Evaluation of Immobilized Metal-Ion Affinity Chromatography and Electrospray Ionization Tandem Mass Spectrometry for Recovery and Identification of Copper(II)-Binding Ligands in Seawater Using the Model Ligand 8-Hydroxyquinoline

Nixon, Richard L.; Ross, Andrew R. S.

doi:10.3389/fmars.2016.00246

Cited by 9 publications

(3 citation statements)

References 47 publications

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“…To structurally characterize and confirm potential sources of Cu binding organic ligands in the SoG, CLE-ACSV (i.e., under multiple detection windows) should be combined with other techniques, such as HPLC-ESI-MS (McCormack et al, 2003;Ross et al, 2003;Nixon and Ross, 2016), allowing comparisons of speciation data from field samples and those from phytoplankton and bacteria cultures (Whitby et al, 2018). Additionally, ligand parameters should be complemented with concentrations of potential ligands, such as thiols and humic substances (Laglera and Tovar-Sańchez, 2012;Whitby et al, 2018), as well as DOC, CDOM across a wider range of wavelengths, suspended particulate matter, colloidal trace metal fractions (Bertine and VernonClark, 1996;Kogut and Voelker, 2003;Moriyasu and Moffett, 2022) and other proxies, while considering time delays between biological parameters and Cu ligand parameters (Dryden et al, 2007), informed by cell cultures (Leal et al, 1999;Gordon et al, 2000).…”

Section: Possible Ligand Sources In Sogmentioning

confidence: 99%

Seasonal dissolved copper speciation in the Strait of Georgia, British Columbia, Canada

et al. 2022

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The Strait of Georgia (SoG) is a semi-enclosed, urban basin with seasonally dependent estuarine water circulation, dominantly influenced by Northeast Pacific waters and the Fraser River. To establish a baseline and understand the fate and potential toxicity of Cu in the SoG, we determined seasonal and spatial depth profiles of dissolved Cu (dCu) speciation, leading to estimates of the free hydrated copper (Cu2+) concentrations, as a proxy for Cu toxicity. The concentration of dCu was largely controlled by conservative mixing of the ocean and freshwater endmembers in the SoG. In all samples, ligand concentrations exceeded dCu, by a ratio greater than 1.5, resulting in the complexation of 99.98% of the dCu by strong binding organic ligands. The concentrations of Cu2+ were less than 10-13.2 M, significantly lower than the well-established Cu toxicity threshold (10-12 M Cu2+) for microorganisms. Our results indicate that ambient Cu-binding ligands effectively buffer Cu2+ concentrations within the Strait of Georgia, posing no threat to marine life. In almost 90% of the samples, the ligands were best classified as a single ligand class, with a logKCuL,Cu2+cond between 12.5 and 14.1. The concentrations of these single class ligands were greatest in warm, low salinity, nutrient depleted waters, suggesting that either terrestrially sourced ligands dominate dCu speciation in the SoG, or freshwater sources in the SoG establish the conditions that promote the production of Cu binding ligands in its surface waters. The remaining 10% of the samples were from the euphotic zone, where we detected a stronger ligand class, L1, of logKCuL1,Cu2+cond between 13.5 and 14.3, and a weaker ligand class, L2, of logKCuL2,Cu2+cond between 11.5 and 12.3. In these surface samples, logKCuL1,Cu2+cond and logKCuL2,Cu2+cond were positively correlated with temperature, while L2 concentrations were positively correlated with chromophoric dissolved organic matter of terrestrial origin. This study is the first to perform hierarchal clustering of a trace metal speciation dataset and enabled the distinction of 6 clusters across season, depth, and region of the SoG, highlighting the influence of freshwater and open ocean ligand sources, conservative mixing dynamics, and particulate Cu concentrations on dCu speciation within estuarine basins.

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Section: Possible Ligand Sources In Sogmentioning

confidence: 99%

Seasonal dissolved copper speciation in the Strait of Georgia, British Columbia, Canada

et al. 2022

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“…CSV provides the concentration and complexation strength of the pool of copper ligands, but no molecular level information about the compounds is obtained. Only recently have mass spectrometric techniques begun to be used to characterize CuLs in seawater Nixon & Ross, 2016;Waska et al, 2015;. While these studies have yielded some molecular level information about CuLs such as their molecular weight, formula, and structural functionalities, we have yet to obtain the complete structure of any CuL species in seawater, nearly 6 decades after it was first proposed that soluble Cu was chelated by organics.…”

Section: Methods To Measure Copper Speciationmentioning

confidence: 99%

“…In the past several years, techniques using mass spectrometry have advanced and are being used to investigate the molecular level speciation of copper. These methodologies employ an array of techniques to extract copper ligands and simplify the seawater matrix, such as solid phase extraction Waska et al, 2015; and immobilized metal-ion affinity chromatography (IMAC; Nixon & Ross, 2016;. The extracts are then analyzed using soft ionization mass spectrometry (MS) methods such as matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) MS, and Fourier transform ion cyclotron resonance (FT-ICR) MS.…”

Section: Figure 12mentioning

confidence: 99%

Molecular characterization of organically bound copper in the marine environment

Babcock-Adams¹

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Marine microbes require copper (Cu) for a variety of key enzymes and can therefore experience limitation when concentrations are low. However, when Cu concentrations are too high, it becomes toxic causing decreased cell growth and even cell death. Laboratory culture experiments have shown that a diverse array of microbes produce organic ligands that complex Cu (CuL) and buffer the free ion concentration, which is the most bioavailable fraction. In this way, the microbes impose a control on the speciation of Cu, decreasing the toxic effects of Cu and making seawater conditions favorable for growth. Studies have shown that CuL complexes produced in laboratory cultures have similar complexation strengths to those found in seawater samples, which suggests a biological source of CuLs in seawater where dissolved Cu is almost entirely bound by organic ligands. However, information about individual CuL complexes is lacking which limits our understanding of the sources, sinks, and cycling of dissolved Cu. In order to fill this gap in knowledge, molecular level information about CuL complexes produced in culture and found in seawater must be obtained. To investigate this, liquid chromatography (LC) was coupled to two mass spectrometers (MS), an inductively coupled plasma (ICP) MS and an electrospray ionization (ESI) MS. By using data supplied by both techniques, the molecular charateristics of CuLs were determined laboratory cultures of the marine diatom Phaeodactylum tricornutum and the cyanobacterium Synechococcus, as well as investigating the distribution of CuLs in natural seawater samples along a line from 56°N to 20°S, along 152°W through the north and central Pacific Ocean. The CuLs identified in laboratory cultures had molecular formulae and fragmentation patterns characteristic of linear tetrapyrroles, a group of organic compounds commonly found in biological systems. This identification was further supported by absorbance and nuclear magnetic resonance spectroscopy. The distribution of CuLs in the Pacific Ocean showed a highly dynamic and complex mixture of ligands, closely tied to biological cycles.

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Fe(III)-based immobilized metal–affinity chromatography (IMAC) method for the separation of the catechol siderophore from Bacillus tequilensis CD36

Jiang

Gao

et al. 2018

3 Biotech

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Catechol siderophore plays an important role in microbial ecology, agriculture, and medicine, but its research is often limited by the difficulty in acquisition of it in large quantities. Based on evidence from the coordination chemistry and chemical biology, catechol siderophore could chelate Fe with high affinity. Therefore, Fe(III)-based immobilized metal-affinity chromatography (IMAC) was applied to capture siderophore from the culture filtrate of CD36. The ethanol-precipitated sample and the separated sample from Fe(III)-based IMAC were analyzed by liquid chromatography-mass spectrometry. According to the result, the pure siderophore DHB-Gly-Thr could be extracted from the ethanol-precipitated sample. Compared with other purifications, Fe(III)-based IMAC was convenient and had fewer steps. In addition, it also reduced the use of toxic chemical solvents in some traditional extraction process, such as extraction and ion exchange chromatography. Fe(III)-based IMAC was successfully used in separation of the catechol siderophore from CD36. The results revealed that Fe(III)-based IMAC was an efficient and environmentally friendly method for the separation and purification of catechol siderophore.

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Evaluation of Immobilized Metal-Ion Affinity Chromatography and Electrospray Ionization Tandem Mass Spectrometry for Recovery and Identification of Copper(II)-Binding Ligands in Seawater Using the Model Ligand 8-Hydroxyquinoline

Cited by 9 publications

References 47 publications

Seasonal dissolved copper speciation in the Strait of Georgia, British Columbia, Canada

Seasonal dissolved copper speciation in the Strait of Georgia, British Columbia, Canada

Molecular characterization of organically bound copper in the marine environment

Fe(III)-based immobilized metal–affinity chromatography (IMAC) method for the separation of the catechol siderophore from Bacillus tequilensis CD36

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