Trace-metaldynamics in response of increase CO₂ and iron availability in a coastal mesocosm experiment

A mesocosm experiment was performed in the Raunefjord (Norway) to study changes in dissolved Cu (dCu) and Fe (dFe), and in the elemental composition of particles during an Emiliania huxleyi dominated bloom. The CO2 treatments consisted of present (LC; 390 ppmV) and predicted levels (HC; 900 ppmV) and iron conditions were created with the addition of the siderophore desferoxamine B (DFB). Our results showed the DFB addition enhanced the solubility of Fe in this fjord environment. Initially, dFe was comparable among treatments but after the addition, the HC and/or +DFB treatments presented higher levels and finally, the only ones maintaining high dFe were the +DFB treatments. Unlike dCu presented indistinguishable levels in all mesocosms over time. Particulate metals were normalised to P and Al to evaluate the relative influence of biotic and abiotic sources. The Fe:P ratios decreased with time and compared to published phytoplankton ratios suggest Fe storage. On the other hand, Fe:Al ratios were relatively closer to the crustal ratios suggesting that the abiotic source was more important for this metal. Trends for other metals will be discussed.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Biogeochemical cycling of polybrominated diphenyl ethers (PBDEs) in the Strait of Georgia

The temporal and spatial distribution of dissolved and particulate PBDEs seawater concentration has been monitored in the Strait of Georgia (SoG) since 2013. We aim to determine the sources, sinks and biogeochemical cycling of PBDE congeners in the water column in SoG. Particulate PBDEs concentrations show high temporal and spatial variability, indicating that the outfalls from the waste water treatment plants are major point sources. Changes in congener distributions in relation to total particulate PBDE concentrations suggest that the less brominated congeners desorb from sewage particles and add to the dissolved PBDEs pool more rapidly than the more brominated congeners. We also measured very low particulate PBDE concentrations during phytoplankton blooms, which suggest slow kinetics of adsorption or uptake of dissolved PBDEs by phytoplankton. In contrast, the concentrations of dissolved PBDEs in the SoG are more uniform and indicate that the outfalls from waste water treatment plants are not major direct point sources. Other potential sources include atmospheric deposition and desorption from effluent particles after their dispersion. A depth profile of dissolved PBDEs shows higher concentrations of the BDE-47, 99 and 153 at the surface, indicating contributions from the atmosphere or from the Fraser River. However, their highest concentrations were found at, or above, the buoyancy depth of the outfall plume from the Iona Waste Water Treatment Plant. Results obtained to date suggest a differential partitioning of PBDE congeners after their discharge from waste water treatment plants. Less brominated congeners are preferentially desorbed from sewage particles and are preferentially transported towards the surface by the estuarine circulation of the SoG, while the more brominated congeners predominantly remain associated with particles and accumulate on the seafloor. This working hypothesis will be further tested by measuring the kinetics of adsorption/desorption of PBDEs on phytoplankton and sewage particles using C-14 labelled PBDE congeners

The effects of ocean acidification and siderophore additions on trace-metal dynamics during an Emiliania Huxleyi- dominated bloom in a coastal mesocosm experiment

The combined impacts of high CO2 and changes in trace metal availability on plankton remain largely unknown. A 22 days mesocosm experiment was carried out in the Raunefjord, off Bergen, Norway (June 2012) to investigate the interactive effects of increased CO2 and changes in iron availability in the pelagic community. Twelve mesocosms covered by PAR and UVR transparent lids were used. The CO2 treatments consisted of present (LC; 390 ppmV) and predicted levels for year 2100 (HC; 900 ppmV). On day 7, half of the mesocoms were amended with the siderophore desferoxamine B (DFB) at 70 nM (final concentration). We studied changes in dissolved Cu (dCu) and Fe (dFe), and in the elemental composition of particles. Dissolved Fe and dCu were measured by chemiluminescence flow injection analysis, while particulate metals were determined by high-resolution inductively coupled mass spectrometry. The metals were normalised to P and Al to evaluate the relative influence of biotic and abiotic sources. Samples were taken throughout a bloom of the coccolithophore E. huxleyi. Further details will be discussed.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Diatom Proteomics Reveals Unique Acclimation Strategies to Mitigate Fe Limitation

Phytoplankton growth rates are limited by the supply of iron (Fe) in approximately one third of the open ocean, with major implications for carbon dioxide sequestration and carbon (C) biogeochemistry. To date, understanding how alteration of Fe supply changes phytoplankton physiology has focused on traditional metrics such as growth rate, elemental composition, and biophysical measurements such as photosynthetic competence (Fv/Fm). Researchers have subsequently employed transcriptomics to probe relationships between changes in Fe supply and phytoplankton physiology. Recently, studies have investigated longer-term (i.e. following acclimation) responses of phytoplankton to various Fe conditions. In the present study, the coastal diatom, Thalassiosira pseudonana, was acclimated (10 generations) to either low or high Fe conditions, i.e. Fe-limiting and Fe-replete. Quantitative proteomics and a newly developed proteomic profiling technique that identifies low abundance proteins were employed to examine the full complement of expressed proteins and consequently the metabolic pathways utilized by the diatom under the two Fe conditions. A total of 1850 proteins were confidently identified, nearly tripling previous identifications made from differential expression in diatoms. Given sufficient time to acclimate to Fe limitation, T. pseudonana up-regulates proteins involved in pathways associated with intracellular protein recycling, thereby decreasing dependence on extracellular nitrogen (N), C and Fe. The relative increase in the abundance of photorespiration and pentose phosphate pathway proteins reveal novel metabolic shifts, which create substrates that could support other well-established physiological responses, such as heavily silicified frustules observed for Fe-limited diatoms. Here, we discovered that proteins and hence pathways observed to be down-regulated in short-term Fe starvation studies are constitutively expressed when T. pseudonana is acclimated (i.e., nitrate and nitrite transporters, Photosystem II and Photosystem I complexes). Acclimation of the diatom to the desired Fe conditions and the comprehensive proteomic approach provides a more robust interpretation of this dynamic proteome than previous studies.This work was supported by National Science Foundation grants OCE1233014 (BLN) and the Office of Polar Programs Postdoctoral Fellowship grant 0444148 (BLN). DRG was supported by National Institutes of Health 5P30ES007033-10. AH and MTM were supported by Natural Sciences and Engineering Research Council of Canada. RFS and PWB were supported by the New Zealand Royal Society Marsden Fund and the Ministry of Science. This work is supported in part by the University of Washington's Proteomics Computer Resource Centre (UWPR95794). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript

Canadian Arctic Archipelago shelf-ocean interactions: a major iron source to Pacific derived waters transiting to the Atlantic

Author Posting. © American Geophysical Union, 2021. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 35(10), (2021): e2021GB007058, https://doi.org/10.1029/2021GB007058.Continental shelves are important sources of iron (Fe) in the land-dominated Arctic Ocean. To understand the export of Fe from the Arctic to Baffin Bay (BB) and the North Atlantic, we studied the alteration of the Fe signature in waters transiting the Canadian Arctic Archipelago (CAA). During its transit through the CAA, inflowing Arctic Waters from the Canada Basin become enriched in Fe as result of strong sediment resuspension and enhanced sediment-water interactions (non-reductive dissolution). These high Fe waters are exported to BB, where approximately 10.7 kt of Fe are delivered yearly from Lancaster Sound. Furthermore, if the two remaining main CAA pathways (Jones Sound and Nares Strait) are included, this shelf environment would be a dominant source term of Fe (dFe + pFe: 26–90 kt y−1) to Baffin Bay. The conservative Fe flux estimate (26 kt y−1) is 1.7–38 times greater than atmospheric inputs, and may be crucial in supporting primary production and nitrogen fixation in BB and beyond.This work was supported by the Natural Sciences and Engineering Research Council of Canada (Grant NSERC-CCAR), the Northern Scientific Training Program, and by the University of British Columbia through a Four Year Fellowship to B. Rogalla.2022-03-2

Using 67Cu to Study the Biogeochemical Cycling of Copper in the Northeast Subarctic Pacific Ocean

Microbial copper (Cu) nutrition and dissolved Cu speciation were surveyed along Line P, a coastal to open ocean transect that extends from the coast of British Columbia, Canada, to the high-nutrient-low-chlorophyll (HNLC) zone of the northeast subarctic Pacific Ocean. Steady-state size fractionated Cu uptake rates and Cu:C assimilation ratios were determined at in situ Cu concentrations and speciation using a 67Cu tracer method. The cellular Cu:C ratios that we measured (~30 µmol Cu mol C-1) are similar to recent estimates using synchrotron x-ray fluorescence (SXRF), suggesting that the 67Cu method can determine in situ metabolic Cu demands. We examined how environmental changes along the Line P transect influenced Cu metabolism in the sub-microplankton community. Cellular Cu:C assimilation ratios and uptake rates were compared with net primary productivity, bacterial abundance and productivity, total dissolved Cu, Cu speciation, and a suite of other chemical and biological parameters. Total dissolved Cu concentrations ([Cu]d) were within a narrow range (1.46 to 2.79 nM), and Cu was bound to a ~5-fold excess of strong ligands with conditional stability constants ( ) of ~1014. Free Cu2+ concentrations were low (pCu 14.4 to 15.1), and total and size fractionated net primary productivity (NPPV; µg C L-1 d-1) were negatively correlated with inorganic Cu concentrations ([Cu′]). We suggest this is due to greater Cu′ drawdown by faster growing phytoplankton populations. Using the relationship between [Cu′] drawdown and NPPV, we calculated a regional photosynthetic Cu:C drawdown export ratio between 1.5 and 15 µmol Cu mol C-1, and a mixed layer residence time (2.5 to 8 years) that is similar to other independent estimates (2-12 years). Total particulate Cu uptake rates were between 22 and 125 times faster than estimates of Cu export; this is possibly mediated by rapid cellular Cu uptake and efflux by phytoplankton and bacteria or the effects of grazers and bacterial remineralization on dissolved Cu. These results provide a more detailed understanding of the interactions between Cu speciation and microorganisms in seawater, and present evidence that marine phytoplankton modify Cu speciation in the open ocean

Dissolved Cu concentrations in the Strait of Georgia: trends, speciation, and accumulation by local calanoid copepods

Most research on the effects of copper (Cu) on marine ecosystems has focused on benthic organisms and Cu concentrations in the sediments. In contrast, little is known about the effects of dissolved copper (dCu) in pelagic food webs. In most marine waters, more than 99.9% of dCu is bound to organic ligands. These ligands diminish dCu toxicity to aquatic organisms by lowering the concentrations of inorganic dCu, the most bioavailable species of Cu. For the past year, we have studied seasonal trends of dCu concentrations in the Strait of Georgia and have measured and characterized its speciation in seawater. Measurements taken in 2016 ranged from 5.4 to 23.3nM dCu, which are comparable to those found in San Francisco Bay and Puget Sound. Additionally, the highest concentrations were measured when the Fraser River flow rates were the fastest. Dissolved Cu levels were highest in the surface layer (0-50m), followed by the deep layer (200m to the bottom), with the lowest levels occurring in the intermediate waters. The concentrations in the intermediate layer coincide with those in the incoming low dCu- waters from the Pacific Ocean. Furthermore, using 64Cu as a radiotracer, we have measured uptake rates of Cu, from the dissolved and the particulate fractions, by local calanoid copepods exposed to in situ Cu levels. Our data show that copepods can easily accumulate Cu from the dissolved phase. This research provides much-needed information on dissolved Cu in a region historically known to harbor smelting and mining activities, and currently active maritime trade

Effects of Copper Availability on the Physiology of Marine Heterotrophic Bacteria

Marine heterotrophic bacteria play a crucial role in the cycling of energy and nutrients in the ocean. Copper (Cu) belongs to the repertoire of essential trace nutrients for bacterial growth, yet physiological responses of marine heterotrophic bacteria to Cu deficiency remain unexplored. Here, we examined these responses in oceanic and coastal isolates of heterotrophic bacteria from ecologically significant microbial clades (Flavobacteriia class from Bacteroidetes phylum, and marine Roseobacter clade within Alphaproteobacteria class and Alteromonadales within Gammaproteobacteria class, both from Proteobacteria phylum). Bacterial growth, Cu quotas (Cu:P), macronutrient content and stoichiometry (cellular C, N, P, S, and C:N, S:P), as well as carbon metabolism (respiration, productivity, carbon demand, growth efficiency) were monitored across a gradient of Cu conditions, characteristic of coastal and open-ocean surface waters. Cu deficiency had most severe effects on a Flavobacteriia member Dokdonia sp. strain Dokd-P16 for which we observed significant reductions in growth, C metabolism and Cu quotas. Other strains did not significantly reduce their growth rate, but adjusted their Cu content and some C metabolic rates (Ruegeria pomeroyi DSS-3, Roseobacter clade) or were unaffected (Pseudoalteromonas sp. strains PAlt-P26 and PAlt-P2, Alteromonadales clade). These diverse bacterial responses were accompanied by constant cellular composition of major elements and stoichiometric ratios. Changes in bacterial Cu quotas occurred within a modest range (∼5-fold range) relative to the 50-fold variation in total Cu in the media. We hypothesize that this may reflect a well-controlled Cu homeostasis in marine heterotrophic bacteria. In a preliminary assessment, we found that Cu quotas of bacteria and those of eukaryotic phytoplankton are not statistically different. However, compared to eukaryotic phytoplankton, the variability of Cu quotas in marine heterotrophic bacteria is smaller, which could reflect differences in their Cu homeostasis. Using Cu quotas obtained in our study, we assessed the contribution of bacterial Cu to the biogenic Cu pool in an oceanic euphotic zone in the NE Pacific. These preliminary estimates suggest that up to 50% of the biogenic Cu could be contained in the biomass of marine heterotrophic bacteria. Our study sheds light on the interactions between Cu and marine heterotrophic bacteria, demonstrating the potential for Cu to influence microbial ecology and for microbes to play role in Cu biolgeochemical cycle

Diatom Proteomics Reveals Unique Acclimation Strategies to Mitigate Fe Limitation

Phytoplankton growth rates are limited by the supply of iron (Fe) in approximately one third of the open ocean, with major implications for carbon dioxide sequestration and carbon (C) biogeochemistry. To date, understanding how alteration of Fe supply changes phytoplankton physiology has focused on traditional metrics such as growth rate, elemental composition, and biophysical measurements such as photosynthetic competence (Fv/Fm). Researchers have subsequently employed transcriptomics to probe relationships between changes in Fe supply and phytoplankton physiology. Recently, studies have investigated longer-term (i.e. following acclimation) responses of phytoplankton to various Fe conditions. In the present study, the coastal diatom, Thalassiosira pseudonana, was acclimated (10 generations) to either low or high Fe conditions, i.e. Fe-limiting and Fe-replete. Quantitative proteomics and a newly developed proteomic profiling technique that identifies low abundance proteins were employed to examine the full complement of expressed proteins and consequently the metabolic pathways utilized by the diatom under the two Fe conditions. A total of 1850 proteins were confidently identified, nearly tripling previous identifications made from differential expression in diatoms. Given sufficient time to acclimate to Fe limitation, T. pseudonana up-regulates proteins involved in pathways associated with intracellular protein recycling, thereby decreasing dependence on extracellular nitrogen (N), C and Fe. The relative increase in the abundance of photorespiration and pentose phosphate pathway proteins reveal novel metabolic shifts, which create substrates that could support other well-established physiological responses, such as heavily silicified frustules observed for Fe-limited diatoms. Here, we discovered that proteins and hence pathways observed to be down-regulated in short-term Fe starvation studies are constitutively expressed when T. pseudonana is acclimated (i.e., nitrate and nitrite transporters, Photosystem II and Photosystem I complexes). Acclimation of the diatom to the desired Fe conditions and the comprehensive proteomic approach provides a more robust interpretation of this dynamic proteome than previous studies

Functional toll-like receptor 4 overexpression in papillary thyroid cancer by MAPK/ERK-induced ETS1 transcriptional activity

Emerging evidence suggests that unregulated Toll-like receptors (TLRs) signaling promotes tumor survival signals, thus favoring tumor progression. Here, the mechanism underlying TLR4 overexpression in papillary thyroid carcinomas (PTCs) mainly harboring the BRAFV600E mutation was studied. TLR4 was over expressed in PTCs compared to non-neoplastic thyroid tissue. Moreover, paired clinical specimens of primary PTC and its lymph node metastasis showed a significant up regulation of TLR4 levels in the metastatic tissues. In agreement, conditional BRAFV600E expression in normal rat thyroid cells and mouse thyroid tissue up regulated TLR4 expression levels. Furthermore, functional TLR4 expression was demonstrated in PTC cells by increased NF-κB transcriptional activity in response to the exogenous TLR4-agonist lipopolysaccharide (LPS). Of note, The Cancer Genome Atlas (TCGA) data analysis revealed that BRAFV600E-positive tumors with high TLR4 expression were associated with shorter disease-free survival. Transcriptomic data analysis indicated a positive correlation between TLR4 expression levels and MAPK/ERK signaling activation. Consistently, chemical blockade of MAPK/ERK signaling abrogated BRAFV600E-induced TLR4 expression. A detailed study of the TLR4 promoter revealed a critical MAPK/ERK-sensitive Ets binding-site involved in BRAFV600E responsiveness. Subsequent investigation revealed that the Ets-binding factor ETS1 is critical for BRAFV600E-induced MAPK/ERK signaling-dependent TLR4 gene expression. Together, these data indicate that functional TLR4 over expression in PTCs is a consequence of thyroid tumor-oncogenic driver dysregulation of MAPK/ERK/ETS1 signaling.Fil: Peyret, Victoria. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Bioquímica Clínica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Nazar, Magalí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Martín, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Quintar, Amado Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Ciencias de la Salud. Universidad Nacional de Córdoba. Instituto de Investigaciones en Ciencias de la Salud; ArgentinaFil: Fernandez, Elmer Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Area de Ciencias Agrarias, Ingeniería, Ciencias Biológicas y de la Salud de la Universidad Católica de Córdoba; ArgentinaFil: Geysels, Romina Celeste. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Fuziwara, Cesar. Universidade de Sao Paulo; BrasilFil: Montesinos, Maria del Mar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Maldonado, Cristina Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Ciencias de la Salud. Universidad Nacional de Córdoba. Instituto de Investigaciones en Ciencias de la Salud; ArgentinaFil: Santisteban, Pilar. Consejo Superior de Investigaciones Científicas. Universidad Autónoma de Madrid. Centro de Investigación Biomédica en Red Cáncer; EspañaFil: Kimura, Edna T.. Universidade de Sao Paulo; BrasilFil: Pellizas, Claudia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Nicola, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Masini, Ana María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentin