Speciation of Uranium by Electrospray Ionization Mass Spectrometry: Comparison with Time-Resolved Laser-Induced Fluorescence

Moulin, Christophe; Charron, N.; Plancque, Gabriel; Virelizier, H.

doi:10.1366/0003702001950201

Cited by 60 publications

(48 citation statements)

References 25 publications

(22 reference statements)

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“…No other direct speciation methods are currently available for measuring specific U species in natural surface waters. Techniques such as electrospray ionization mass spectrometry [42] or photothermal (displacement) spectroscopy [43] may prove useful for determining U speciation in natural waters after further development. and uranyl-humic complexes in water [115] Size exclusion chromatography (± inductively coupled plasma mass spectrometry) Dissolved and colloidal U (U complexation with humic and fulvic acids) in water [27] Ion exchange chromatography (± inductively coupled plasma mass spectrometry)…”

Section: Watermentioning

confidence: 99%

Uranium Speciation and Bioavailability in Aquatic Systems: An Overview

Markich

2002

The Scientific World JOURNAL

200

142

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The speciation of uranium (U) in relation to its bioavailability is reviewed for surface waters (fresh-and seawater) and their sediments. A summary of available analytical and modeling techniques for determining U speciation is also presented. U(VI) is the major form of U in oxic surface waters, while U(IV) is the major form in anoxic waters. The bioavailability of U (i.e., its ability to bind to or traverse the cell surface of an organism) is dependent on its speciation, or physicochemical form. U occurs in surface waters in a variety of physicochemical forms, including the free metal ion (U 4+ or UO 2 2+ ) and complexes with inorganic ligands (e.g., uranyl carbonate or uranyl phosphate), and humic substances (HS) (e.g., uranyl fulvate) in dissolved, colloidal, and/or particulate forms. Although the relationship between U speciation and bioavailability is complex, there is reasonable evidence to indicate that UO 2 2+ and UO 2 OH + are the major forms of U(VI) available to organisms, rather than U in strong complexes (e.g., uranyl fulvate) or adsorbed to colloidal and/or particulate matter. U(VI) complexes with inorganic ligands (e.g., carbonate or phosphate) and HS apparently reduce the bioavailability of U by reducing the activity of UO 2 2+ and UO 2 OH + . The majority of studies have used the results from thermodynamic speciation modeling to support these conclusions. Time-resolved laser-induced fluorescence spectroscopy is the only analytical technique able to directly determine specific U species, but is limited in use to freshwaters of low pH and ionic strength. Nearly all of the available information relating the speciation of U to its bioavailability has been derived using simple, chemically defined experimental freshwaters, rather than natural waters. No data are available for estuarine or seawater. Furthermore, there are no available data on the relationship between U speciation and bioavailability in sediments. An understanding of this relationship has been hindered due to the lack of direct quantitative U speciation techniques for particulate phases. More robust analytical techniques for determining the speciation of U in natural surface waters are needed before the relationship between U speciation and bioavailability can be clarified.

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Section: Watermentioning

confidence: 99%

Uranium Speciation and Bioavailability in Aquatic Systems: An Overview

Markich

2002

The Scientific World JOURNAL

200

142

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“…Charged uranyl coordination complexes can be formed using electrospray-ionization (ESI), which has proven to be a highly versatile means for introducing these species into the gas phase. Recent research by our group [22][23][24][25][26], that of Moulin [27,28], and Pasilis [29] have demonstrated the great utility of ESI for forming a variety of dioxouranium V and VI complexes. ESI usually produces multiple species, however, complexes of interest can be isolated on the basis of mass-to-charge ratio using selective ion ejection/storage capabilities of a trapped ion mass spectrometer.…”

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confidence: 99%

Variable denticity in carboxylate binding to the uranyl coordination complexes

Groenewold

Jong

Stipdonk

2010

J. Am. Soc. Mass Spectrom.

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Tris-carboxylate complexes of uranyl [UO 2 ] 2ϩ with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transform ion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetato uranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric ϪCO 2 stretches of the monodentate and bidentate acetate, CH 3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the predominant conformer of the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate and two bidentate benzoate ligands.

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“…One major difficulty is the paucity of methods that can be used to distinguish specific molecular species at low concentration in solution. Electrospray ionization mass spectrometry (ESI-MS) can provide molecular weight and structural information and has been used successfully for molecular characterization of U(VI) complexes with ligands of environmental or biological interest [1][2][3][4][5]. However, much fundamental work on the complex gas-phase chemistry of U(VI) and U(VI)-containing species remains to be done before ESI-MS can be used to characterize U(VI) species in natural waters.…”

mentioning

confidence: 99%

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry

Pasilis

Somogyi

Herrmann

et al. 2006

J. Am. Soc. Mass Spectrom.

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Electrospray ionization (ESI) of uranyl nitrate solutions generates a wide variety of positively and negatively charged ions, including complex adducts of uranyl ions with methoxy, hydroxy, and nitrate ligands. In the positive ion mode, ions detected by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry are sensitive to instrumental tuning parameters such as quadrupole operating frequency and trapping time. Positive ions correspond to oligomeric uranyl nitrate species that can be characterized as having a general formula of

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Speciation of Uranium by Electrospray Ionization Mass Spectrometry: Comparison with Time-Resolved Laser-Induced Fluorescence

Cited by 60 publications

References 25 publications

Uranium Speciation and Bioavailability in Aquatic Systems: An Overview

Uranium Speciation and Bioavailability in Aquatic Systems: An Overview

Variable denticity in carboxylate binding to the uranyl coordination complexes

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry

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