Cryogenic laser induced fluorescence characterization of U(VI) in Hanford vadose zone pore waters

Zheming Wang, John M. Zachara, Wassana Yantasee, Paul L. Gassman, Chongxuan Liu, Alan G. Joly

Research output: Contribution to journalArticle

116 Citations (Scopus)

Abstract

Ambient and liquid helium temperature laser-induced time-resolved uranyl fluorescence spectroscopy was applied to study the speciation of aqueous uranyl solutions containing carbonate and phosphate and two porewater samples obtained by ultracentrifugation of U(VI)-contaminated sediments. The significantly enhanced fluorescence signal intensity and spectral resolution found at liquid helium temperature allowed, for the first time, direct fluorescence spectroscopic observation of the higher aqueous uranyl complexes with carbonate: UO2(CO3)22-, UO2(CO 3)34-, and (UO2)2(OH) 3CO3-. The porewater samples were nonfluorescent at room temperature. However, at liquid helium temperature, both porewater samples displayed strong, well-resolved fluorescence spectra. Comparisons of the spectroscopic characteristics of the porewaters with those of the standard uranyl-carbonate complexes confirmed that U(VI) in the porewaters existed primarily as UO2(CO3)34- along with a small amount of other minor components, such as dicalcium-urano-tricarbonate complex, Ca2UO2(CO 3)3, consistent with thermodynamic calculation. The U(VI)-carbonate complex is apparently the mobile species responsible for the subsurface migration of U(VI), even though the majority of the in-ground U(VI) inventory at the site from which the samples were obtained exists as intragrain U(VI)-silicate precipitates.

Original languageEnglish (US)
Pages (from-to)5591-5597
Number of pages7
JournalEnvironmental Science and Technology
Volume38
Issue number21
DOIs
StatePublished - Nov 1 2004
Externally publishedYes

Fingerprint

laser induced fluorescence
Carbonates
vadose zone
Cryogenics
Helium
porewater
Fluorescence
Water
Lasers
helium
carbonate
fluorescence
Liquids
liquid
Silicates
Temperature
temperature
Spectral resolution
Fluorescence spectroscopy
fluorescence spectroscopy

ASJC Scopus subject areas

  • Environmental Engineering
  • Environmental Science(all)
  • Environmental Chemistry

Cite this

Cryogenic laser induced fluorescence characterization of U(VI) in Hanford vadose zone pore waters. / Wang, Zheming; Zachara, John M.; Yantasee, Wassana; Gassman, Paul L.; Liu, Chongxuan; Joly, Alan G.

In: Environmental Science and Technology, Vol. 38, No. 21, 01.11.2004, p. 5591-5597.

Research output: Contribution to journalArticle

Wang, Zheming ; Zachara, John M. ; Yantasee, Wassana ; Gassman, Paul L. ; Liu, Chongxuan ; Joly, Alan G. / Cryogenic laser induced fluorescence characterization of U(VI) in Hanford vadose zone pore waters. In: Environmental Science and Technology. 2004 ; Vol. 38, No. 21. pp. 5591-5597.
@article{af2c59ec2e61471ca904c523a2e734e8,
title = "Cryogenic laser induced fluorescence characterization of U(VI) in Hanford vadose zone pore waters",
abstract = "Ambient and liquid helium temperature laser-induced time-resolved uranyl fluorescence spectroscopy was applied to study the speciation of aqueous uranyl solutions containing carbonate and phosphate and two porewater samples obtained by ultracentrifugation of U(VI)-contaminated sediments. The significantly enhanced fluorescence signal intensity and spectral resolution found at liquid helium temperature allowed, for the first time, direct fluorescence spectroscopic observation of the higher aqueous uranyl complexes with carbonate: UO2(CO3)22-, UO2(CO 3)34-, and (UO2)2(OH) 3CO3-. The porewater samples were nonfluorescent at room temperature. However, at liquid helium temperature, both porewater samples displayed strong, well-resolved fluorescence spectra. Comparisons of the spectroscopic characteristics of the porewaters with those of the standard uranyl-carbonate complexes confirmed that U(VI) in the porewaters existed primarily as UO2(CO3)34- along with a small amount of other minor components, such as dicalcium-urano-tricarbonate complex, Ca2UO2(CO 3)3, consistent with thermodynamic calculation. The U(VI)-carbonate complex is apparently the mobile species responsible for the subsurface migration of U(VI), even though the majority of the in-ground U(VI) inventory at the site from which the samples were obtained exists as intragrain U(VI)-silicate precipitates.",
author = "Zheming Wang and Zachara, {John M.} and Wassana Yantasee and Gassman, {Paul L.} and Chongxuan Liu and Joly, {Alan G.}",
year = "2004",
month = "11",
day = "1",
doi = "10.1021/es049512u",
language = "English (US)",
volume = "38",
pages = "5591--5597",
journal = "Environmental Science & Technology",
issn = "0013-936X",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Cryogenic laser induced fluorescence characterization of U(VI) in Hanford vadose zone pore waters

AU - Wang, Zheming

AU - Zachara, John M.

AU - Yantasee, Wassana

AU - Gassman, Paul L.

AU - Liu, Chongxuan

AU - Joly, Alan G.

PY - 2004/11/1

Y1 - 2004/11/1

N2 - Ambient and liquid helium temperature laser-induced time-resolved uranyl fluorescence spectroscopy was applied to study the speciation of aqueous uranyl solutions containing carbonate and phosphate and two porewater samples obtained by ultracentrifugation of U(VI)-contaminated sediments. The significantly enhanced fluorescence signal intensity and spectral resolution found at liquid helium temperature allowed, for the first time, direct fluorescence spectroscopic observation of the higher aqueous uranyl complexes with carbonate: UO2(CO3)22-, UO2(CO 3)34-, and (UO2)2(OH) 3CO3-. The porewater samples were nonfluorescent at room temperature. However, at liquid helium temperature, both porewater samples displayed strong, well-resolved fluorescence spectra. Comparisons of the spectroscopic characteristics of the porewaters with those of the standard uranyl-carbonate complexes confirmed that U(VI) in the porewaters existed primarily as UO2(CO3)34- along with a small amount of other minor components, such as dicalcium-urano-tricarbonate complex, Ca2UO2(CO 3)3, consistent with thermodynamic calculation. The U(VI)-carbonate complex is apparently the mobile species responsible for the subsurface migration of U(VI), even though the majority of the in-ground U(VI) inventory at the site from which the samples were obtained exists as intragrain U(VI)-silicate precipitates.

AB - Ambient and liquid helium temperature laser-induced time-resolved uranyl fluorescence spectroscopy was applied to study the speciation of aqueous uranyl solutions containing carbonate and phosphate and two porewater samples obtained by ultracentrifugation of U(VI)-contaminated sediments. The significantly enhanced fluorescence signal intensity and spectral resolution found at liquid helium temperature allowed, for the first time, direct fluorescence spectroscopic observation of the higher aqueous uranyl complexes with carbonate: UO2(CO3)22-, UO2(CO 3)34-, and (UO2)2(OH) 3CO3-. The porewater samples were nonfluorescent at room temperature. However, at liquid helium temperature, both porewater samples displayed strong, well-resolved fluorescence spectra. Comparisons of the spectroscopic characteristics of the porewaters with those of the standard uranyl-carbonate complexes confirmed that U(VI) in the porewaters existed primarily as UO2(CO3)34- along with a small amount of other minor components, such as dicalcium-urano-tricarbonate complex, Ca2UO2(CO 3)3, consistent with thermodynamic calculation. The U(VI)-carbonate complex is apparently the mobile species responsible for the subsurface migration of U(VI), even though the majority of the in-ground U(VI) inventory at the site from which the samples were obtained exists as intragrain U(VI)-silicate precipitates.

UR - http://www.scopus.com/inward/record.url?scp=7544222387&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=7544222387&partnerID=8YFLogxK

U2 - 10.1021/es049512u

DO - 10.1021/es049512u

M3 - Article

C2 - 15575276

AN - SCOPUS:7544222387

VL - 38

SP - 5591

EP - 5597

JO - Environmental Science & Technology

JF - Environmental Science & Technology

SN - 0013-936X

IS - 21

ER -