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Cadmium (Cd) has a nutrient-like distribution in the ocean, similar to the macronutrient phosphate. Significant isotope fractionation induced by the biological cycling of Cd makes it a potential tracer for nutrients and productivity. However, the Cd flux and Cd isotope composition of marine sediments may also be influenced by local redox conditions and partial remineralization of organically hosted Cd. These confounding factors are under-constrained and render it challenging to use Cd as a reliable paleoproxy. To understand the relative importance of each of these processes, we examined the Cd isotope systematics of 69 modern sediments deposited across a wide range of environments. We complement these data with four profiles of particulate Cd isotope compositions from the Southern Ocean. We report three main results. First, we show that the sedimentary flux of Cd is tightly coupled to that of organic matter. Second, most Cd burial occurs in regions with some bottom-water oxygen, and the flux of CdS to anoxic regions is, globally, minor. Finally, we find that remineralization can substantially modify sedimentary Cd isotope compositions, though it is challenging to relate pelagic and sedimentary processes. For example, we find that the relationship between sedimentary Cd isotope compositions and surface seawater [Cd] is the reverse of that predicted by isotope reactor models. Likewise, sedimentary Cd isotope compositions are anti-correlated with bottom-water oxygen. While this pattern is consistent with preferential remineralization of isotopically heavy Cd, profiles of marine particulate matter reveal the reverse, whereby the Cd isotope composition of large particles, which are most likely to reach the seafloor, becomes increasingly ‘heavy’ with depth. These results highlight how productivity, redox, and remineralization all influence the flux and isotope composition of Cd to marine sediments. While our study suggests that there is no simple way to relate sedimentary Cd isotopes to surface nutrient utilization, our data point toward several potential controls that could form the basis of novel proxies for local redox conditions and remineralization. 

Thallium isotopes reveal that rapid marine oxygen fluctuations in the Late Ordovician oceans are linked to mass extinction pulses. 

Abstract Pyrite framboids (spherical masses of nanoscale pyrite) are among the earliest textures of pyrite to form in sediments. It has been proposed that their trace-element (TE) contents can be used to track the TE composition of the water column in which they formed. However, it is not clear how these TEs are associated with the framboidal pyrite grains. For instance, it is important to know whether they are incorporated uniformly or are enriched in different regions of the framboid. We used high-resolution scanning transmission electron microscopy to identify chemical zoning within pyrite framboids. We found that initial, nanoscale pyrite euhedral crystals, which make up the volumetric majority of the framboids, are covered/infilled by later pyrite that templates on the earlier pyrite. Further, this later pyrite is enriched in TEs, suggesting that many TEs are incorporated in pyrite relatively late (during early diagenesis; not in the water column). This observation suggests that although chemical analyses of pyrite framboids may provide ocean-water chemistry trends through time, the details are complex. Specifically, the TEs found in pyrite may be linked to adsorption onto organic matter, detrital material, and authigenic minerals such as Fe- and Mn-oxide phases followed by desorption in the sediments or release via dissolution and incorporation into pyrite as overgrowths on the initial nanoscale euhedral crystals that make up framboids. While the use of pyrite chemistry to understand past ocean conditions remains promising, and even diagenetic additions may not preclude the utility of pyrite for reconstructing ancient ocean conditions, care must be taken in interpretations because the end concentration may be influenced by diagenesis.