skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: In-situ analysis of sub-nanomolar level of Fe(II) in open-ocean waters
Abstract Iron (Fe) in seawater is an essential micronutrient for marine phytoplankton, and Fe deficiency limits their growth in high-nutrient, low-chlorophyll areas. The bioavailability of Fe for phytoplankton largely depends on its chemical speciation in seawater. In surface water, the reduction of Fe(III) to Fe(II) is an important step in the uptake of Fe by phytoplankton. However, the marine biogeochemical cycle of Fe(II) in the open ocean has not been fully investigated. In oxic open-ocean waters, Fe(II) is rapidly oxidized and exists at sub-nanomolar levels, making it difficult to determine the Fe(II) concentration of seawater. In this study, we applied the flow analytical method of determining the Fe(II) concentration of seawater using luminol chemiluminescence in an in-situ analyzer (geochemical anomaly monitoring system, GAMOS). In the onboard laboratory, we successfully detected sub-nanomolar levels of Fe(II) in seawater using the GAMOS. In the central Indian Ocean, this analyzer was deployed at a depth of 1000 m to determine the Fe(II) concentration in the water column. During deployment, the detection limit (0.48 nM) was insufficient to determine the concentration. Therefore, we need to lower the blank values and enhance the stability of signal of the in-situ analytical method for application to open-ocean seawater samples. Graphical abstract  more » « less
Award ID(s):
2140395
PAR ID:
10648542
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
Springer
Date Published:
Journal Name:
Analytical Sciences
Volume:
40
Issue:
11
ISSN:
0910-6340
Page Range / eLocation ID:
2017 to 2025
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. We describe considerations and strategies for developing a nuclear magnetic resonance (NMR) sample preparation method to extract low molecular weight metabolites from high‐salt spent media in a model coculture system of phytoplankton and marine bacteria. Phytoplankton perform half the carbon fixation and oxygen generation on Earth. A substantial fraction of fixed carbon becomes part of a metabolite pool of small molecules known as dissolved organic matter (DOM), which are taken up by marine bacteria proximate to phytoplankton. There is an urgent need to elucidate these metabolic exchanges due to widespread anthropogenic transformations on the chemical, phenotypic, and species composition of seawater. These changes are increasing water temperature and the amount of CO2absorbed by the ocean at energetic costs to marine microorganisms. Little is known about the metabolite‐mediated, structured interactions occurring between phytoplankton and associated marine bacteria, in part because of challenges in studying high‐salt solutions on various analytical platforms. NMR analysis is problematic due to the high‐salt content of both natural seawater and culture media for marine microbes. High‐salt concentration degrades the performance of the radio frequency coil, reduces the efficiency of some pulse sequences, limits signal‐to‐noise, and prolongs experimental time. The method described herein can reproducibly extract low molecular weight DOM from small‐volume, high‐salt cultures. It is a promising tool for elucidating metabolic flux between marine microorganisms and facilitates genetic screens of mutant microorganisms. 
    more » « less
  2. Abstract Metal cations are potent environmental pollutants that negatively impact human health and the environment. Despite advancements in sensor design, the simultaneous detection and discrimination of multiple heavy metals at sub‐nanomolar concentrations in complex analytical matrices remain a major technological challenge. Here, the design, synthesis, and analytical performance of three highly emissive conjugated polyelectrolytes (CPEs) functionalized with strong iminodiacetate and iminodipropionate metal chelates that operate in challenging environmental samples such as seawater are demonstrated. When coupled with array‐based sensing methods, these polymeric sensors discriminate among nine divalent metal cations (CuII, CoII, NiII, MnII, FeII, ZnII, CdII, HgII, and PbII). The unusually high and robust luminescence of these CPEs enables unprecedented sensitivity at picomolar concentrations in water. Unlike previous array‐based sensors for heavy metals using CPEs, the incorporation of distinct π‐spacer units within the polymer backbone affords more pronounced differences in each polymer's spectroscopic behavior upon interaction with each metal, ultimately producing better analytical information and improved differentiation. To demonstrate the environmental and biological utility, a simple two‐component sensing array is showcased that can differentiate nine metal cation species down to 500 × 10−12 min aqueous media and to 100 × 10−9 min seawater samples collected from the Gulf of Mexico. 
    more » « less
  3. Iodine intersects with the marine biogeochemical cycles of several major elements and can influence air quality through reactions with tropospheric ozone. Iodine is also an element of interest in paleoclimatology, whereby iodine-to-calcium ratios in marine carbonates are widely used as a proxy for past ocean redox state. While inorganic iodine in seawater is found predominantly in its reduced and oxidized anionic forms, iodide (I) and iodate (IO3), the rates, mechanisms and intermediate species by which iodine cycles between these inorganic pools are poorly understood. Here, we address these issues by characterizing the speciation, composition and cycling of iodine in the upper 1,000 m of the water column at Station ALOHA in the subtropical North Pacific Ocean. We first obtained high-precision profiles of iodine speciation using isotope dilution and anion exchange chromatography, with measurements performed using inductively coupled plasma mass spectrometry (ICP-MS). These profiles indicate an apparent iodine deficit in surface waters approaching 8% of the predicted total, which we ascribe partly to the existence of dissolved organic iodine that is not resolved during chromatography. To test this, we passed large volumes of seawater through solid phase extraction columns and analyzed the eluent using high-performance liquid chromatography ICP-MS. These analyses reveal a significant pool of dissolved organic iodine in open ocean seawater, the concentration and complexity of which diminish with increasing water depth. Finally, we analyzed the rates of IO3formation using shipboard incubations of surface seawater amended with129I. These experiments suggest that intermediate iodine species oxidize to IO3much faster than Idoes, and that rates of IO3formation are dependent on the presence of particles, but not light levels. Our study documents the dynamics of iodine cycling in the subtropical ocean, highlighting the critical role of intermediates in mediating redox transformations between the major inorganic iodine species. 
    more » « less
  4. Abstract Iron (Fe) availability impacts marine primary productivity, potentially influencing the efficiency of the biological carbon pump. Stable Fe isotope analysis has emerged as a tool to understand how Fe is sourced and cycled in the water column; however its application to sediment records is complicated by overlapping isotope signatures of different sources and uncertainties in establishing chronologies. To overcome these challenges, we integrate Fe and osmium isotope measurements with multi‐element geochemical analysis and statistical modeling. We apply this approach to reconstruct the history of Fe delivery to the South Pacific from three pelagic clay sequences spanning 93 million years. Our analysis reveals five principal Fe sources—dust, distal background, two distinct hydrothermal inputs, and a magnesium‐rich volcanic ash. Initially, hydrothermal inputs dominated Fe deposition, but as the sites migrated away from their respective mid‐ocean ridges, other sources became prominent. Notably, from 66 to 40 million years ago (Ma), distal background Fe was the primary source before a shift to increasing dust dominance around 30 Ma. This transition implies that Fe in South Pacific seawater has been dust‐dominated since ≈30 Ma, despite extremely low dust deposition rates today. We speculate that the shift to episodic and low Fe fluxes in the South Pacific and Southern Ocean over the Cenozoic helped shape an ecological niche that favored phytoplankton that adapted to these conditions, such as diatoms. Our analysis highlights how Fe delivery to the ocean is driven by large‐scale tectonic and climatic shifts, while also influencing climate through its integral role in marine phytoplankton and Earth's biogeochemical cycles. 
    more » « less
  5. Abstract Iron is an essential micronutrient for phytoplankton and plays an integral role in the marine carbon cycle. The supply and bioavailability of iron are therefore important modulators of climate over glacial-interglacial cycles. Inputs of iron from the Antarctic continental shelf alleviate iron limitation in the Southern Ocean, driving hotspots of productivity. Glacial meltwater fluxes can deliver high volumes of particulate iron. Here, we show that glacier meltwater provides particles rich in iron(II) to the Antarctic shelf surface ocean. Particulate iron(II) is understood to be more bioavailable to phytoplankton, but less stable in oxic seawater, than iron(III). Using x-ray microscopy, we demonstrate co-occurrence of iron and organic carbon-rich phases, suggesting that organic carbon retards the oxidation of potentially-bioavailable iron(II) in oxic seawater. Accelerating meltwater fluxes may provide an increasingly important source of bioavailable iron(II)-rich particles to the Antarctic surface ocean, with implications for the Southern Ocean carbon pump and ecosystem productivity. 
    more » « less