) and 18% (p = 0.006) with CA.RN. Calcemia was raised about 9% (p = 0.002) by both sets of treatment. There was no significant difference between the two treatments. Thus CA can reduce P and PTH without need for a restricted protein diet which may be accompanied by complications on long term utilisation.