Forecasting Photo-Dissolution for Future Oil Spills at Sea: Effects of Oil Properties and Composition.

Photo-dissolution, the photochemical production of water-soluble species from oil, can transfer oil-derived dissolved organic carbon (DOC) from floating surface slicks to the underlying seawater. Photo-dissolution was likely a quantitatively relevant fate process for the Macondo crude oil spilled during the 2010 Deepwater Horizon spill, but the importance of photo-dissolution for other oils is poorly constrained. This study evaluated the photo-dissolution reactivities (apparent quantum yields) and modeled rates for oils with diverse physical properties and chemical compositions, including an ultra low sulfur fuel oil (ULSFO). Photo-dissolution from UV (310 nm) light was strongly positively correlated with the fraction of small, gas-oil range compounds (

Extending trait dispersion across trophic levels: Predator assemblages act as top-down filters on prey communities.

Studies of community assembly typically focus on the effects of abiotic environmental filters and stabilizing competition on functional trait dispersion within single trophic levels. Predation is a well-known driver of community diversity and composition, yet the role of functionally diverse predator communities in filtering prey community traits has received less attention. We examined functionally diverse communities of predators (fishes) and prey (epifaunal crustaceans) in eelgrass (Zostera marina) beds in two northern California estuaries to evaluate the filtering effects of predator traits on community assembly and how filters acting on predators influence their ability to mediate prey community assembly. Fish traits related to bottom orientation were correlated with more clustered epifauna communities, and epifauna were generally overdispersed while fishes were clustered, suggesting prey may be pushed to disparate areas of trait space to avoid capture by benthic sit-and-wait predators. We also found correlations between the trait dispersions of predator and prey communities that strengthened after accounting for the effects of habitat filters on predator dispersion, suggesting that habitat filtering effects on predator species pools may hinder their ability to affect prey community assembly. Our results present compelling observational evidence that specific predator traits have measurable impacts on the community assembly of prey, inviting experimental tests of predator trait means on community assembly and explicit comparisons of how the relative effects of habitat filters and intraguild competition on predators impact their ability to affect prey community assembly. Integrating our understanding of traits at multiple trophic levels can help us better predict the impacts of community composition on food web dynamics as regional species pools shift with climate change and anthropogenic introductions.

Minimizing the Environmental Impacts of Plastic Pollution through Ecodesign of Products with Low Environmental Persistence.

While plastic pollution threatens ecosystems and human health, the use of plastic products continues to increase. Limiting its harm requires design strategies for plastic products informed by the threats that plastics pose to the environment. Thus, we developed a sustainability metric for the ecodesign of plastic products with low environmental persistence and uncompromised performance. To do this, we integrated the environmental degradation rate of plastic into established material selection strategies, deriving material indices for environmental persistence. By comparing indices for the environmental impact of on-the-market plastics and proposed alternatives, we show that accounting for the environmental persistence of plastics in design could translate to societal benefits of hundreds of millions of dollars for a single consumer product. Our analysis identifies the materials and their properties that deserve development, adoption, and investment to create functional and less environmentally impactful plastic products.

Distinct microbial communities degrade cellulose diacetate bioplastics in the coastal ocean.

IMPORTANCE: Cellulose diacetate (CDA) is a promising alternative to conventional plastics due to its versatility in manufacturing and low environmental persistence. Previously, our group demonstrated that CDA is susceptible to biodegradation in the ocean on timescales of months. In this study, we report the composition of microorganisms driving CDA degradation in the coastal ocean. We found that the coastal ocean harbors distinct bacterial taxa implicated in CDA degradation and these taxa have not been previously identified in prior CDA degradation studies, indicating an unexplored diversity of CDA-degrading bacteria in the ocean. Moreover, the shape of the plastic article (e.g., a fabric, film, or foam) and plasticizer in the plastic matrix selected for different microbial communities. Our findings pave the way for future studies to identify the specific species and enzymes that drive CDA degradation in the marine environment, ultimately yielding a more predictive understanding of CDA biodegradation across space and time.

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.

Formulation Controls the Potential Neuromuscular Toxicity of Polyethylene Photoproducts in Developing Zebrafish.

Sunlight transforms plastic into water-soluble products, the potential toxicity of which remains unresolved, particularly for vertebrate animals. We evaluated acute toxicity and gene expression in developing zebrafish larvae after 5 days of exposure to photoproduced (P) and dark (D) leachates from additive-free polyethylene (PE) film and consumer-grade, additive-containing, conventional, and recycled PE bags. Using a "worst-case" scenario, with plastic concentrations exceeding those found in natural waters, we observed no acute toxicity. However, at the molecular level, RNA sequencing revealed differences in the number of differentially expressed genes (DEGs) for each leachate treatment: thousands of genes (5442 P, 577 D) for the additive-free film, tens of genes for the additive-containing conventional bag (14 P, 7 D), and none for the additive-containing recycled bag. Gene ontology enrichment analyses suggested that the additive-free PE leachates disrupted neuromuscular processes via biophysical signaling; this was most pronounced for the photoproduced leachates. We suggest that the fewer DEGs elicited by the leachates from conventional PE bags (and none from recycled bags) could be due to differences in photoproduced leachate composition caused by titanium dioxide-catalyzed reactions not present in the additive-free PE. This work demonstrates that the potential toxicity of plastic photoproducts can be product formulation-specific.

Diffusion-Ordered Spectroscopy for Rapid and Facile Determination of Consumer Plastic Molecular Weight.

Molecular weight (MW) is a key control of plastic polymer properties and their fate in the environment. However, the primary tool used to determine plastic MW, gel permeation chromatography (GPC), has major limitations, such as low precision and accuracy, requirements for dedicated instrumentation, production of high volumes of hazardous waste, and large sample sizes. In this study, we describe, validate, and apply a diffusion-ordered spectroscopy (DOSY) method for polymer MW determinations, with a focus on applications for consumer plastics. Several experimental conditions were systematically optimized and tested to validate the DOSY method, including the selection of pulse sequences, the effect of sample concentration, cross-validation with multiple sets of external standards, and long-term instrumental stability. Validation was performed for a wide range of polymers, solvents, and temperatures, highlighting its potential for broad applicability. A preliminary screening of polystyrene and polyethylene terephthalate consumer products revealed widely varying MWs (up to two-fold) for products made of the same polymer type. A preliminary experiment was also conducted to track the decrease in polystyrene MW via photochemical chain scission reactions, finding a 20% reduction in MW after less than 1 week of irradiation. Collectively, our results demonstrate the potential for DOSY to provide high-throughput, accurate, and precise measures of polymer MW, as well as the evolution of polymer MW during environmental weathering processes, such as photochemical degradation. We conclude with a discussion of (i) the many advantages of DOSY compared to GPC, (ii) future developments to enhance the depth of information obtained from DOSY, and (iii) approaches to broaden the accessibility of this promising analytical method to the research community.

Adenosine Receptors Expression in Human Retina and Choroid with Age-related Macular Degeneration.

Purpose: Adenosine signaling modulates ocular inflammatory processes, and its antagonism mitigates neovascularization in both newborns and preclinical models of ocular neovascularization including age-related macular degeneration (AMD). The adenosine receptor expression patterns have not been well characterized in the human retina and choroid. Methods: Here we examined the expression of adenosine receptor subtypes within the retina and choroid of human donor eyes with and without AMD. Antibodies specifically targeting adenosine receptor subtypes A1, A2A, A2B, and A3 were used to assess their expression patterns. Quantitative real-time PCR analysis was used to confirm gene expression of these receptors within the normal human retina and choroid. Results: We found that all four receptor subtypes were expressed in several layers of the retina, and within the retinal pigment epithelium and choroid. The expression of A1 receptors was more prominent in the inner and outer plexiform layers, where microglia normally reside, and supported by RNA expression in the retina. A2A and A2B showed similar expression patterns with prominent expression in the vasculature and retinal pigment epithelium. No dramatic differences in expression of these receptors were observed in eyes from patients with dry or wet AMD compared to control, with the exception A3 receptors. Eyes with dry AMD lost expression of A3 in the photoreceptor outer segments compared with eyes from control or wet AMD. Conclusion: The ocular presence of adenosine receptors is consistent with their proposed role in modulation of inflammation in both the retina and choroid, and their potential targeting for AMD treatment.

[Chronic posttraumatic shoulder instability]. / Chronische posttraumatische Schulterinstabilität.

Chronic posttraumatic shoulder instability is characterized by trauma-associated, recurrent dislocations. Surgical treatment is indicated in most cases but it remains controversial how risk factors should be weighted to decide between arthroscopic Bankart repair (ABR), Latarjet or alternative procedures. Known risk factors for recurrence are patient age, hyperlaxity, sports profile and bone loss. Surgical techniques are discussed in detail. The ABR leads to high patient satisfaction and return to sports; however, in association with risk factors, recurrent dislocations are seen even several years later. Latarjet or bone block procedures lead to high patient satisfaction, sustainable stability as a revision procedure, but can also be primarily indicated for chronic instability depending on risk factors. Early complications are more frequent but of a minor nature in most cases. All techniques are known for a serious learning curve. If performed well, they do not seem to increase the risk of arthritis, which is most affected by the number of lifetime dislocations and higher energy trauma.

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.

Synergy between Sunlight, Titanium Dioxide, and Microbes Enhances Cellulose Diacetate Degradation in the Ocean.

Sunlight chemically transforms marine plastics into a suite of products, with formulation─the specific mixture of polymers and additives─driving rates and products. However, the effect of light-driven transformations on subsequent microbial lability is poorly understood. Here, we examined the interplay between photochemical and biological degradation of fabrics made from cellulose diacetate (CDA), a biobased polymer used commonly in consumer products. We also examined the influence of ∼1% titanium dioxide (TiO2), a common pigment and photocatalyst. We sequentially exposed CDA to simulated sunlight and native marine microbes to understand how photodegradation influences metabolic rates and pathways. Nuclear magnetic resonance spectroscopy revealed that sunlight initiated chain scission reactions, reducing CDA's average molecular weight. Natural abundance carbon isotope measurements demonstrated that chain scission ultimately yields CO2, a newly identified abiotic loss term of CDA in the environment. Measurements of fabric mass loss and enzymatic activities in seawater implied that photodegradation enhanced biodegradation by performing steps typically facilitated by cellulase. TiO2 accelerated CDA photodegradation, expediting biodegradation. Collectively, these findings (i) underline the importance of formulation in plastic's environmental fate and (ii) suggest that overlooking synergy between photochemical and biological degradation may lead to overestimates of marine plastic persistence.

Assessing pyrethroid resistance status in the Culex pipiens complex (Diptera: Culicidae) from the northwest suburbs of Chicago, Illinois using Cox regression of bottle bioassays and other detection tools.

Culex pipiens complex is an important vector of epizootic and zoonotic pathogens, including West Nile virus. Chicago, Illinois and its suburbs have suffered high incidence of human West Nile virus infections in the past. This makes abatement programs in and around the Chicago area an essential service. The control of Cx. pipiens is often complicated by rapidly evolving resistance to pyrethroids, which are the most widely used chemical class in US mosquito abatement programs. The present study assessed Sumithrin® resistance in Cx. pipiens collected from five locations around Cook County, Illinois, neighboring the city limits of Chicago. According to CDC guidelines, samples from all five locations demonstrated some resistance to Sumithrin®. When assessed with Anvil®, a formulated product made of Sumithrin® synergized with piperonyl butoxide, susceptibility was rescued in mosquitoes from three out of the five locations, suggesting involvement of mixed-function oxidases and/or carboxylesterases in Sumithrin® resistance at these locations. Not all locations had susceptibility rescued by Anvil®, but these locations had relatively low knockdown resistance allele frequencies, suggesting that mechanisms other than knockdown resistance may be involved. Enzyme activities did not reveal any marked trends that could be related back to mortality in the bottle bioassays, which highlights the need for multiple types of assays to infer enzymatic involvement in resistance. Future directions in pyrethroid resistance management in Chicago area Cx. pipiens are discussed.

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.

The biogeography of community assembly: latitude and predation drive variation in community trait distribution in a guild of epifaunal crustaceans.

While considerable evidence exists of biogeographic patterns in the intensity of species interactions, the influence of these patterns on variation in community structure is less clear. Studying how the distributions of traits in communities vary along global gradients can inform how variation in interactions and other factors contribute to the process of community assembly. Using a model selection approach on measures of trait dispersion in crustaceans associated with eelgrass (Zostera marina) spanning 30° of latitude in two oceans, we found that dispersion strongly increased with increasing predation and decreasing latitude. Ocean and epiphyte load appeared as secondary predictors; Pacific communities were more overdispersed while Atlantic communities were more clustered, and increasing epiphytes were associated with increased clustering. By examining how species interactions and environmental filters influence community structure across biogeographic regions, we demonstrate how both latitudinal variation in species interactions and historical contingency shape these responses. Community trait distributions have implications for ecosystem stability and functioning, and integrating large-scale observations of environmental filters, species interactions and traits can help us predict how communities may respond to environmental change.

Sunlight-driven dissolution is a major fate of oil at sea.

Oxygenation reactions initiated by sunlight can transform insoluble components of crude oil at sea into water-soluble products, a process called photo-dissolution. First reported a half century ago, photo-dissolution has never been included in spill models because key parameters required for rate modeling were unknown, including the wavelength and photon dose dependence. Here, we experimentally quantified photo-dissolution as a function of wavelength and photon dose, making possible a sensitivity analysis of environmental variables in hypothetical spill scenarios and a mass balance assessment for the 2010 Deepwater Horizon (DwH) spill. The sensitivity analysis revealed that rates were most sensitive to oil slick thickness, season/latitude, and wavelength and less sensitive to photon dose. We estimate that 3 to 17% (best estimate 8%) of DwH surface oil was subject to photo-dissolution, comparable in magnitude to other widely recognized fate processes. Our findings invite a critical reevaluation of surface oil budgets for both DwH and future spills at sea.

Revised microbial and photochemical triple-oxygen isotope effects improve marine gross oxygen production estimates.

The biogeochemical fluxes that cycle oxygen (O2) play a critical role in regulating Earth's climate and habitability. Triple-oxygen isotope (TOI) compositions of marine dissolved O2 are considered a robust tool for tracing oxygen cycling and quantifying gross photosynthetic O2 production. This method assumes that photosynthesis, microbial respiration, and gas exchange with the atmosphere are the primary influences on dissolved O2 content, and that they have predictable, fixed isotope effects. Despite its widespread use, there are major elements of this approach that remain uncharacterized, including the TOI dynamics of respiration by marine heterotrophic bacteria and abiotic O2 sinks such as the photochemical oxidation of dissolved organic carbon (DOC). Here, we report the TOI fractionation for O2 utilization by two model marine heterotrophs and by abiotic photo-oxidation of representative terrestrial and coastal marine DOC. We demonstrate that TOI slopes associated with these processes span a significant range of the mass-dependent domain (λ = 0.499 to 0.521). A sensitivity analysis reveals that even under moderate productivity and photo-oxidation scenarios, true gross oxygen production may deviate from previous estimates by more than 20% in either direction. By considering a broader suite of oxygen cycle reactions, our findings challenge current gross oxygen production estimates and highlight several paths forward to better understanding the marine oxygen and carbon cycles.

Divergent Forms of Pyroplastic: Lessons Learned from the M/V X-Press Pearl Ship Fire.

In late May 2021, the M/V X-Press Pearl container ship caught fire while anchored 18 km off the coast of Colombo, Sri Lanka and spilled upward of 70 billion pieces of plastic or "nurdles" (∼1680 tons), littering the country's coastline. Exposure to combustion, heat, chemicals, and petroleum products led to an apparent continuum of changes from no obvious effects to pieces consistent with previous reports of melted and burned plastic (pyroplastic) found on beaches. At the middle of this continuum, nurdles were discolored but appeared to retain their prefire morphology, resembling nurdles that had been weathered in the environment. We performed a detailed investigation of the physical and surface properties of discolored nurdles collected on a beach 5 days after the ship caught fire and within 24 h of their arrival onshore. The color was the most striking trait of the plastic: white for nurdles with minimal alteration from the accident, orange for nurdles containing antioxidant degradation products formed by exposure to heat, and gray for partially combusted nurdles. Our color analyses indicate that this fraction of the plastic released from the ship was not a continuum but instead diverged into distinct groups. Fire left the gray nurdles scorched, with entrained particles and pools of melted plastic, and covered in soot, representing partial pyroplastics, a new subtype of pyroplastic. Cross sections showed that the heat- and fire-induced changes were superficial, leaving the surfaces more hydrophilic but the interior relatively untouched. These results provide timely and actionable information to responders to reevaluate cleanup end points, monitor the recurrence of these spilled nurdles, gauge short- and long-term effects of the spilled nurdles to the local ecosystem, and manage the recovery of the spill. These findings underscore partially combusted plastic (pyroplastic) as a type of plastic pollution that has yet to be fully explored despite the frequency at which plastic is burned globally.