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North Atlantic Deep Water (NADW), the return flow component of the Atlantic Meridional Overturning Circulation (AMOC), is a major inter-hemispheric ocean water mass with strong climate effects but the evolution of its source components on million-year timescales is poorly known. Today, two major NADW components that flow southward over volcanic ridges to the east and west of Iceland are associated with distinct contourite drift systems that are forming off the coast of Greenland and on the eastern flank of the Reykjanes (mid-Atlantic) Ridge. Here we provide direct records of the early history of this drift sedimentation based on cores collected during International Ocean Discovery Programme (IODP) Expeditions 395C and 395. We find rapid acceleration of drift deposition linked to the eastern component of NADW, known as Iceland–Scotland Overflow Water at 3.6 million years ago (Ma). In contrast, the Denmark Strait Overflow Water feeding the western Eirik Drift has been persistent since the Late Miocene. These observations constrain the long-term evolution of the two NADW components, revealing their contrasting independent histories and allowing their links with climatic events such as Northern Hemisphere cooling at 3.6 Ma, to be assessed.more » « lessFree, publicly-accessible full text available May 5, 2026
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Based on Coulomb's Law alone, electrostatic repulsion between two anions is expected to prevent their dimerization. Contrary to that idea, this Tutorial Review will present evidence showing that anion–anion dimers of protic hydroxyanions can form readily, and describe conditions that facilitate their formation. From X-ray crystal structures, we learn that hydroxyanions dimerize and oligomerize by overcoming long-range electrostatic opposition. Common examples are hydroxyanions of phosphate, sulfate, and carbonate, often in partnership with charged and neutral receptors. Short-range hydrogen bonds between anionic donors and acceptors are defined as anti-electrostatic hydrogen bonds (AEHBs) with insight from theoretical studies. While anion dimers are difficult to identify unequivocally in solution, these solution dimers have recently been definitively identified. The development of the supramolecular chemistry of anion–anion dimers has led to applications in hierarchical assemblies, such as supramolecular polymers and hydrogen bonded organic frameworks.more » « less
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Natural and anthropogenic activities result in the production of polycyclic aromatic hydrocarbons (PAHs), persistent pollutants that negatively impact the environment and human health. Rapid and reliable methods for the detection and discrimination of these compounds remains a technological challenge owing to their relatively featureless properties, structural similarities, and existence as complex mixtures. Here, we demonstrate that the inner filter effect (IFE), in combination with conjugated polymer (CP) array-based sensing, offers a straightforward approach for the quantitative and qualitative profiling of PAHs. The sensor array was constructed from six fluorescent fluorene-based copolymers, which incorporate side chains with peripheral 2-phenylbenzimidazole substituents that provide spectral overlap with PAHs and give rise to a pronounced IFE. Subtle structural differences in copolymer structure result in distinct spectral signatures, which provide a unique “chemical fingerprint” for each PAH. The discriminatory power of the array was evaluated using linear discriminant analysis (LDA) and principal component analysis (PCA) in order to discriminate between 16 PAH compounds identified as priority pollutants by the US Environmental Protection Agency (EPA). This array is the first multivariate system reliant on the modulation of the spectral signatures of CPs through the IFE for the detection and discrimination of closely related polynuclear aromatic species.more » « less
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