Skip to main content Accessibility help

Solid-phase speciation of Zn in road dust sediment

  • J. E. S. Barrett (a1), K. G. Taylor (a1), K. A. Hudson-Edwards (a2) and J. M. Charnock (a3)


X-ray absorption spectroscopy, scanning electron microscopy (SEM) and X-ray diffractometry (XRD) have been used to study the solid-phase speciation of Zn in urban road dust sediments (RDS) in Manchester, UK. X-ray absorption near-edge structure (XANES) analysis using linear combination modelling suggest that the soluble species Zn(NO3)2·6H2O and ZnCl2 represent 70—83%, and Zn-sorbed goethite 17—30%, of the Zn species present. The presence of goethite is not corroborated by extended X-ray absorption fine structure (EXAFS) modelled first shell scattering Zn—O distances of 2.01—2.03 Å, but this may be due to distortion of the Zn octahedra on the goethite surface, or the existence of Zn-sorbed species with other metal hydrous oxides, as inferred by the EXAFS-modelled second shell Fe and Al scatterers. Analysis by EXAFS also suggests that metallic Zn-Cu-Sn-Pb and Zn-silicate phases are present in the RDS, and this is corroborated by SEM and XRD. Other phases suggested by EXAFS include ZnO, franklinite, Zn-sorbed birnessite and zinc formate. Differences between the XANES and other results suggest that model compounds such as Zn-bearing phyllosilicates and metallic Zn phases may have been missing from the XANES fitting. Long-term low-level exposure to the RDS Zn phases identified may lead to an increased risk of cardiovascular or pulmonary diseases.


Corresponding author


Hide All
Adamson, I.Y.R., Prieditis, H., Hedgecock, C. and Vincent, R. (2000) Zinc is the toxic factor in the lung response to an atmospheric particulate sample. Toxicology and Applied Pharmacology, 166, 111–119.
Alexander, B.H., Checkoway, H., Wechsler, L., Heyer, N.J., Muhm, J.M. and O’Keeffe, T.P. (1996) Lung cancer in chromate-exposed aerospace workers. Journal of Occupational and Environmental Medicine, 38, 1253–1258.
Barrett, J.E., Taylor, K.G., Hudson-Edwards, K.A. and Charnock, J.M. (2010) Solid-phase speciation of Pb in urban road dust sediment: a XANES and EXAFS study. Environmental Science & Technology, 44, 2940–2946.
Bear, I.J., Grey, I.E., Madsen, I.C., Newnham, I.E. and Rogers, L.J. (1986) Structures of the basic zinc sulfates 3Zn(OH)2.ZnSO4.mH2O, m = 3 and 5. Acta Crystallographica Section, B42, 39–.
Bochatay, L. and Persson, P. (2000) Metal ion coordination at the water-manganite (g-MnOOH) interface II. An EXAFS study of zinc (II). Journal of Colloid and Interface Science, 229, 593–599.
Boudesocque, S., Guillon, E., Aplincourt, M., Marceau, E. and Stievano, L. (2007) Sorption of Cu(II) onto vineyard soils: macroscopic and spectroscopic investigations. Colloid and Interface Science, 307, 40–49.
Calderón-Garcidueñas, L., Reed, W., Maronpot, R.R., Henríquez-Roldán, C., Delgado-Chavez, R., Calderón-Garcidueñas, A., Dragustinovis, I., Franco-Lira, M., Aragón-Flores, M., Solt, A.C., Altenburg, M., Torres-Jardón, R. and Swenberg, J.A. (2004) Brain inflammation and Alzheimer’s-like pathology in individuals exposed to severe air pollution. Toxicologic Pathology, 32, 650–658.
Charlesworth, S.M. and Lees, J.A. (1999) The distribution of heavy metals in deposited dusts and sediments, Coventry, UK. Environmental Geochemistry and Health, 21, 97–115.
Chisholm-Brause, C.J., Hayes, K.F., Roe, A.L., Brown, G.E., Jr., Parks, G.A. and Leckie, J.O. (1990) Spectroscopic investigation of Pb(II) complexes at the g-Al2O3/water interface. Geochimica et Cosmochimica Acta, 54, 1897–1909.
Clozel, B., Ruban, V., Durand, C. and Conil, P. (2006) Origin and mobility of heavy metals in contaminated sediments from retention and infiltration ponds. Applied Geochemistry, 21, 1781–1798.
Ferrari, A., Braibanti, A., Lanfredi, A.M.M. and Tiripicchio, A. (1967) Crystal structures of nitrates of divalent hexaquocations. I. Hexaquozinc nitrate. Acta Crystallographica, 22, 240–246.
Fletcher, D.A., McMeeking, R.F. and Parkin, D. (1996) The United Kingdom Chemical Database Service. Journal of Chemical Information and Computer Sciences, 749–.
Garcia-Martinez, O., Rojas, R.M., Vila, E. and Martin de Vidales, J.L. (1993) Microstructural characterization of nanocrystals of ZnO and CuO obtained from basic salts. Solid State Ionics, 63–65, 449–.
Gaudon, M., Pailhé, N., Wattiaux, A. and Demourgues, A. (2009) Structural defects in AFe2O4 (A = Zn, Mg) spinels. Materials Research Bulletin, 44, 484–.
Galasso, S.L. and Dyck, R.H. (2007) The role of zinc in cerebral ischemia. Molecular Medicine, 13, 380–387.
Ghose, S. (1964) The crystal structure of hydrozincite, Zn5(OH)6(CO3)2 . Acta Crystallographica, 17, 1051–1057.
Gibson, M.J. and Farmer, J.G. (1984) Chemical partitioning of trace metal contaminants in urban street dirt. Science of the Total Environment, 33, 49–57.
Gilmour, P.S., Nyska, A., Schladweiler, M.C., McGee, J.K., Wallenborn, J.G., Richards, J.H. and Kodavanti, U.P. (2006) Cardiovascular and blood coagulative effects of pulmonary zinc exposure. Toxicology and Applied Pharmacology, 221, 41–52.
Gourdon, O., Gout, D., Williams, D.J., Proffen, T., Hobbs, S. and Miller, G.J. (2007) Atomic distributions in the g-brass structure of the Cu-Zn system: a structural and theoretical study. Inorganic Chemistry, 46, 251–260.
Groat, L.A. (1996) The crystal structure of namuwite, a mineral with Zn in tetrahedral and octahedral coordination, and its relationship to the synthetic basic zinc sulfates. American Mineralogist, 81, 238–243.
Grice, J.D. and Dunn, P.J. (1989) Sclarite, a new mineral from Franklin, New Jersey, with essential octahedrally and tetrahedrally coordinated zinc: description and structure refinement. American Mineralogist, 74, 1355–1359.
Harrison, R.M., Laxen, D.P.H. and Wilson, S.J. (1981) Chemical associations of lead, cadmium, copper, and zinc in street dusts and roadside soils. Environmental Science & Technology, 15, 1378–1383.
Hesterberg, D., Sayers, D.E., Zhou, W., Plummer, G.M. and Robarge, W.P. (1997) X-ray absorption spectroscopy of lead and zinc speciation in a contaminated groundwater aquifer. Environmental Science & Technology, 31, 2840–2846.
Hopke, P.K., Lamb, R.E. and Natusch, D.F.S. (1980) Multielemental characterization of urban roadway dust. Environmental Science & Technology, 14, 164–171.
Huang, X., Atwood, C.S., Moir, R.D., Hartshorn, M.A., Vonsattel, J.-P., Tanzi, R.E. and Bush, A.I. (1997) Zinc-induced Alzheimer's Ab1–40 aggregation is mediated by conformational factors. The Journal of Biological Chemistry, 272, 26464–26470.
Juillot, F., Morin, G., Ildefonse, P., Trainor, T.P., Benedetti, M., Galoisy, L., Calas, G. and Brown, G.E., Jr. (2003) Occurrence of Zn/Al hydrotalcite in smelter-impacted soils from northern France: Evidence from EXAFS spectroscopy and chemical extractions. American Mineralogist, 88, 509–526.
Khan, T., Murty, B.V.R. and Schubert, K. (1970) über die struktur der mischung platin-kupfer-zink. Journal of the Less Common Metals, 21, 293–303.
Kirpichtchikova, T. A., Manceau, A., Spadini, L., Panfili, F., Marcus, M.A. and Jacquet, T. (2006) Speciation and solubility of heavy metals in contaminated soil using X-ray microfluorescence, EXAFS spectroscopy, chemical extraction, and thermodynamic modeling. Geochimica et Cosmochimica Acta, 70, 2163–2190.
Kodavanti, U.P., Schladweiler, M.C., Gilmour, P.S., Wallenborn, J.G., Mandavilli, B.S., Ledbetter, A.D., Christiani, D.C., Runge, M.S., Karoly, E.D., Costa, D.L., Peddada, S., Jaskot, R., Richards, J.H., Thomas, R., Madamanchi, N.R. and Nyska, A. (2008) The role of particulate matter-associated zinc in cardiac injury in rats. Environmental Health Perspectives, 16, 13–21.
Li, X., Shen, Z., Wai, O.W.H. and Li, Y.-S. (2001) Chemical forms of Pb, Zn and Cu in the sediment profiles of the Pearl River estuary. Marine Pollution Bulletin, 42, 215–223.
Manceau, A., Chateigner, D. and Gates, W.P. (1998) Polarized EXAFS, distance-valence least-squares modeling (DVLS) and quantitative texture analysis approached to the structural refinements of Garfield nontronite. Physics and Chemistry of Minerals, 25, 347–36.
Manceau, A., Lanson, B., Schlegel, M.L., Harge, J.C., Musso, M., Eybert-Bérard, L., Hazemann, J.-L., Chateigner, D. and Lamble, G.M. (2000) Quantitative Zn speciation in smelter-contaminated soils by EXAFS spectroscopy. American Journal of Science, 300, 289–343.
Manceau, A., Marcus, M.A. and Tamura, N. (2002) Quantitative speciation of heavy metals in soils and sediments by synchrotron X-ray techniques. Pp. 341–428 in: Applications of Synchrotron Radiation i n Low-temperature Geochemistry and Environmental Science (Fenter, P.A., Rivers, M.L., Sturchio, N.C. and Sutton, S.R., editors). Reviews in Mineralogy and Geochemistry, 49. Mineralogical Society of America, Washington DC, and the Geochemical Society, St. Louis, Missouri, USA.
O’Day, P., Carroll, S.A. and Waychunas, G.A. (1998) Rock-water interactions controlling zinc, cadmium, and lead concentrations in surface waters and sediments U.S. Tri-state Mining District. 1. Molecular identification using X-ray absorption spectroscopy. Environmental Science & Technology, 32, 943–955.
Parkman, R.H., Charnock, J.M., Bryan, N.D., Livens, F.R. and Vaughan, D.J. (1999) Reactions of copper and cadmium ions in aqueous solutions with goethite, lepidocrocite, mackinawite and pyrite. American Mineralogist, 84, 407–419.
Prieditis, H. and Adamson, I.Y.R. (2002) Comparative pulmonary toxicity of various soluble metals found in urban particulate dusts. Experimental Lung Research, 28, 563–576.
Robertson, D.J., Taylor, K.G. and Hoon, S.R. (2003) Geochemical and mineral characterisation of urban sediment particulates, Manchester, UK. Applied Geochemistry, 18, 269–282.
Samudralwar, D.L., Diprete, C.C., Ni, B.-F., Ehmann, W.D. and Markesbery, W.R. (1995) Elemental imbalances in the olfactory pathway in Alzheimer's disease. Journal of the Neurological Sciences, 130, 139–145.
Sarret, G., Manceau, A., Spadini, L., Roux, J.-C., Hazemann, J.-L., Soldo, Y., Eybert-Bérard, L. and Menthonnex, J.J. (1998) Structural determination of Zn and Pb binding sites in Penicillium chrysogenum cell walls by EXAFS spectroscopy. Environmental Science & Technology, 32, 1648–1655.
Schlegel, M.L., Manceau, A. and Charlet, L. (1997) EXAFS Study of Zn and ZnEDTA sorption at the goethite (α-FeOOH)/water interface. Journal de Physique IV, 7(C2), 824–.
Schlegel, M.L., Manceau, A., Charlet, L., Chateigner, D. and Hazemann, J.-L. (2001a) Sorption of metal ions on clay minerals. III. Nucleation and epitaxial growth of Zn phyllosilicate on the edges of hectorite. Geochimica et Cosmochimica Acta, 65, 4155–4170.
Schlegel, M.L., Manceau, A., Charlet, L. and Hazemann, J.-L. (2001b) Adsorption mechanisms of Zn on hectorite as a function of time, pH and ionic strength. America Journal of Science, 301, 798–830.
Shabanzadeh, A.P-., Shuaib, A., Yang, T., Salam, A. and Wang, C.X. (2004) Effect of zinc in ischemic brain injury in an embolic model of stroke in rats. Neuroscience Letters, 356, 69–71.
Shimizu, S., Murakami, Y. and Kachi, S. (1976) Lattice softening and martensitic transformation in Cu-Ni-Zn b phase alloys. Journal of the Physical Society of Japan, 41, 79–84.
Strozyk, D., Launer, L.J., Adlard, P.A., Cherny, R.A., Tsatsanis, A., Volitakis, I., Blennowd, K., Petrovitch, H., White, L.R. and Bush, A.I. (2009) Zinc and copper modulate Alzheimer Ab levels in human cerebrospinal fluid. Neurobiology of Aging, 30, 1069–1077.
Taylor, K.G. and Owens, P.N. (2009) Sediments in urban river basins: a review of sediment-contaminant dynamics in an environmental system conditioned by human activities. Journal of Soils and Sediments, 9, 281–303.
Taylor, K.G. and Robertson, D.J. (2009) Electron microbeam analysis of urban road-deposited sediment, Manchester, UK: improved source discrimination and metal speciation assessment Applied Geochemistry, 24, 1261–1269.
Teo, B.K. (1986) EXAFS: Basic Principles and Data Analysis (Inorganic Chemistry Concept v. 9. Springer-Verlag, NewYork, USA.
Thorpe, A. and Harrison, R.M. (2008) Sources and properties of non-exhaust particulate matter from road traffic: a review. Science of the Total Environment, 400, 270–282.
Trainor, T.P., Brown, G.E., Jr. and Parks, G.A. (2000) Adsorption and precipitation of aqueous Zn(II) on alumina powders. Journal of Colloid and Interface Science, 231, 359–372.
Viertelhaus, M., Adler, P., Clérac, R., Anson, C.E. and Powell, A.K. (2005) Iron(II) formate [Fe(O2CH)2]· 1/3HCO2H: amesoporous magnet – solvothermal syntheses and crystal structures of the isomorphous framework metal (II) formates [M(O2CH)2]·n(solvent) (M = Fe, Co, Ni, Zn, Mg). European Journal of Inorganic Chemistry, 2005, 692–703.
Wadsley, A.D. (1955) The crystal structure of chalcophanite, ZnMn 3O7. 3H2O. Acta Crystallographica, 8, 165–172.
Wallenborn, J.G., Evansky, P., Shannahan, J.H., Vallanat, B., Ledbetter, A.D., Schladweiler, M.C., Richards, J.H., Gottipolu, R.R., Nyska, A. and Kodavanti, U.P. (2008) Subchronic inhalation of zinc sulfate induces cardiac changes in healthy rats. Toxicology and Applied Pharmacology, 232, 69–77.
Waychunas, G.A., Fuller, C.C. and Davis, J.A. (2002) Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite: I. X-ray absorption extended fine structure spectroscopy analysis. Geochimica et Cosmochimica Acta, 66, 1119–1137.
Waychunas, G.A., Fuller, C.C., Davis, J.A. and Rehr, J.J. (2003) Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite: II. XANES analysis and simulation. Geochimica et Cosmochimica Acta, 67, 1031–1043.
Xia, K., Bleam, W. and Helmke, P.A. (1997) Studies of the nature of binding sites of first row transition elements bound to aquatic and soil humic substances using X-ray absorption spectroscopy. Geochimica et Cosmochimica Acta, 61, 2223–2235.


Related content

Powered by UNSILO

Solid-phase speciation of Zn in road dust sediment

  • J. E. S. Barrett (a1), K. G. Taylor (a1), K. A. Hudson-Edwards (a2) and J. M. Charnock (a3)


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed.