The interplay between regeneration and scavenging fluxes drives ocean iron cycling

Despite recent advances in observational data coverage, quantitative constraints on how different physical and biogeochemical processes shape dissolved iron distributions remain elusive, lowering confidence in future projections for iron-limited regions. Here we show that dissolved iron is cycled rapidly in Pacific mode and intermediate water and accumulates at a rate controlled by the strongly opposing fluxes of regeneration and scavenging. Combining new data sets within a watermass framework shows that the multidecadal dissolved iron accumulation is much lower than expected from a meta-analysis of iron regeneration fluxes. This mismatch can only be reconciled by invoking significant rates of iron removal to balance iron regeneration, which imply generation of authigenic particulate iron pools. Consequently, rapid internal cycling of iron, rather than its physical transport, is the main control on observed iron stocks within intermediate waters globally and upper ocean iron limitation will be strongly sensitive to subtle changes to the internal cycling balance

Return of naturally sourced Pb to Atlantic surface waters

Anthropogenic emissions completely overwhelmed natural marine lead (Pb) sources during the past century, predominantly due to leaded petrol usage. Here, based on Pb isotope measurements, we reassess the importance of natural and anthropogenic Pb sources to the tropical North Atlantic following the nearly complete global cessation of leaded petrol use. Significant proportions of up to 30-50% of natural Pb, derived from mineral dust, are observed in Atlantic surface waters, reflecting the success of the global effort to reduce anthropogenic Pb emissions. The observation of mineral dust derived Pb in surface waters is governed by the elevated atmospheric mineral dust concentration of the North African dust plume and the dominance of dry deposition for the atmospheric aerosol flux to surface waters. Given these specific regional conditions, emissions from anthropogenic activities will remain the dominant global marine Pb source, even in the absence of leaded petrol combustion

Global Spatial and Temporal Variation of Cd:P in Euphotic Zone Particulates

Concentrations of Cd and P were determined in particle samples collected using the multiple unit large volume in situ filtration system (MULVFS) from 50 profiles at 34 different locations throughout the Atlantic, Pacific, and Southern Oceans since 1991. Consistent methodology has been used. This data set of Cd:P in size fractionated particles gives insight into the processes that lead to differences in regional Cd:P particle values as well as how the formation and remineralization of these particles lead to dissolved deep water ratios that increase from the North Atlantic to the North Pacific. With large spatial and temporal variation, this data set allows us to study the effects of an El Niño, upwelling, large-scale in situ Fe fertilization, low-oxygen conditions, and seasonal variation on the Cd:P in particles. Overall, Cd:P tends to be higher (~1–2 mmol/mol) in particles gathered in biologically dynamic waters and is much lower (typically ~0.1 mmol/mol) in oligotrophic regions. Using multiple linear regression analysis, we investigate how euphotic zone parameters important to photosynthesis including nitrate, phosphate, silicate, temperature, and euphotic zone depth affect the Cd:P ratio in particles. Using the results of the analysis, we create global seasonal maps of predicted particulate Cd:P distributions. We find that three factors—local dissolved nitrate, silicate concentrations, and euphotic zone depth—can predict 59% of the variation in particulate Cd:P. We verified our projections using in situ filtration samples collected during GEOTRACES expeditions GA03 (North Atlantic) and GP16 (South Pacific)

Comparison of particulate trace element concentrations in the North Atlantic Ocean as determined with discrete bottle sampling and in situ pumping

The oceanic geochemical cycles of many metals are controlled, at least in part, by interactions with particulate matter, and measurements of particulate trace metals are a core component of the international GEOTRACES program. Particles can be collected by several methods, including in-line filtration from sample bottles and in situ pumping. Both approaches were used to collect particles from the water column on the U.S. GEOTRACES North Atlantic Zonal Transect cruises. Statistical comparison of 91 paired samples collected at matching stations and depths indicate mean concentrations within 5% for Fe and Ti, within 10% for Cd, Mn and Co, and within 15% for Al. Particulate concentrations were higher in bottle samples for Cd, Mn and Co but lower in bottle samples for Fe, Al and Ti, suggesting that large lithogenic particles may be undersampled by bottles in near-shelf environments. In contrast, P was 58% higher on average in bottle samples. This is likely due to a combination of analytical offsets between lab groups, differences in filter pore size, and potential loss of labile P from pump samples following misting with deionized water. Comparable depth profiles were produced by the methods across a range of conditions in the North Atlantic

Atmospheric Input and Seasonal Inventory of Dissolved Iron in the Sargasso Sea: Implications for Iron Dynamics in Surface Waters of the Subtropical Ocean

Constraining the role of dust deposition in regulating the concentration of the essential micronutrient iron in surface ocean waters requires knowledge of the flux of seawater-soluble iron in aerosols and the replacement time of dissolved iron (DFe) in the euphotic zone. Here we estimate these quantities using seasonally resolved DFe data from the Bermuda Atlantic Time-series Study region and weekly-scale measurements of iron in aerosols and rain from Bermuda during 2019. In response to seasonal changes in vertical mixing, primary production and dust deposition, surface DFe concentrations vary from ∼0.2 nM in early spring to >1 nM in late summer, with DFe inventories ranging from ∼30 to ∼80 μmol/m2, respectively, over the upper 200 m. Assuming the upper ocean approximates steady state for DFe on an annual basis, our aerosol and rainwater data require a mean euphotic-zone residence time of ∼0.8–1.9 years for DFe with respect to aeolian input

Global niche of marine anaerobic metabolisms expanded by particle microenvironments

In ocean waters, anaerobic microbial respiration should be confined to the anoxic waters found in coastal regions and tropical oxygen minimum zones, where it is energetically favourable. However, recent molecular and geochemical evidence has pointed to a much broader distribution of denitrifying and sulfate-reducing microbes. Anaerobic metabolisms are thought to thrive in microenvironments that develop inside sinking organic aggregates, but the global distribution and geochemical significance of these microenvironments is poorly understood. Here, we develop a new size-resolved particle model to predict anaerobic respiration from aggregate properties and seawater chemistry. Constrained by observations of the size spectrum of sinking particles, the model predicts that denitrification and sulfate reduction can be sustained throughout vast, hypoxic expanses of the ocean, and could explain the trace metal enrichment observed in particles due to sulfide precipitation. Globally, the expansion of the anaerobic niche due to particle microenvironments doubles the rate of water column denitrification compared with estimates based on anoxic zones alone, and changes the sensitivity of the marine nitrogen cycle to deoxygenation in a warming climate