Motta Laura C.

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Last Name
Motta
First Name
Laura C.
ORCID
0000-0002-4098-904X

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Now showing 1 - 2 of 2
  • Article
    Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding
    (Nature Research, 2023-07-18) Motta, Laura C. ; Autschbach, Jochen
    Actinide-ligand bonds with high multiplicities remain poorly understood. Decades ago, an effect known as 6p pushing from below (PFB) was proposed to enhance actinide covalency. A related effect—also poorly understood—is inverse trans influence (ITI). The present computational study of actinide-ligand covalent interactions with high bond multiplicities quantifies the energetic contributions from PFB and identifies a hitherto overlooked fourth bonding interaction for 2nd-row ligands in the studied organometallic systems. The latter are best described by a terminal O/N ligand exhibiting quadruple bonding interactions with the actinide. The 4th interaction may be characterized as a multi-center or charge-shift bond involving the trans ligand. It is shown in this work that the 4th bonding interaction is a manifestation of ITI, assisted by PFB, and provides a long-sought missing piece in the understanding of actinide chemistry.
  • Article
    Particulate mercury export in the Central Pacific Ocean using 234Th 238U disequilibria
    (Elsevier, 2024-07-24) Umhau, Blaire P. ; Motta, Laura C. ; Blum, Joel D. ; Close, Hilary G. ; Drazen, Jeffrey C. ; Popp, Brian N. ; Benitez-Nelson, Claudia R.
    Mercury (Hg) is a potent neurotoxin that enters the food web and may contaminate commercial, recreational, subsistence, and ceremonial fish stocks. Understanding the pathways by which this contamination occurs in marine systems is thus an essential component of minimizing consumer health risk. Our knowledge of the biogeochemical cycling of mercury, however, is relatively limited. Temporal changes in sinking particulate mercury (PHg) fluxes throughout the upper 400 m were examined at Station ALOHA (22°N, 158°W) in the North Pacific Subtropical Gyre (NPSG) and spatially along a north-south transect to the Equator (17.5°N to 5°N x 155°W) using a combination of in situ pumps and Uranium-238/Thorium-234 disequilibria as a tracer of particle export. Our results indicate that Station ALOHA is characterized by seasonally variable export fluxes of PHg, with highest fluxes occurring in May (175 m, 346 pmol m−2 day−1), with the advent of summer zooplankton growth, and in September (400 m, 356 pmol m−2 day−1), coinciding with a diazotroph mediated summer export pulse. PHg fluxes in May and September were higher than those previously measured in the equatorial Pacific at 150 m and continued to be high (> 100 pmol Hg m−2 d−1) down to 400 m, thereby providing a significant source of Hg to the mesopelagic food web. In contrast to Station ALOHA, at 8 and 5°N, PHg fluxes attenuated rapidly with depth, and fluxes were generally lower, with a maximum flux of 86 pmol m−2 d−1 (5°N). Depth profiles at 8 and 5°N were significantly different from one another, with PHg fluxes higher throughout the water column at 5°N and characterized by a subsurface peak in Hg flux 3 times higher than at 8°N (86 vs. 29 pmol Hg m−2 d−1). Monomethylmercury (MeHg) fluxes (max = 1.09 ± 0.57 pmol m−2 d−1) and concentrations (max = 0.14 fmol L−1) comprised only a small percentage of the total PHg pool. These results suggest that PHg cycling significantly differed between the NPSG and near the equator at least during an El Niño year. At Station ALOHA, microbial reworking of small particles below the deep chlorophyll maximum coupled with changes in zooplankton grazing drive seasonal export variability. In contrast near the equator, low fluxes associated with low biological productivity result in significantly lower PHg transport to depth during an El Niño year.