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Coastal upwelling of nutrients and metals along eastern boundary currents fuels some of the most biologically productive marine ecosystems. Although iron is a main driver of productivity in many of these regions, iron cycling and acquisition by microbes remain poorly constrained, in part due to the unknown composition of organic ligands that keep bioavailable iron in solution. In this study, we investigated organic ligand composition in discrete water samples collected across the highly productive California Coastal upwelling system. Siderophores were observed in distinct nutrient regimes at concentrations ranging from 1 pM to 18 pM. Near the shallow continental shelf, ferrioxamine B was observed in recently upwelled, high chlorophyll surface waters while synechobactins were identified within nepheloid layers at 60–90 m depth. In offshore waters characterized by intermediate chlorophyll, iron, and nitrate concentrations, we found amphibactins and an unknown siderophore with a molecular formula of C33H58O8N5Fe. Highest concentrations were measured in the photic zone, however, amphibactins were also found in waters as deep as 1500 m. The distribution of siderophores provides evidence for microbial iron deficiency across a range of nutrient regimes and indicates siderophore production and acquisition is an important strategy for biological iron uptake in iron limited coastal systems. Polydisperse humic ligands were also detected throughout the water column and were particularly abundant near the benthic boundary. Our results highlight the fine‐scale spatial heterogeneity of metal ligand composition in an upwelling environment and elucidate distinct sources that include biological production and the degradation of organic matter in suboxic waters. [ABSTRACT FROM AUTHOR]

Coastal upwelling currents such as the California Current System (CCS) comprise some of the most productive biological systems on the planet. Diatoms dominate these upwelling events in part due to their rapid response to nutrient entrainment. In this region, they may also be limited by the micronutrient iron (Fe), an important trace element primarily involved in photosynthesis and nitrogen assimilation. The mechanisms behind how diatoms physiologically acclimate to the different stages of the upwelling conveyor belt cycle remain largely uncharacterized. Here, we explore their physiological and metatranscriptomic response to the upwelling cycle with respect to the Fe limitation mosaic that exists in the CCS. Subsurface, natural plankton assemblages that would potentially seed surface blooms were examined over wide and narrow shelf regions. The initial biomass and physiological state of the phytoplankton community had a large impact on the overall response to simulated upwelling. Following on‐deck incubations under varying Fe physiological states, our results suggest that diatoms quickly dominated the blooms by "frontloading" nitrogen assimilation genes prior to upwelling. However, diatoms subjected to induced Fe limitation exhibited reductions in carbon and nitrogen uptake and decreasing biomass accumulation. Simultaneously, they exhibited a distinct gene expression response which included increased expression of Fe‐starvation induced proteins and decreased expression of nitrogen assimilation and photosynthesis genes. These findings may have significant implications for upwelling events in future oceans, where changes in ocean conditions are projected to amplify the gradient of Fe limitation in coastal upwelling regions. [ABSTRACT FROM AUTHOR]

Abstract: The metabolic activity and growth of phytoplankton taxa drives their ecological function and contribution to biogeochemical processes. We present the first quantitative, taxon‐resolved silica production rates, growth rates, and silica content estimates for co‐occurring diatoms along two cross‐shelf transects off the California coast using the fluorescent tracer 2‐(4‐pyridyl)‐5‐((4‐(2‐dimethylaminoethylaminocarbamoyl)methoxy)phenyl)oxazole, and confocal microscopy. Taxon contribution to total diatom community silica production was predominantly a function of the surface area (SA) of new frustule that each taxon created as opposed to cell abundance or frustule thickness. The influential role of SA made large diatoms disproportionately important to community silica production over short time scales (< 1 d). In some cases, large taxa that comprised only ∼ 15% of numerical cell abundance accounted for over 50% of total community silica production. Over longer time scales relevant to bloom dynamics, the importance of SA declines and growth rate becomes the dominant influence on contribution to production. The relative importance of SA and growth rate in relation to silica production was modeled as the time needed for a smaller, faster‐growing taxon to create more SA than a larger, slower‐growing taxon. Differences in growth rate between the taxa effected the model outcome more than differences in SA. Shifts in relative silica production among taxa are time restricted by finite resources that limit the duration of a bloom. These patterns offer clues as to how taxa respond to their environment and the consequences for both species succession and the potential diatom contribution to elemental cycling. [ABSTRACT FROM AUTHOR]

The California Current System is a diatom‐dominated region characterized by seasonal coastal upwelling and additional elevated mesoscale activity. Cyclonic mesoscale eddies in the region trap productive coastal waters with their planktonic communities and transport them offshore with limited interaction with surrounding waters, effectively acting as natural mesocosms, where phytoplankton populations undergo ecological succession as eddies age. This study examines diatom community composition within two mesoscale cyclonic eddies that formed in the same region of the California Current System 2 months apart and in the California Current waters surrounding them. The diatom communities were analyzed in the context of shifting environmental gradients and through a lens of community succession to expand our understanding of biophysical interactions in California Current System cyclonic eddies. Diatom communities within each eddy were different from non‐eddy communities and varied in concert with salinity and dissolved iron (Fe) concentrations. The younger, nearshore eddy displayed higher macronutrient and dissolved Fe concentrations, had higher values for diatom Shannon diversity and evenness, and had nutrient ratios indicative of either eventual silicic acid (Si) or Fe limitation or possibly co‐limitation. The older, offshore eddy displayed low macronutrient and dissolved Fe concentrations, was likely nitrate‐limited, and had lower diatom Shannon diversity and evenness indices. Sequences from the genus Rhizosolenia, some of which form vertically migrating mats to bypass nitrate limitation, dominated in the older eddy. This is of potential significance as the prevalence of Rhizosolenia mats could impact estimates of carbon cycling and export in the wider California coastal area. [ABSTRACT FROM AUTHOR]

Samples for organic copper (Cu)-binding ligand characterization were collected along the 2013 U.S. GEOTRACES Pacific (GP16) cruise transect from Peru to Tahiti. Full depth profiles of Cu speciation were collected across a dynamic range in oceanographic conditions including a highly productive coastal region, an oxygen deficient zone, a high nutrient low chlorophyll (HNLC) region, an oligotrophic region and a hydrothermal vent plume. Surface waters from Peru to Tahiti exhibited elevated dissolved Cu and ligand concentrations near Peru and then decreased in concentration (< 1 nM) offshore toward the oligotrophic waters. There was also an apparent shelf sediment source of strong Cu-binding ligands near the coast of Peru. Throughout most of the transect dissolved Cu and ligand concentrations were lower in the upper waters and increased with depth, with the highest concentrations near the ocean bottom. The hydrothermal vent sampled during the cruise did not seem to be a source for dissolved Cu but there was a slight elevation of Cu-binding ligands at the vent site. Similar vertical patterns in Cu-binding ligands were seen in both the GP16 dataset and the North Atlantic GEOTRACES (GA03) cruise, with notable differences in deep waters of the Pacific. The older water masses of the Pacific were highlighted by higher concentrations of dissolved Cu, Cu-binding ligands, and the free Cu ion (Cu2+) relative to the deep Atlantic. Excess Cu ligands in both GP16 and GA03 point to a possible fraction of Cu accumulating in the deep Pacific that is inert to ligand exchange, suggesting older waters might contain a high fraction of unreactive Cu. • Strong copper-binding ligands detected near the shelf of Peru. • Offshore oligotrophic waters found to have lowest dissolved copper and copper-binding ligand concentrations • Comparison of copper speciation data between the Atlantic (GA03) and Pacific (GP16) U.S. GEOTRACES transects • Evidence for exchange-inert dissolved copper fraction accumulating in older Pacific deep waters [ABSTRACT FROM AUTHOR]

Diatoms are prominent eukaryotic phytoplankton despite being limited by the micronutrient iron in vast expanses of the ocean. As iron inputs are often sporadic, diatoms have evolved mechanisms such as the ability to store iron that enable them to bloom when iron is resupplied and then persist when low iron levels are reinstated. Two iron storage mechanisms have been previously described: the protein ferritin and vacuolar storage. To investigate the ecological role of these mechanisms among diatoms, iron addition and removal incubations were conducted using natural phytoplankton communities from varying iron environments. We show that among the predominant diatoms, Pseudo-nitzschia were favored by iron removal and displayed unique ferritin expression consistent with a long-term storage function. Meanwhile, Chaetoceros and Thalassiosira gene expression aligned with vacuolar storage mechanisms. Pseudo-nitzschia also showed exceptionally high iron storage under steady-state high and low iron conditions, as well as following iron resupply to iron-limited cells. We propose that bloom-forming diatoms use different iron storage mechanisms and that ferritin utilization may provide an advantage in areas of prolonged iron limitation with pulsed iron inputs. As iron distributions and availability change, this speculated ferritin-linked advantage may result in shifts in diatom community composition that can alter marine ecosystems and biogeochemical cycles. [ABSTRACT FROM AUTHOR]

Summary: Frequent blooms of phytoplankton occur in coastal upwelling zones creating hotspots of biological productivity in the ocean. As cold, nutrient‐rich water is brought up to sunlit layers from depth, phytoplankton are also transported upwards to seed surface blooms that are often dominated by diatoms. The physiological response of phytoplankton to this process, commonly referred to as shift‐up, is characterized by increases in nitrate assimilation and rapid growth rates. To examine the molecular underpinnings behind this phenomenon, metatranscriptomics was applied to a simulated upwelling experiment using natural phytoplankton communities from the California Upwelling Zone. An increase in diatom growth following 5 days of incubation was attributed to the genera Chaetoceros and Pseudo‐nitzschia. Here, we show that certain bloom‐forming diatoms exhibit a distinct transcriptional response that coordinates shift‐up where diatoms exhibited the greatest transcriptional change following upwelling; however, comparison of co‐expressed genes exposed overrepresentation of distinct sets within each of the dominant phytoplankton groups. The analysis revealed that diatoms frontload genes involved in nitrogen assimilation likely in order to outcompete other groups for available nitrogen during upwelling events. We speculate that the evolutionary success of diatoms may be due, in part, to this proactive response to frequently encountered changes in their environment. [ABSTRACT FROM AUTHOR]

Abstract: A 3‐day shipboard incubation experiment was conducted in the California Current System in July 2014 to investigate the cycling of iron (Fe), copper (Cu), nickel (Ni), cadmium (Cd), manganese (Mn), cobalt (Co), lead (Pb), and scandium (Sc) under a range of light and particle conditions. Filtered (< 0.2 μm) and unfiltered treatments were incubated under the following light conditions: Dark, light (“UV”), and light without the ultraviolet (UV) wavelengths (“noUV”). The experiment was sampled for carbon and Fe uptake rates, dissolved trace metal concentrations (Fe, Cu, Ni, Cd, Mn, Co, Pb, Sc), Fe and Cu speciation, size‐fractionated concentrations of Cd and Fe, and diatom community composition from DNA sequencing. Exposure to UV light increased phytoplankton Fe uptake in the first 24 h of the incubation relative to the noUV treatment, suggesting that a fraction of the ambient ligand‐bound Fe was photoreactive. Fe‐binding organic ligand production was observed in the unfiltered light treatments in association with increasing chlorophyll a, and evidence for Cu‐binding ligand production in these treatments was also observed. Biological uptake of Cd and Co was observed along with scavenging of dissolved Pb. Manganese appeared to be rapidly oxidized by Mn‐oxidizing bacteria with concomitant drawdown of dissolved Ni. Scandium displayed similar trends to Fe, reinforcing the limited observations of the physicochemical similarities between these two elements in seawater. Overall, this study highlights distinct impacts of photochemical processes, scavenging, and biological effects on marine trace metal cycling in an environment characterized by seasonal upwelling. [ABSTRACT FROM AUTHOR]

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen. [ABSTRACT FROM AUTHOR]

Most of the lead (Pb) in today's ocean is from human activities, although natural sources contribute small amounts of Pb that are usually masked by massive anthropogenic emissions. In the U.S. GEOTRACES East Pacific Section (GP16), anthropogenic Pb is observed throughout the water column, and as seen elsewhere in the Pacific, Pb concentrations are highest in the upper hundreds of meters of the ocean and generally decrease with depth. Thermocline Pb concentrations are higher in the eastern portion of the section near the South American coast, decreasing with distance from the South American continent, as previously reported for redox sensitive trace elements (e.g., Mn). High precision Pb isotope ratios show that there has been a change over the past few decades in the source of Pb in the westernmost upper waters, shifting from an American-Australian type Pb intermixture to a Chinese-American-type Pb intermixture. Although it is known from the study of hydrothermal solutions and sediments that there is a large primary Pb flux from high temperature ridge crest hydrothermal springs, most of this Pb precipitates near the hydrothermal vents and very little escapes into the open water column. In fact, hydrothermal ferromanganese oxyhydroxides precipitated from the hot spring emissions strip anthropogenic Pb out of the water column, resulting in the lowest Pb concentrations ever observed in the ocean (a few tenths of a picomole/kg) in the high 3He-plume to the west of the East Pacific Rise. Deeper waters have similarly low Pb concentrations, probably as a result of the sinking veil of hydrothermal-source ferromanganese oxyhydroxides. Core top sediments from this section and previous work show clear evidence of less-radiogenic Mid Ocean Ridge Basalt (MORB) Pb distinct from the crustal and anthropogenic Pb seen in non-ridge crest sediments, specifically, low values of 206Pb/207Pb (1.189), 208Pb/207Pb (2.449), and 206Pb/204Pb (18.42), compared to ~1.195, ~2.475, and ~ 18.75 respectively for the non- hydrothermal sediments. Near bottom dissolved (<0.2 μm filter) water column Pb (with concentrations <2 pmol kg−1) at the ridge crest and in the near-downstream neutrally-buoyant hydrothermal plume show 206Pb/207Pb - 208Pb/206Pb trends that are lower than observed throughout the rest of the water column and fall within the mixing end- member isotope ratios of less radiogenic MORB and more radiogenic anthropogenic Pb sources. Thus there is a very small leakage (~1%) of primary high temperature hydrothermal Pb into the water column. But at the westernmost station (36), which shows a diluted continuation of the 3He, manganese (Mn), and iron (Fe) plume from 2200 to 2700 m, the >2200 m Pb isotope ratios deeper than 2000 m return to the non-hydrothermal ratios with no remaining detectable MORB. • In GT Section GP16, anthropogenic Pb is observed throughout the water column, as seen throughout the Pacific. • Pb isotope ratios show a recent change in the source of Pb in the westernmost upper waters. • Hydrothermal FeMn oxyhydroxides strip anthropogenic Pb and most hydrothermal Pb emissions out of the water column. • There is a very small (~1%) leakage of primary high temperature hydrothermal MORB-derived Pb into the water column. [ABSTRACT FROM AUTHOR]

Trace element (TE) fluxes and their residence times (Fe, Mn, Cu, Pb, Cd, and V) within the surface ocean were determined along the GEOTRACES East Pacific Zonal Transect (GP16/EPZT) and found to reflect the diverse physical and geochemical conditions encountered across the track. The TE flux from atmospheric deposition, vertical mixing, and upwelling into the mixed layer and into the particle production zone (PPZ) along the GEOTRACES EPZT transect were evaluated with 7Be-based methods developed in earlier works. A horizontal input flux is driven from east to west by the South Equatorial Current (SEC), and estimated advection velocities were applied to horizontal gradients in the distributions of several TEs to approximate this term. There is a minimum in atmospheric deposition in the central gyre, with higher fluxes to the east due to large near-shore aerosol TE loadings, and higher to the west due to greater precipitation-driven deposition velocities (V b). The 7Be-derived vertical diffusion (K z) values range from 2.5 to 39 m2/d (0.29 × 10−4 to 4.5 × 10−4 m2/s) with higher values generally within the nearshore upwelling region and the lowest values within the stratified central gyre. Manganese displayed a well-defined gradient extending from the nearshore stations into the central gyre such that the advective term is a major component of the total input flux, particularly within the central gyre. Relative to other inputs the atmospheric input of soluble Mn is only of minor importance. Unlike Mn, there is no discernable horizontal gradient in the dissolved Fe data and therefore, there is no horizontal component of flux. Nearshore removal processes are more intense for dissolved Fe than for dissolved Mn and as a result, dissolved Mn remains elevated much farther offshore than does dissolved Fe. For the stratified mid-ocean gyre stations, the total input of Fe from all sources is relatively small compared to the inshore stations, and atmospheric deposition becomes the dominant mode of input. Aerosol Fe solubility determined by a 25% acetic acid leach with hydroxylamine hydrochloride was much greater than that derived from a leach using ultra-pure deionized water. This led to significant differences in the residence time of Fe calculated for the mid-ocean gyre using these different solubilities. Generally, each element displays relatively short (weeks–months) residence times within the nearshore region of robust upwelling, reflecting large input terms and rapid removal. Moving offshore, total input fluxes decrease and the residence times of the TEs increase markedly until the western edge of the transect. There, relaxation of ocean stratification permits greater upward turbulent flux and greater rainfall leads to greater atmospheric input of TEs. • Trace element fluxes to the surface ocean were determined along the GEOTRACES EPZT. • Trace element residence times in the surface ocean were determined along the transect. • Trace element properties reflected diverse physical and geochemical conditions. [ABSTRACT FROM AUTHOR]