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  • 11
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    Adsorption of biologically critical trace elements to the marine cyanobacterium Synechococcus sp. PCC 7002: Implications for marine trace metal cycling (2019)
    Elsevier
    In:  Chemical Geology, 525 . pp. 28-36.
    Details
    Publication Date: 2022-01-31
    Description: Highlights • The adsorption of Co, Ni, Cu, and Zn to Synechococcus sp PCC 7002 was studied using a surface complexation modelling approach. • A surface complexation model was developed to determine the thermodynamic binding constants of Co, Ni, Cu, and Zn to Synechococcus. • The surface complexation model was able to accurately predict the competitive adsorptionof the four metals to Synechococcus. • Synechococcus could have been an important exit channel for trace elements into ancient sediments such as BIF Marine bacterial plankton play a key role in elemental cycling through their ability to bind, assimilate, metabolize, and modify the redox state of trace metals in seawater. Of those processes, arguably the least studied are the mechanisms underpinning trace metal adsorption to planktonic marine bacteria, despite a plethora of literature pertaining to terrestrial species. Recently, Liu et al. (2015) demonstrated that the marine cyanobacterium Synechococcus sp. PCC 7002 has the capacity to remove appreciable amounts of Cd2+, a proxy for other divalent cations, from seawater by adsorption. In this study, we build on that work and employ a surface complexation modelling (SCM) approach using titration and pH adsorption edge experiments to calculate the thermodynamic binding constants of four bioessential transition metals (Co, Ni, Cu, Zn) to Synechococcus in simulated seawater. Based on the titration results, the major functional groups involved in metal binding were carboxyl groups with a pKa of 5.59 and phosphoryl groups with a pKa of 7.61. Metal adsorption experiments indicate that Synechococcus can bind considerable concentrations of Zn, Cu, Ni, and Co at pH 8. When all four metals are simultaneously added to solution, the same adsorption pattern of Zn 〉 Cu 〉 Ni 〉 Co is maintained, and accurately predicted by the SCM. Based on average marine cell densities and turnover rates of Synechococcus cells in the photic zone, we calculate that Synechococcus, in the absence of competing ligands such as dissolved organic matter (DOM), has the theoretical capacity to remove nearly all of the free metal cations from seawater. These observations highlight the surface reactivity of marine cyanobacteria as a potentially important vector for the transfer of dissolved metals from the photic zone to deeper waters or the seafloor in modernoceans, but they also have implications for the Precambrian oceans as sinking cyanobacteria could have acted as an exit channel for trace elements into ancient sediments including banded iron formations (BIF).
    Type: Article , PeerReviewed
    Format: text
    DOI: 10.1016/j.chemgeo.2019.05.021
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 12
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    Surface reactivity of the cyanobacterium Synechocystis sp. PCC 6803 – Implications for trace metals transport to the oceans (2021)
    Elsevier
    Details
    Publication Date: 2024-02-07
    Description: Highlights • The adsorption of Cd to Synechocystis sp. PCC 6803 was investigated at both marine and freshwater ionic strength. • The thermodynamic binding constants of Cd to Synechocystis were calculated using a surface complexation modeling approach. • Synechocystis and other planktonic cyanobacteria may be an important vector of trace metals transport to marine settings. Cyanobacteria are abundant in nearly every surface environment on Earth. Understanding their chemical reactivity and metal binding capacity with varying ionic strength (IS) is paramount to understanding trace metal cycling in natural environments. We conducted an investigation on the cell surface reactivity of the freshwater cyanobacterium Synechocystis sp. PCC 6803 at freshwater (0.01 M NaCl) and marine (0.56 M NaCl) IS. Potentiometric titration data were used to develop a multiple discrete site, non-electrostatic surface complexation model (SCM), and corresponding cell surface functional group identities were verified using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Synechocystis cells were best modeled in FITEQL 4.0 using a non-electrostatic 2-site protonation model. Cadmium (Cd) adsorption experiments paired with SCM was utilized to calculate the binding constants of Cd. Synechocystis surface functional groups demonstrated a stronger affinity for Cd across the entire pH range studied (3–9) at freshwater IS, with the greatest difference at circumneutral pH (6–8) where Cd adsorption in freshwater IS was 60% greater than at marine IS. These data combined with the ubiquitous distribution of Synechocystis in freshwater and brackish environments suggest that these organisms could play an important role in trace metal cycling in environments with large salinity gradients, such as estuaries and deltas, and could act as a transport mechanism for trace metals from terrestrial to marine settings.
    Type: Article , PeerReviewed
    Format: text
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 13
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    A SURROGATE APPROACH TO STUDYING THE CHEMICAL REACTIVITY OF BURROW MUCOUS LININGS IN MARINE SEDIMENTS (2011)
    Society for Sedimentary Geology (SEPM)
    Details
    Publication Date: 2011-09-01
    Description: Many infaunal marine invertebrates produce mucous excretions, composed primarily of the glycoprotein mucin, that play important roles in burrow stabilization. As with other biopolymers, the ionization of mucin provides highly reactive organic ligands that enable the sorption of metal cations from seawater. Owing to the difficulties in its isolation, however, the specific role of mucin in the adsorptive properties of animal secretions in marine environments is poorly understood. Here we apply a surface complexation approach to model proton and Cd adsorption behavior of partially purified Type III porcine gastric mucin (PGM), a commercially available analog to natural infaunal mucus. FTIR, proton and cadmium adsorption experiments indicate that Type III PGM mimics the acid-base and metal complexation behavior of natural mucous gels excreted by terebellid polychaete worms. At marine pH, nearly two-thirds of the total ligands in mucin-type glycoproteins are deprotonated and thus available to participate in metal cation adsorption reactions. Importantly, the concentration of available organic ligands in mucin exceeds (by up to 5 times) that of a variety of other metal-reactive organic compounds comprising the organic fraction of marine sediments. A substantial fraction of the dissolved organic matter in the bioturbated zone of marine sediments occurs in the form of mucin-associated glycoproteins; the availability of such organic materials may strongly influence the distribution of cations at the burrow margin.
    Print ISSN: 0883-1351
    Electronic ISSN: 0883-1351
    Topics: Geosciences
    Published by Society for Sedimentary Geology (SEPM)
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  • 14
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    Mineral ecophysiological data provide growing evidence for microbial activity in banded-iron formations (2011)
    Geological Society of America (GSA)
    Details
    Publication Date: 2011-08-01
    Description: The phosphorus composition of banded-iron formations (BIFs) has been used as a proxy for Precambrian seawater composition and the paleoeredox state of Earth's surface environment. However, it is unclear whether the phosphorus in BIFs originally entered the sediment as a sorbed component of the iron oxyhydroxide particles, or whether it was incorporated into the biomass of marine phytoplankton. We conducted high-resolution mineral analyses and report here the first detection of an Fe(III) acetate salt, as well as nanocrystals of apatite in association with magnetite, in the 2.48 Ga Dales Gorge Member of the Brockman Iron Formation (a BIF), Hamersley, Western Australia. The clusters of apatite are similar in size and morphology to biogenic apatite crystals resulting from biomass decay in Phanerozoic marine sediments, while the formation of an Fe(III) acetate salt and magnetite not only implies the original presence of biomass in the BIF sediments, but also that organic carbon likely served as an electron donor during bacterial Fe(III) reduction. This study is important because it suggests that phytoplankton may have played a key role in the transfer of phosphorus (and other trace elements) from the photic zone to the seafloor.
    Print ISSN: 0091-7613
    Electronic ISSN: 1943-2682
    Topics: Geosciences
    Published by Geological Society of America (GSA)
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  • 15
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    Iron in Earth Surface Systems: A Major Player in Chemical and Biological Processes (2011)
    Mineralogical Society of America
    Details
    Publication Date: 2011-04-01
    Description: As an essential nutrient and energy source for the growth of microbial organisms, iron is metabolically cycled between reduced and oxidized chemical forms. The resulting flow of electrons is invariably tied to reactions with other redox-sensitive elements, including oxygen, carbon, nitrogen, and sulfur. Therefore, iron is intimately involved in the geochemistry, mineralogy, and petrology of modern aquatic systems and their associated sediments, particulates, and porewaters. In the geological past, iron played an even greater role in marine geochemistry, as evidenced by the vast deposits of Precambrian iron-rich sediments, the "banded iron formations." These deposits are now being used as proxies for understanding the chemical composition of the ancient oceans and atmosphere.
    Print ISSN: 1811-5209
    Electronic ISSN: 1811-5217
    Topics: Geosciences
    Published by Mineralogical Society of America
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  • 16
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    IRON IN MICROBIAL METABOLISMS (2011)
    Mineralogical Society of America
    Details
    Publication Date: 2011-04-01
    Description: Microbes are intimately involved in the iron cycle. First, acquisition of iron by microorganisms for biochemical requirements is a key process in the iron cycle in oxygenated, circumneutral pH environments, where the solubility of Fe(III) (oxyhydr)oxides is extremely low. Second, a number of aerobic (using O2) and anaerobic (living in the absence of O2) autotrophic bacteria gain energy for growth from the oxidation of dissolved and solid-phase Fe(II) compounds to Fe(III) (oxyhydr)oxides. Third, heterotrophic Fe(III)-reducing bacteria close the chemical loop by reducing solid-phase Fe(III) minerals back to dissolved and solid-phase Fe(II). Together these metabolic processes control the partitioning of the Earth's fourth most abundant crustal element, and they are additionally tied to the cycling of several major nutrients (e.g. carbon, oxygen, nitrogen, sulfur) and trace elements (e.g. phosphorus, nickel) in modern and ancient environments.
    Print ISSN: 1811-5209
    Electronic ISSN: 1811-5217
    Topics: Geosciences
    Published by Mineralogical Society of America
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  • 17
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    Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017)
    Details
    Publication Date: 2022-05-25
    Description: © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Earth-Science Reviews 172 (2017): 140-177, doi:10.1016/j.earscirev.2017.06.012.
    Description: Iron formations (IF) represent an iron-rich rock type that typifies many Archaean and Proterozoic supracrustal successions and are chemical archives of Precambrian seawater chemistry and postdepositional iron cycling. Given that IF accumulated on the seafloor for over two billion years of Earth’s early history, changes in their chemical, mineralogical, and isotopic compositions offer a unique glimpse into environmental changes that took place on the evolving Earth. Perhaps one of the most significant events was the transition from an anoxic planet to one where oxygen was persistently present within the marine water column and atmosphere. Linked to this progressive global oxygenation was the evolution of aerobic microbial metabolisms that fundamentally influenced continental weathering processes, the supply of nutrients to the oceans, and, ultimately, diversification of the biosphere and complex life forms. Many of the key recent innovations in understanding IF genesis are linked to geobiology, since biologically assisted Fe(II) oxidation, either directly through photoferrotrophy, or indirectly through oxygenic photosynthesis, provides a process for IF deposition from mineral precursors. The abundance and isotope composition of Fe(II)-bearing minerals in IF additionally suggests microbial Fe(III) reduction, a metabolism that is deeply rooted in the Archaea and Bacteria. Linkages among geobiology, hydrothermal systems, and deposition of IF have been traditionally overlooked, but now form a coherent model for this unique rock type. This paper reviews the defining features of IF and their distribution through the Neoarchaean and Palaeoproterozoic. This paper is an update of previous reviews by Bekker et al. (2010, 2014) that will improve the quantitative framework we use to interpret IF deposition. In this work, we also discuss how recent discoveries have provided new insights into the processes underpinning the global rise in atmospheric oxygen and the geochemical evolution of the oceans.
    Description: KOK, TJW, RH, CAP and AB would like to thank the Natural Sciences and Engineering Research Council of Canada (NSERC) for its financial support. LJR gratefully acknowledges the support of a Vanier Canada Graduate Scholarship. CMJ, DSH, NJP and TWL acknowledge support from the NASA Astrobiology Institute. SVL acknowledges support from the European Institute for Marine Studies (LabexMER, ANR-10-LABX-19). HT and PBHO thank ASSMANG Ltd for providing research funding.
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 18
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    Authigenic iron oxide proxies for marine zinc over geological time and implications for eukaryotic metallome evolution (2013)
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of John Wiley & Sons for personal use, not for redistribution. The definitive version was published in Geobiology 11 (2013): 295-306, doi:10.1111/gbi.12036.
    Description: Here we explore enrichments in paleomarine Zn as recorded by authigenic iron oxides including Precambrian iron formations, ironstones and Phanerozoic hydrothermal exhalites. This compilation of new and literature-based iron formation analyses track dissolved Zn abundances and constrain the magnitude of the marine reservoir over geological time. Overall, the iron formation record is characterized by a fairly static range in Zn/Fe ratios throughout the Precambrian, consistent with the shale record (Scott et al., 2013, Nature Geoscience, 6, 125-128). When hypothetical partitioning scenarios are applied to this record, paleomarine Zn concentrations within about an order of magnitude of modern are indicated. We couple this examination with new chemical speciation models used to interpret the iron formation record. We present two scenarios: first, under all but the most sulfidic conditions and with Zn binding organic ligand concentrations similar to modern oceans, the amount of bioavailable Zn remained relatively unchanged through time. Late proliferation of Zn in eukaryotic metallomes has previously been linked to marine Zn biolimitation, but under this scenario, the expansion in eukaryotic Zn metallomes may be better linked to biologically intrinsic evolutionary factors. In this case zinc’s geochemical and biological evolution may be decoupled, and viewed as a function of increasing need for genome regulation and diversification of Zn-binding transcription factors. In the second scenario, we consider Archean organic ligand complexation in such excess that it may render Zn bioavailability low. However, this is dependent on Zn organic ligand complexes not being bioavailable, which remains unclear. In this case, although bioavailability may be low, sphalerite precipitation is prevented, thereby maintaining a constant Zn inventory throughout both ferruginous and euxinic conditions. These results provide new perspectives and constraints 50 on potential couplings between the trajectory of biological and marine geochemical coevolution.
    Description: This work was supported by a NSERC Discovery Grant to KOK, a NSERC PDF to SVL, a NSERC CGSM to LJR, and an NSF-EAR-PDF to NJP. MAS acknowledges support from the Gordon and Betty Moore Foundation Grant #2724. This work was also supported by grants from the Deutsche Forschungsgemeinschaft (DFG) to A.K. (KA 1736/4-1 and 12-1).
    Keywords: Paleomarine zinc ; Metallome evolution ; Metalloenzymes ; Eukaryotic evolution ; Iron formations
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
    Format: application/pdf
    Format: application/vnd.ms-excel
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  • 19
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    Trace elements at the intersection of marine biological and geochemical evolution (2017)
    Details
    Publication Date: 2022-05-26
    Description: © The Author(s), 2016. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Earth-Science Reviews 163 (2016): 323-348, doi:10.1016/j.earscirev.2016.10.013.
    Description: Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages have yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth’s ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies.
    Description: LJR gratefully acknowledges the support of a Vanier Canada Graduate Scholarship. Discovery Grants from the Natural Sciences and Engineering Research Council of Canada (NSERC) to CAP, BK, DSA, SAC, and KOK supported this work. This material is based upon work supported by the National Aeronautics and Space Administration through the NASA Astrobiology Institute under Cooperative Agreement No. NNA15BB03A issued through the Science Mission Directorate. NJP receives support from the Alternative Earths NASA Astrobiology Institute. Funding from the NASA Astrobiology Institute, and the NSF FESD and ELT programs to TWL, and the Region of Brittany and LabexMER funding to SVL are also gratefully acknowledged. AB thanks the Society of Independent Thinkers.
    Keywords: Iron formations ; Black shales ; Eukaryotes ; Prokaryotes ; Evolution ; Trace elements ; Biolimitation ; Precambrian
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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