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

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 116 (2015): 272-282, doi:10.1016/j.dsr2.2014.11.005.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.This work was funded by grants from the US National Science Foundation to BST (OCE-0928289) and PJL (OCE-0963026) as part of the US GEOTRACES North Atlantic Zonal Transect program

Elevated Trace Metal Content of Prokaryotic Communities Associated with Marine Oxygen Deficient Zones

Little is known about the trace metal content of marine prokaryotes, in part due to their co-occurrence with more abundant particulate phases in the upper ocean, such as phytoplankton and biogenic detritus, lithogenic minerals, and authigenic Mn and Fe oxyhydroxides. We attempt to isolate these biomass signals in particulate data from the US GEOTRACES Eastern Pacific Zonal Transect (cruise GP16) in the Eastern Tropical South Pacific (ETSP), which exhibited consistent maxima in P and other bioactive trace metals, and minima in particulate Mn, in the oxygen deficient zones (ODZs) of 13 stations. Nitrite maxima and nitrate deficits indicated the presence of denitrifying prokaryotic biomass within ETSP ODZs, and deep secondary fluorescence maxima at the upper ODZ boundaries of 10 stations also suggested the presence of low-light, autotrophic communities. ODZs were observed as far west as 99 degrees W, more than 2300 km from the South American coast, where eolian lithogenic and lateral/resuspended sedimentary inputs were negligible, presenting a unique opportunity to examine prokaryotic metal stoichiometries. ODZ particulate P maxima can rival gyre mixed layer biomass concentrations, are highly sensitive to oxygen, and are in excess of amounts scavengable by local Fe oxyhydroxides and acid-volatile sulfides. Even after correction for lithogenic and ferruginous-scavenged metals, ODZ P-maxima are often enriched in Cd, Co, Cu, Ni, V, and Zn, exhibiting particulate trace metal ratios to P that exceed mixed layer biomass ratios by factors of 2-9. ODZ prokaryotic communities may be largely hidden, TM-rich pools involved in the marine cycles of these bioactive trace metals

Authigenic Iron Is a Significant Component of Oceanic Labile Particulate Iron Inventories

Particulate phases transport trace metals (TM) and thereby exert a major control on TM distribution in the ocean. Particulate TMs can be classified by their origin as lithogenic (crustal material), biogenic (cellular), or authigenic (formed in situ), but distinguishing these fractions analytically in field samples is a challenge often addressed using operational definitions and assumptions. These different phases require accurate characterization because they have distinct roles in the biogeochemical iron cycle. Particles collected from the upper 2,000 m of the northwest subtropical Atlantic Ocean over four seasonal cruises throughout 2019 were digested with a chemical leach to operationally distinguish labile particulate material from refractory lithogenics. Direct measurements of cellular iron (Fe) were used to calculate the biogenic contribution to the labile Fe fraction, and any remaining labile material was defined as authigenic. Total particulate Fe (PFe) inventories varied \u3c15% between seasons despite strong seasonality in dust inputs. Across seasons, the total PFe inventory (±1SD) was composed of 73 ± 13% lithogenic, 18 ± 7% authigenic, and 10 ± 8% biogenic Fe above the deep chlorophyll maximum (DCM), and 69 ± 8% lithogenic, 30 ± 8% authigenic, and 1.1 ± 0.5% biogenic Fe below the DCM. Data from three other ocean regions further reveal the importance of the authigenic fraction across broad productivity and Fe gradients, comprising ca. 20%-27% of total PFe

Metal contents of phytoplankton and labile particulate material in the North Atlantic Ocean

Citation only. Published in Progress in Oceanography 137 (2015): 261-283, doi: 10.1016/j.pocean.2015.07.00

Taxonomic and nutrient controls on phytoplankton iron quotas in the ocean

Phytoplankton iron contents (i.e., quotas) directly link biogeochemical cycles of iron and carbon and drive patterns of nutrient limitation, recycling, and export. Ocean biogeochemical models typically assume that iron quotas are either static or controlled by dissolved iron availability. We measured iron quotas in phytoplankton communities across nutrient gradients in the Pacific Ocean and found that quotas diverged significantly in taxon‐specific ways from laboratory‐derived predictions. Iron quotas varied 40‐fold across nutrient gradients, and nitrogen‐limitation allowed diatoms to accumulate fivefold more iron than co‐occurring flagellates even under low iron availability. Modeling indicates such “luxury” uptake is common in large regions of the low‐iron Pacific Ocean. Among diatoms, both pennate and centric genera accumulated luxury iron, but the cosmopolitan pennate genus Pseudo‐nitzschia maintained iron quotas 10‐fold higher than co‐occurring centric diatoms, likely due to enhanced iron storage. Biogeochemical models should account for taxonomic and macronutrient controls on phytoplankton iron quotas

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

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 116 (2015): 272-282, doi:10.1016/j.dsr2.2014.11.005.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.This work was funded by grants from the US National Science Foundation to BST (OCE-0928289) and PJL (OCE-0963026) as part of the US GEOTRACES North Atlantic Zonal Transect program

Dissolved and Particulate Trace Elements in Late Summer Arctic Melt Ponds

Melt ponds are a prominent feature of Arctic sea ice during the summer and play a role in the complex interface between the atmosphere, cryosphere and surface ocean. During melt pond formation and development, micronutrient and contaminant trace elements (TEs) from seasonally accumulated atmospheric deposition are mixed with entrained sedimentary and marine-derived material before being released to the surface ocean during sea ice melting. Here we present particulate and size-fractionated dissolved (truly soluble and colloidal) TE data from five melt ponds sampled in late summer 2015, during the US Arctic GEOTRACES (GN01) cruise. Analyses of salinity, δ18O, and 7Be indicate variable contributions to the melt ponds from snowmelt, melting sea ice, and surface seawater. Our data highlight the complex TE biogeochemistry of late summer Arctic melt ponds and the variable importance of different sources for specific TEs. Dissolved TE concentrations indicate a strong influence from seawater intrusion for V, Ni, Cu, Cd, and Ba. Ultrafiltration methods reveal dissolved Fe, Zn, and Pb to be mostly colloidal (0.003–0.2 μm), while Mn, Co, Ni, Cu, and Cd are dominated by a truly soluble (\u3c0.003 μm) fraction. Isotopically light dissolved Fe in some melt ponds suggests that photochemical and/or biologically driven redox cycling also takes place. Comparisons of particulate TE/Al ratios to mean crustal values indicate influences from lithogenic sources, including natural aerosols and/or sedimentary material, with significant enrichments for some elements, including Ni, Cu, Zn, Cd and Pb, that may result from anthropogenic aerosols, biogenic material, and/or in situ scavenging of dissolved TEs. Our results indicate that melt ponds represent a transitional environment in which some atmospherically-derived TEs undergo physical and/or chemical changes before their release to the surface ocean. As a result, the ongoing changes in sea ice areal extent, thickness, and melt season length are likely to influence the bioavailability of atmospheric TE input to the surface Arctic Ocean, with material released from snow and sea ice via melt ponds earlier in the summer and with more extensive direct deposition to the ocean surface