Spectroscopic Evidence for Ni(Ii) Surface Speciation at the Iron Oxyhydroxides-Water Interface

Journal Article · Mon May 11 04:00:00 EDT 2009 · Environ. Sci. Tech. 42:1151,2008

OSTI ID:958622

Arai, Y

Understanding in situ metal surface speciation on mineral surfaces is critical to predicting the natural attenuation of metals in the subsurface environment. In this study, we have demonstrated the novel Ni K-edge X-ray absorption spectroscopy (XAS) measurements needed to understand Ni(II) surface speciation in three synthetic iron oxyhydroxides (ferrihydrite, goethite, and hematite). The adsorption of Ni gradually increases with increasing pH from 5 to 8, and the adsorption edge appears at near the point of zero salt effect (PZSE) of the solids. The results of XAS analysis indicate four different Ni inner-sphere surface species are present. While total Ni surface species in hematite at pH 6.85 surfaces consist of {approx}63% face-sharing (interatomic distance of Ni-Fe (R{sub Ni-Fe}) {approx}2.9 {angstrom}) and {approx}37% corner-sharing (R{sub Ni-Fe} 4.0 {angstrom}) surface species on iron octahedra, a combination of two different edge-sharing (between NiO{sub 6} and FeO{sub 6} octahedra, in chains or in rows) and corner-sharing surface species are observed in goethite and ferrihydrite at pH 5.09-6.89. In ferrihydrite, approximately 70% of surface species are edge-sharing surface species (in chains) (R{sub Ni-Fe} 3.0 {angstrom}), followed by {approx}30% of edge-sharing species (in rows) (R{sub Ni-Fe} {approx}3.2 {angstrom}) and {approx}3-5% of corner-sharing surface species (R{sub Ni-Fe} 4.0{angstrom}). Goethite contains {approx}54% edge-sharing (R{sub Ni-Fe} 3.0 {angstrom}), {approx}26% edge-sharing (R{sub Ni-Fe} {approx}3.2 {angstrom}), and 20% corner-sharing surface species. These findings indicate that the reactivity and surface speciation of Ni are sensitive to the crystallinity of iron oxyhydroxides. The spectroscopic evidence for multi-Ni surface speciation should be factored into predictions of the transport of Ni in soil-water environments.

• Research Organization: Stanford Linear Accelerator Center (SLAC)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC02-76SF00515
• OSTI ID: 958622
• Report Number(s): SLAC-REPRINT-2009-066
• Journal Information: Environ. Sci. Tech. 42:1151,2008, Journal Name: Environ. Sci. Tech. 42:1151,2008 Journal Issue: 4 Vol. 42; ISSN ESTHAG; ISSN 0013-936X
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
ABSORPTION SPECTROSCOPY
CHEMICAL STATE
ENVIRONMENTAL TRANSPORT
GOETHITE
HEMATITE
IRON HYDROXIDES
NATURAL ATTENUATION
NICKEL
Other
ENV
PH VALUE
SORPTIVE PROPERTIES
X-RAY SPECTROSCOPY