Divergent forms of pyroplastic: lessons learned from the M/V X-Press Pearl ship fire

© The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in James, B., de Vos, A., Aluwihare, L., Youngs, S., Ward, C., Nelson, R., Michel, A., Hahn, M., & Reddy, C. Divergent forms of pyroplastic: lessons learned from the M/V X-Press Pearl ship fire. ACS Environmental Au, 2(5), (2022): 467–479, https://doi.org/10.1021/acsenvironau.2c00020.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.This work was supported by the Postdoctoral Scholar Program at the Woods Hole Oceanographic Institution (WHOI), with funding provided by the Weston Howland Jr. Postdoctoral Scholarship. Additional support was provided by the WHOI Marine Microplastics Catalyst Program, the WHOI Marine Microplastics Innovation Accelerator Program, the WHOI Investment in Science Fund, the March Marine Initiative (a program of March Limited, Bermuda), The Seaver Institute, Gerstner Philanthropies, the Wallace Research Foundation, the Richard Saltonstall Charitable Foundation, the Harrison Foundation, Hollis and Ermine Lovell Charitable Foundation, and the Richard Grand Foundation. AdV was supported by funding from the Schmidt Foundation

An Expanded Evaluation of Protein Function Prediction Methods Shows an Improvement In Accuracy

Background: A major bottleneck in our understanding of the molecular underpinnings of life is the assignment of function to proteins. While molecular experiments provide the most reliable annotation of proteins, their relatively low throughput and restricted purview have led to an increasing role for computational function prediction. However, assessing methods for protein function prediction and tracking progress in the field remain challenging. Results: We conducted the second critical assessment of functional annotation (CAFA), a timed challenge to assess computational methods that automatically assign protein function. We evaluated 126 methods from 56 research groups for their ability to predict biological functions using Gene Ontology and gene-disease associations using Human Phenotype Ontology on a set of 3681 proteins from 18 species. CAFA2 featured expanded analysis compared with CAFA1, with regards to data set size, variety, and assessment metrics. To review progress in the field, the analysis compared the best methods from CAFA1 to those of CAFA2. Conclusions: The top-performing methods in CAFA2 outperformed those from CAFA1. This increased accuracy can be attributed to a combination of the growing number of experimental annotations and improved methods for function prediction. The assessment also revealed that the definition of top-performing algorithms is ontology specific, that different performance metrics can be used to probe the nature of accurate predictions, and the relative diversity of predictions in the biological process and human phenotype ontologies. While there was methodological improvement between CAFA1 and CAFA2, the interpretation of results and usefulness of individual methods remain context-dependent

An expanded evaluation of protein function prediction methods shows an improvement in accuracy

Background: A major bottleneck in our understanding of the molecular underpinnings of life is the assignment of function to proteins. While molecular experiments provide the most reliable annotation of proteins, their relatively low throughput and restricted purview have led to an increasing role for computational function prediction. However, assessing methods for protein function prediction and tracking progress in the field remain challenging. Results: We conducted the second critical assessment of functional annotation (CAFA), a timed challenge to assess computational methods that automatically assign protein function. We evaluated 126 methods from 56 research groups for their ability to predict biological functions using Gene Ontology and gene-disease associations using Human Phenotype Ontology on a set of 3681 proteins from 18 species. CAFA2 featured expanded analysis compared with CAFA1, with regards to data set size, variety, and assessment metrics. To review progress in the field, the analysis compared the best methods from CAFA1 to those of CAFA2. Conclusions: The top-performing methods in CAFA2 outperformed those from CAFA1. This increased accuracy can be attributed to a combination of the growing number of experimental annotations and improved methods for function prediction. The assessment also revealed that the definition of top-performing algorithms is ontology specific, that different performance metrics can be used to probe the nature of accurate predictions, and the relative diversity of predictions in the biological process and human phenotype ontologies. While there was methodological improvement between CAFA1 and CAFA2, the interpretation of results and usefulness of individual methods remain context-dependent. Keywords: Protein function prediction, Disease gene prioritizationpublishedVersio

Discovering hydrothermalism from Afar: In Situ methane instrumentation and change-point detection for decision-making

Seafloor hydrothermalism plays a critical role in fundamental interactions between geochemical and biological processes in the deep ocean. A significant number of hydrothermal vents are hypothesized to exist, but many of these remain undiscovered due in part to the difficulty of detecting hydrothermalism using standard sensors on rosettes towed in the water column or robotic platforms performing surveys. Here, we use in situ methane sensors to complement standard sensing technology for hydrothermalism discovery and compare sensors on a towed rosette and an autonomous underwater vehicle (AUV) during a 17 km long transect in the Northern Guaymas Basin in the Gulf of California. This transect spatially intersected with a known hydrothermally active venting site. These data show that methane signalled possible hydrothermal-activity 1.5–3 km laterally (100–150 m vertically) from a known vent. Methane as a signal for hydrothermalism performed similarly to standard turbidity sensors (plume detection 2.2–3.3 km from reference source), and more sensitively and clearly than temperature, salinity, and oxygen instruments which readily respond to physical mixing in background seawater. We additionally introduce change-point detection algorithms—streaming cross-correlation and regime identification—as a means of real-time hydrothermalism discovery and discuss related data supervision technologies that could be used in planning, executing, and monitoring explorative surveys for hydrothermalism.</jats:p

Chain-length dependent organisation in mixtures of hydrogenous and fluorous ionic liquids

As part of an ongoing study of the structure and properties of mixtures of ionic liquids in which one component has a hydrocarbon chain and the other a semiperfluorocarbon chain, we now report a study of the mixtures [C8MIM]1-x[C10MIM-F17]x[Tf2N], [C10MIM]1-x[C8MIM-F13]x[Tf2N] and [C10MIM]1-x[C10MIM-F17]x[Tf2N], where [C8MIM][Tf2N] is 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide, [C10MIM][Tf2N] is 1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C8MIM-F13][Tf2N] is 1-(1H,1H,2H,2H-perfluorooctyl)-3-methylimidizolium bis(trifluoromethylsulfonyl)imide and [C10MIM-F17][Tf2N] is 1-(1H,1H,2H,2H-perfluorodecyl)-3-methylimidizolium bis(trifluoromethylsulfonyl)imide. The mixtures were investigated using small-angle X-ray (SAXS) and neutron (SANS) scattering complemented by molecular dynamics simulations (with viscosity and surface tension measurements also possible for the mixtures [C10MIM]1-x[C8MIM-F13]x[Tf2N]). Unlike previous studies of [C8MIM]1-x[C8MIM-F13]x[Tf2N], where no strong evidence of alkyl/fluoroalkyl chain segregation or triphilic behaviour was seen (Elstone et al., J. Phys. Chem. B, 2023, 127, 7394-7407), these new mixtures showed the formation of small aggregates of varying sizes of each component, even though all were co-miscible across the full range of compositions. Thus, while a clear polar non-polar peak (PNPP) was observed at large or small values of x, at intermediate compositions the small-angle neutron scattering at low q was dominated by scattering from these small aggregates, with little or no evidence of the PNPP at some compositions. The origins of this behaviour are discussed in terms of inter-chain interactions

The synthesis of deuteriated tri-tert-butyl phosphine

The synthesis of deuteriated tri‐tert‐butyl phosphine is reported. This synthesis is an adaptation of the known procedure for tri‐tert‐butyl phosphine via a Grignard intermediate

Discovering hydrothermalism from afar: in situ methane instrumentation and change-point detection for decision-making

Seafloor hydrothermalism plays a critical role in fundamental interactions between geochemical and biological processes in the deep ocean. A significant number of hydrothermal vents are hypothesized to exist, but many of these remain undiscovered due in part to the difficulty of detecting hydrothermalism using standard sensors on rosettes towed in the water column or robotic platforms performing surveys. Here, we use in situ methane sensors to complement standard sensing technology for hydrothermalism discovery and compare sensing equipment on a towed rosette and autonomous underwater vehicle (AUV) during a 17 km long transect in the Northern Guaymas Basin. This transect spatially intersected with a known hydrothermally active venting site. These data show that methane signaled possible hydrothermal activity 1.5-3 km laterally (100-150m vertically) from a known vent. Methane as a signal for hydrothermalism performed similarly to standard turbidity sensors (plume detection 2.2-3.3 km from reference source), and more sensitively and clearly than temperature, salinity, and oxygen instruments which readily respond to physical mixing in background seawater. We additionally introduce change-point detection algorithms---streaming cross-correlation and regime identification---as a means of real-time hydrothermalism discovery and discuss related data monitoring technologies that could be used in planning, executing, and monitoring explorative surveys for hydrothermalism.NSF OCE OTIC: #1842053 Woods Hole Oceanographic Institution: Innovative Technology Award NOAA Ocean Exploration: #NA18OAR0110354 Schmidt Marine Technology Partners: #G-21-62431 NASA: #NNX17AB31G NSF OCE: #0838107 Gordon and Betty Moore Foundation: #9208 NDSEG: Graduate Fellowship MIT Martin Family Society of Fellows: Graduate Fellowship Microsoft: Graduate Research Fellowship DOE/National Nuclear Security Administration: #DE-NA000392 MIT EAPS: Houghton Fun

Understanding the Liquid Structure in Mixtures of Ionic Liquids with Semiperfluoroalkyl or Alkyl Chains

By mixing ionic liquids (ILs), it is possible to fine-tune their bulk and interfacial structure. This alters their physical properties and solvation behavior and is a simple way to prepare a collection of ILs whose properties can be tuned to optimize a specific application. In this study, mixtures of perfluorinated and alkylated ILs have been prepared, and links between composition, properties, and nanostructure have been investigated. These different classes of ILs vary substantially in the flexibility and polarizability of their chains. Thus, a range of useful structural and physical property variations are accessible through mixing that will expand the library of IL mixtures available in an area that to this point has received relatively little attention. In the experiments presented herein, the physical properties and bulk structure of mixtures of 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide [C8MIM][Tf2N] and 1-(1H,1H,2H,2H-perfluorooctyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C8MIM-F13][Tf2N] have been prepared. The bulk liquid structure was investigated using a combination of small-angle X-ray and neutron scattering (SAXS and SANS, respectively) experiments in combination with atomistic molecular dynamics simulations and the measurement of density and viscosity. We observed that the addition of [C8MIM-F13][Tf2N] to [C8MIM][Tf2N] causes changes in the nanostructure of the IL mixtures that are dependent on composition so that variation in the characteristic short-range correlations is observed as a function of composition. Thus, while the length scales associated with the apolar regions (polar non-polar peak─PNPP) increase with the proportion of [C8MIM-F13][Tf2N] in the mixtures, perhaps surprisingly given the greater volume of the fluorocarbon chains, the length scale of the charge-ordering peak decreases. Interestingly, consideration of the contact peak shows that its origins are both in the direct anion···cation contact length scale and the nature (and hence volume) of the chains appended to the imidazolium cation