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We applied reaction microscopy to elucidate fast non-adiabatic dissociation dynamics of deuterated water molecules after direct photo-double ionization at 61 eV with synchrotron radiation. For the very rare D+ + O+ + D breakup channel, the particle momenta, angular, and energy distributions of electrons and ions, measured in coincidence, reveal distinct electronic dication states and their dissociation pathways via spin–orbit coupling and charge transfer at crossings and seams on the potential energy surfaces. Notably, we could distinguish between direct and fast sequential dissociation scenarios. For the latter case, our measurements reveal the geometry and orientation of the deuterated water molecule with respect to the polarization vector that leads to this rare 3-body molecular breakup channel. Aided by multi-reference configuration-interaction calculations, the dissociation dynamics could be traced on the relevant potential energy surfaces and particularly their crossings and seams. This approach also unraveled the ultrafast time scales governing these processes. 

Abstract The North Pacific has played an important role in ongoing discussions on the origin of the global correlation between oceanic dissolved Zn and Si, while data in the North Pacific have remained sparse. Here, we present dissolved Zn and δ⁶⁶Zn data from the US GEOTRACES GP15 meridional transect along 152°W from Alaska to the South Pacific. In the south (<20°N) Zn and Si exhibit a tight linear correlation reflecting strong Southern Ocean influence, while in the north (>20°N) an excess of Zn relative to Si in upper and intermediate waters is due to regeneration of Zn together with PO₄. Using a mechanistic model, we show that reversible scavenging is required as an additional process transferring Zn from the upper to the deep ocean, explaining the deep Zn maximum below the PO₄maximum. This mechanism applied for reversible scavenging also provides an explanation for the observed isotope distribution: (a) fractionation during ligand binding and subsequent removal of residual heavy Zn in the upper ocean, drives the upper ocean toward lower δ⁶⁶Zn, while (b) release of heavy Zn then coincides with the PO₄maximum where carrier particles regenerate, causing a mid‐depth δ⁶⁶Zn maximum. In the upper ocean, seasonal physical stratification is an additional important process influencing shallow δ⁶⁶Zn signals. At the global scale, this mechanism invoking fractionation during ligand binding coupled with reversible scavenging offers a global explanation for isotopically light Zn at shallow depths and corresponding elevated mid‐depth δ⁶⁶Zn signals, seen dominantly in ocean regions away from strong Southern Ocean control. 

Abstract The abundance and size distribution of marine particles control a range of biogeochemical and ecological processes in the ocean, including carbon sequestration. These quantities are the result of complex physical‐biological interactions that are difficult to observe, and their spatial and temporal patterns remain uncertain. Here, we present a novel analysis of particle size distributions (PSDs) from a global compilation of in situ Underwater Vision Profiler 5 (UVP5) optical measurements. Using a machine learning algorithm, we extrapolate sparse UVP5 observations to the global ocean from well‐sampled oceanographic variables. We reconstruct global maps of PSD parameters (biovolume [BV] and slope) for particles at the base of the euphotic zone. These reconstructions reveal consistent global patterns, with high chlorophyll regions generally characterized by high particle BV and flatter PSD slope, that is, a high relative abundance of large versus small particles. The resulting negative correlations between particle BV and slope further suggests synergistic effects on size‐dependent processes such as sinking particle fluxes. Our approach and estimates provide a baseline for an improved understanding of particle cycles in the ocean, and pave the way to global, three‐dimensional reconstructions of PSD and sinking particle fluxes from the growing body of UVP5 observations. 

Abstract The coastal ocean contributes to regulating atmospheric greenhouse gas concentrations by taking up carbon dioxide (CO₂) and releasing nitrous oxide (N₂O) and methane (CH₄). In this second phase of the Regional Carbon Cycle Assessment and Processes (RECCAP2), we quantify global coastal ocean fluxes of CO₂, N₂O and CH₄using an ensemble of global gap‐filled observation‐based products and ocean biogeochemical models. The global coastal ocean is a net sink of CO₂in both observational products and models, but the magnitude of the median net global coastal uptake is ∼60% larger in models (−0.72 vs. −0.44 PgC year⁻¹, 1998–2018, coastal ocean extending to 300 km offshore or 1,000 m isobath with area of 77 million km²). We attribute most of this model‐product difference to the seasonality in sea surface CO₂partial pressure at mid‐ and high‐latitudes, where models simulate stronger winter CO₂uptake. The coastal ocean CO₂sink has increased in the past decades but the available time‐resolving observation‐based products and models show large discrepancies in the magnitude of this increase. The global coastal ocean is a major source of N₂O (+0.70 PgCO₂‐e year⁻¹in observational product and +0.54 PgCO₂‐e year⁻¹in model median) and CH₄(+0.21 PgCO₂‐e year⁻¹in observational product), which offsets a substantial proportion of the coastal CO₂uptake in the net radiative balance (30%–60% in CO₂‐equivalents), highlighting the importance of considering the three greenhouse gases when examining the influence of the coastal ocean on climate.