Soil Research Soil Research Society
Soil, land care and environmental research
RESEARCH ARTICLE

Association of trace elements and dissolution rates of soil iron oxides

D. Ketrot A B , A. Suddhiprakarn A , I. Kheoruenromne A and B. Singh B C

A Department of Soil Science, Faculty of Agriculture, Kasetsart University, Chatuchak, Bangkok 10900, Thailand.

B Faculty of Agriculture and Environment, University of Sydney, NSW 2006, Australia.

C Corresponding author. Email: balwant.singh@sydney.edu.au

Soil Research 52(1) 1-12 http://dx.doi.org/10.1071/SR13092
Submitted: 21 March 2013  Accepted: 2 September 2013   Published: 5 February 2014

Abstract

In this study, nine Oxisols and five Ultisols from Thailand were used to determine the association of major and trace elements with iron (Fe) oxides. The Fe oxides were concentrated and the association of elements (Al, Ca, Cu, Cr, Mg, Mn, Ni, Pb, P, Si, V, Ti, Zn) with Fe was evaluated using batch dissolution in 1 m HCl at 20°C. The dissolution behaviour of Fe oxide concentrates was determined using batch dissolution and flow-through reactors. In addition to Fe, both Al and Ti were present in significant amounts in the Fe oxide concentrates. Manganese was the most abundant trace element, and Cu, Zn, Pb and As concentrations were <250 mg kg–1 in most samples. The dissolution behaviour of Fe-oxide concentrates indicated that Al, Cr and V were mostly substituted for Fe3+ in the structure of goethite and hematite. A significant proportion of Mn, Ni, Co, Pb and Si was also present within the structure of these minerals. Some Mg, Cu, Zn, Ti and Ca was also associated with Fe oxides. The dissolution kinetics of Fe oxide concentrates was well described by three models, i.e. the cube root law, Avrami–Erofejev equation and Kabai equation, with the dissolution rate constants (103k) corresponding to the three models ranging from 0.44 to 6.11 h–1, from 1.01 to 4.40 h–1 and from 0.03 to 4.12 h–1, respectively. The k constants of Fe oxide concentrates in this study were significantly and negatively correlated with the mean crystal dimension derived from [110] and [104] of hematite, the dominant mineral in most samples. The steady-state dissolution rate of a soil Fe-oxide concentrate (sample Kk) was substantially higher than for synthetic goethite under highly acidic conditions; this is possibly due to the greater specific surface area of sample Kk than the synthetic goethite.

Additional keywords: acid dissolution, batch method, Fe oxide concentrate, non-stirred flow through reactor method, total element concentration, tropical red soils.


References

Agbenin JO (2003) Extractable iron and aluminum effects on phosphate sorption in a savanna Alfisols. Soil Science Society of America Journal 67, 589–595.
Extractable iron and aluminum effects on phosphate sorption in a savanna Alfisols.CrossRef | 1:CAS:528:DC%2BD3sXkslChsbo%3D&md5=0a8efe23c1beec2c76a58cbca6b04366CAS | open url image1

Alvarez M, Sileo EE, Rueda EH (2005) Effect of Mn(II) incorporation on the transformation of ferrihydrite to goethite. Chemical Geology 216, 89–97.
Effect of Mn(II) incorporation on the transformation of ferrihydrite to goethite.CrossRef | 1:CAS:528:DC%2BD2MXhs1GntLY%3D&md5=bccaf65bc4a742bfa9ff39bd8e0cca03CAS | open url image1

Alvarez M, Rueda EH, Sileo EE (2007) Simultaneous incorporation of Mn and Al in the goethite structure. Geochimica et Cosmochimica Acta 71, 1009–1020.
Simultaneous incorporation of Mn and Al in the goethite structure.CrossRef | 1:CAS:528:DC%2BD2sXht1Gltrg%3D&md5=4e018649ba32e483024901d5716b81dcCAS | open url image1

Alvarez M, Sileo EE, Rueda EH (2008) Structure and reactivity of synthetic Co-substituted goethites. The American Mineralogist 93, 584–590.
Structure and reactivity of synthetic Co-substituted goethites.CrossRef | 1:CAS:528:DC%2BD1cXksVKjsbo%3D&md5=562c4ffd928006e3ef20082ab77368c8CAS | open url image1

Angove MJ, Wells JD, Johnson BB (1999) The influence of temperature on the adsorption of cadmium(II) and cobalt(II) on goethite. Journal of Colloid and Interface Science 211, 281–290.
The influence of temperature on the adsorption of cadmium(II) and cobalt(II) on goethite.CrossRef | 1:CAS:528:DyaK1MXhtlCisrk%3D&md5=ede2992c6f468c7d972bc36940adc98aCAS | 10049544PubMed | open url image1

Aylmore LAG, Sills ID, Quirk JP (1970) Surface area of homoionic illite and montmorillonite clay mineral as measured by the sorption of nitrogen and carbon dioxide. Clays and Clay Minerals 18, 91–96.
Surface area of homoionic illite and montmorillonite clay mineral as measured by the sorption of nitrogen and carbon dioxide.CrossRef | 1:CAS:528:DyaE3cXlt1ert7w%3D&md5=2bdfb6702f698ef96c130182d75f6254CAS | open url image1

Bibi I, Singh B, Silvester E (2011) Dissolution of illite in saline-acidic solutions at 25°C. Geochimica et Cosmochimica Acta 75, 3237–3249.
Dissolution of illite in saline-acidic solutions at 25°C.CrossRef | 1:CAS:528:DC%2BC3MXltlyktLw%3D&md5=e745ec23dad0f305f319a713a817e85cCAS | open url image1

Bigham JM, Heckendorn SE, Jaynes WF, Smeck NE (1991) Stability of iron oxides in two soils with contrasting colors. Soil Science Society of America Journal 55, 1485–1492.
Stability of iron oxides in two soils with contrasting colors.CrossRef | 1:CAS:528:DyaK38Xmtlyjuw%3D%3D&md5=1f6f2721519b65020e82dfd0f44af9b0CAS | open url image1

Börling K, Otabbong E, Barberis E (2001) Phosphorus sorption in relation to soil properties in some cultivated Swedish soils. Nutrient Cycling in Agroecosystems 59, 39–46.
Phosphorus sorption in relation to soil properties in some cultivated Swedish soils.CrossRef | open url image1

Cervini-Silva J, Sposito G (2002) Steady-state dissolution kinetics of aluminum-goethite in the presence of desferrioxamine-B and oxalate ligands. Environmental Science & Technology 36, 337–342.
Steady-state dissolution kinetics of aluminum-goethite in the presence of desferrioxamine-B and oxalate ligands.CrossRef | 1:CAS:528:DC%2BD38XhtFantw%3D%3D&md5=2ce92b7fe4e1a2a6d7705ca8f8f17b16CAS | open url image1

Cheah SF, Kraemer SM, Cervini-Silva J, Sposito G (2003) Steady-state dissolution kinetics of goethite in the presence of desferrioxamine B and oxalate ligands: implications for the microbial acquisition of iron. Chemical Geology 198, 63–75.
Steady-state dissolution kinetics of goethite in the presence of desferrioxamine B and oxalate ligands: implications for the microbial acquisition of iron.CrossRef | 1:CAS:528:DC%2BD3sXjt1elsLk%3D&md5=61140338af75daf59f32233e0da1ec1dCAS | open url image1

Chiarizia R, Horwitz EP (1991) New formulations for iron oxides dissolution. Hydrometallurgy 27, 339–360.
New formulations for iron oxides dissolution.CrossRef | 1:CAS:528:DyaK38Xpt1ertQ%3D%3D&md5=ef28671a674f69935cdf01f981fa2254CAS | open url image1

Christophi CA, Axe L (2000) Competition of Cd, Cu, and Pb adsorption on goethite. Journal of Environmental Engineering 126, 66–74.
Competition of Cd, Cu, and Pb adsorption on goethite.CrossRef | 1:CAS:528:DyaK1MXotFartLY%3D&md5=b66147d9ada6a464506882a6b59fd036CAS | open url image1

Cornell RM, Giovanoli R (1993) Acid dissolution of hematites of different morphologies. Clay Minerals 28, 223–232.
Acid dissolution of hematites of different morphologies.CrossRef | 1:CAS:528:DyaK3sXmsFektro%3D&md5=70ccbf8e7e02da3c871eda2494534c74CAS | open url image1

Cornell RM, Schwertmann U (2003) ‘The iron oxides: structure, properties, reactions, occurrences and uses.’ 2nd edn (Wiley-VCH Verlag GmbH & Co., KGaA: Weinheim, Germany)

da Motta PEF, Kämpf N (1992) Iron oxide properties as support to soil morphological features for prediction of moisture regimes in Oxisols of Central Brazil. Journal of Plant Nutrition and Soil Science 155, 385–390.
Iron oxide properties as support to soil morphological features for prediction of moisture regimes in Oxisols of Central Brazil.CrossRef | 1:CAS:528:DyaK3sXkt1Grsg%3D%3D&md5=92968276f5236cbda5d27cb0a252ae6dCAS | open url image1

Darunsontaya T, Suddhiprakarn A, Kheoruenromne I, Gilkes RJ (2010) Geochemical properties and the nature of kaolin and iron oxides in upland Oxisols and Ultisols under a tropical monsoonal climate, Thailand. Thai Journal of Agricultural Science 43, 197–215.

Fitzpatrick RW, Roux JL, Schwertmann U (1978) Amorphous and crystalline titanium and iron-titanium oxides in synthetic preparations, at near ambient conditions, and in soil clays. Clays and Clay Minerals 26, 189–201.
Amorphous and crystalline titanium and iron-titanium oxides in synthetic preparations, at near ambient conditions, and in soil clays.CrossRef | 1:CAS:528:DyaE1MXis1GjsA%3D%3D&md5=0821de5b6dac5ec11c6b8d712767af67CAS | open url image1

Fontes MPF, Weed SB (1991) Iron oxides in selected Brazilian Oxisols: I. Mineralogy. Soil Science Society of America Journal 55, 1143–1149.
Iron oxides in selected Brazilian Oxisols: I. Mineralogy.CrossRef | 1:CAS:528:DyaK3MXlsFOqsLg%3D&md5=105c5ba5c3695a79feb06e9750805732CAS | open url image1

Hixson AW, Crowell JH (1931) Dependence of reaction velocity upon surface and agitation. I. Theoretical consideration. Industrial & Engineering Chemistry 23, 923–931.
Dependence of reaction velocity upon surface and agitation. I. Theoretical consideration.CrossRef | 1:CAS:528:DyaA3MXksV2rtw%3D%3D&md5=acf128485dba900280e25394e390e55eCAS | open url image1

Huynh T, Tong AR, Singh B, Kennedy BJ (2003) Cd substituted goethites-a structural investigation by synchrotron X-ray diffraction. Clays and Clay Minerals 51, 397–402.
Cd substituted goethites-a structural investigation by synchrotron X-ray diffraction.CrossRef | 1:CAS:528:DC%2BD3sXmsVajsbg%3D&md5=20ec3fdee602a1df7749ac20893471afCAS | open url image1

Kabai J (1973) Determination of specific activation energies of metal oxides and metal oxide hydrates by measurement of the rate of dissolution. Acta Chimica Academiae Scientiarum Hungaricae 78, 57–73.

Kaur N, Gräfe M, Singh B, Kennedy BJ (2009a) Simultaneous incorporation of Cr, Zn, Cd, and Pb in the goethite structure. Clays and Clay Minerals 57, 234–250.
Simultaneous incorporation of Cr, Zn, Cd, and Pb in the goethite structure.CrossRef | 1:CAS:528:DC%2BD1MXnslSms7Y%3D&md5=ac2d26240fa7cc968e01c7cb228c480eCAS | open url image1

Kaur N, Singh B, Kennedy BJ (2009b) Copper substitution alone and in the presence of chromium, zinc, cadmium and lead in goethite (α-FeOOH). Clay Minerals 44, 293–310.
Copper substitution alone and in the presence of chromium, zinc, cadmium and lead in goethite (α-FeOOH).CrossRef | 1:CAS:528:DC%2BD1MXhsFOgsLbM&md5=de3a7e2255211293590119b0c1597f23CAS | open url image1

Kaur N, Singh B, Kennedy BJ (2010) Dissolution of Cr, Zn, Cd, and Pb single- and multi-metal-substituted goethite: Relationship to structural, morphological, and dehydroxylation properties. Clays and Clay Minerals 58, 415–430.
Dissolution of Cr, Zn, Cd, and Pb single- and multi-metal-substituted goethite: Relationship to structural, morphological, and dehydroxylation properties.CrossRef | 1:CAS:528:DC%2BC3cXhtFyhu77L&md5=8f59d3e9c59ae0d238d6ea00d4f3dd92CAS | open url image1

Klug HP, Alexander LE (1974) ‘X-ray diffraction procedures for polycrystalline and amorphous materials.’ (John Wiley: New York)

Lim-Nunez R, Gilkes RJ (1987) Acid dissolution of synthetic metal-containing goethites and hematites. In ‘Proceedings of the International Clay Conference’. Denver, USA 1985. (Eds LG Schultz, H van Olphen, FA Mumpton) pp. 197–204. (The Clay Mineral Society: Bloomington, IN)

Manceau A, Schlegel ML, Musso M, Sole VA, Gauthier C, Petit PE, Trolard F (2000) Crystal chemistry of trace elements in natural and synthetic goethite. Geochimica et Cosmochimica Acta 64, 3643–3661.
Crystal chemistry of trace elements in natural and synthetic goethite.CrossRef | 1:CAS:528:DC%2BD3cXnsFWhurY%3D&md5=33c7eba74e6162df377182cbf62ad588CAS | open url image1

Marcussen H, Holm PE, Strobel BW, Hansen HC (2009) Nickel sorption to goethite and montmorillonite in presence of citrate. Environmental Science & Technology 43, 1122–1127.
Nickel sorption to goethite and montmorillonite in presence of citrate.CrossRef | 1:CAS:528:DC%2BD1MXhtVaqtrk%3D&md5=7f0e5883d6f5f0ee36a9d4f224745d9dCAS | open url image1

Muggler CC, Van Loef JJ, Buurman P, van Doesburg JDJ (2001) Mineralogical and (sub) microscopic aspects of iron oxides in polygenetic Oxisols from Minas Gerais, Brazil. Geoderma 100, 147–171.
Mineralogical and (sub) microscopic aspects of iron oxides in polygenetic Oxisols from Minas Gerais, Brazil.CrossRef | 1:CAS:528:DC%2BD3MXpsVGhtQ%3D%3D&md5=17246e649a1420d6d785b7684ef25625CAS | open url image1

Parkhurst DL, Appelo CAJ (1999) ‘User’s guide to PHREEQC (version 2)—a computer program for speciation, batch reaction, one-dimensional transport, and inverse geochemical calculations.’ Water-Resources Investigations Report No. 99-4259. (U.S. Geological Survey: Reston, VA)

Perrier N, Gilkes RJ, Colin F (2006) Heating Fe oxide-rich soils increases the dissolution rate of metals. Clays and Clay Minerals 54, 165–175.
Heating Fe oxide-rich soils increases the dissolution rate of metals.CrossRef | 1:CAS:528:DC%2BD28Xkslygsb0%3D&md5=7176038a199492d0166aca76a35f3992CAS | open url image1

Prasetyo BH, Gilkes RJ (1994) Properties of iron oxides from red soils derived from volcanic tuff in west Java. Australian Journal of Soil Research 32, 781–794.
Properties of iron oxides from red soils derived from volcanic tuff in west Java.CrossRef | 1:CAS:528:DyaK2cXmtVCit7k%3D&md5=3c839935a9238219ee75ed00c252db1dCAS | open url image1

Quin TG, Long GJ, Benson CG, Mann S, Williams RJP (1988) Influence of silicon and phosphorus on structural and magnetic properties of synthetic goethite and related oxides. Clays and Clay Minerals 36, 165–175.
Influence of silicon and phosphorus on structural and magnetic properties of synthetic goethite and related oxides.CrossRef | 1:CAS:528:DyaL1cXitVOrs70%3D&md5=c26576d428282bade0ff6f73a8705061CAS | open url image1

Ruan HD, Gilkes RJ (1995) Acid dissolution of synthetic aluminous goethite before and after transformation to hematite by heating. Clay Minerals 30, 55–65.
Acid dissolution of synthetic aluminous goethite before and after transformation to hematite by heating.CrossRef | 1:CAS:528:DyaK2MXltVCjsbc%3D&md5=bddcc3d7a9689704de980bd85003e009CAS | open url image1

Schulze DG (1984) The influence of aluminum on iron oxides. VIII. Unit-cell dimensions of Al-substituted goethites and estimation of Al from them. Clays and Clay Minerals 32, 36–44.
The influence of aluminum on iron oxides. VIII. Unit-cell dimensions of Al-substituted goethites and estimation of Al from them.CrossRef | 1:CAS:528:DyaL2cXovV2huw%3D%3D&md5=d014d1c1efdd62c0aade842050a8e188CAS | open url image1

Schwertmann U (1984) The influence of aluminium on iron oxides; IX. Dissolution of Al-goethites in 6M HCl. Clay Minerals 19, 9–19.
The influence of aluminium on iron oxides; IX. Dissolution of Al-goethites in 6M HCl.CrossRef | 1:CAS:528:DyaL2cXksVWitbk%3D&md5=e5f982a26ed6efd40ac3d27ebef2d36eCAS | open url image1

Schwertmann U (1988) Goethite and hematite formation in the presence of clay minerals and gibbsite at 25°C. Soil Science Society of America Journal 52, 288–291.
Goethite and hematite formation in the presence of clay minerals and gibbsite at 25°C.CrossRef | 1:CAS:528:DyaL1cXhvFShs7o%3D&md5=33c9882e41984215a0a6e265c65f488fCAS | open url image1

Schwertmann U (1991) Solubility and dissolution of iron oxides. Plant and Soil 130, 1–25.
Solubility and dissolution of iron oxides.CrossRef | 1:CAS:528:DyaK3MXhsVajtbo%3D&md5=b453ee69e4eb87f01c66398132c75f62CAS | open url image1

Schwertmann U, Cornell RM (2000) ‘Iron oxides in the laboratory: preparation and characterization.’ 2nd edn (Wiley-VCH Verlag GmbH: Weinheim, Germany)

Schwertmann U, Taylor RM (1989) Iron oxides. In ‘Minerals in soil environments’. (Eds JB Dixon, SB Weed) pp. 379–438, (Soil Science Society of America: Madison, WI)

Schwertmann U, Fitzpatrick RW, Taylor RM, Lewis DG (1979) The influence of aluminum on iron oxides. Part II. Preparation and properties of Al-substituted hematites. Clays and Clay Minerals 27, 105–112.
The influence of aluminum on iron oxides. Part II. Preparation and properties of Al-substituted hematites.CrossRef | 1:CAS:528:DyaE1MXitVOgsbg%3D&md5=da99db79ee19e1ef30f94fab38acc22fCAS | open url image1

Singh B, Gilkes RJ (1991a) Concentration of iron oxides from soil clays by 5M NaOH treatment: the complete removal of sodalite and kaolin. Clay Minerals 26, 463–472.
Concentration of iron oxides from soil clays by 5M NaOH treatment: the complete removal of sodalite and kaolin.CrossRef | 1:CAS:528:DyaK38XhsVartLc%3D&md5=44e66677f21931962c02244852137673CAS | open url image1

Singh B, Gilkes RJ (1991b) Phosphorus sorption in relation to soil properties for the major soils types of South–Western Australia. Australian Journal of Soil Research 29, 603–618.
Phosphorus sorption in relation to soil properties for the major soils types of South–Western Australia.CrossRef | 1:CAS:528:DyaK3MXmslyrsrk%3D&md5=0b79fae6e0235a905a1daadee10b3b78CAS | open url image1

Singh B, Gilkes RJ (1992) Properties and distribution of iron oxides and their association with minor elements in the soils of south-western Australia. Journal of Soil Science 43, 77–98.
Properties and distribution of iron oxides and their association with minor elements in the soils of south-western Australia.CrossRef | 1:CAS:528:DyaK38XkvFCjsLY%3D&md5=e90e940e0b3a6b4320a7e5afe0bb963eCAS | open url image1

Singh B, Sherman DM, Gilkes RJ, Wells MA (2002) Incorporation of Cr, Mn and Ni into goethite (α-FeOOH): mechanism from extended X-ray absorption fine structure spectroscopy. Clay Minerals 37, 639–649.
Incorporation of Cr, Mn and Ni into goethite (α-FeOOH): mechanism from extended X-ray absorption fine structure spectroscopy.CrossRef | 1:CAS:528:DC%2BD3sXhtFCrsg%3D%3D&md5=d58658cccf7ca8e2393ddf70f50b9c64CAS | open url image1

Soil Survey Staff (2006) ‘Keys to Soil Taxonomy.’ 10th edn (USDA-Natural Resources Conservation Service: Washington, DC)

Trakoonyingcharoen P, Kheoruenromne I, Suddhiprakarn A, Gilkes RJ (2005) Phosphate sorption in red Oxisols and red Ultisols in Thailand. Soil Science 170, 716–725.
Phosphate sorption in red Oxisols and red Ultisols in Thailand.CrossRef | 1:CAS:528:DC%2BD2MXhtVGntbvJ&md5=11e8f4d4491547d5ff77119b205665a2CAS | open url image1

Trakoonyingcharoen P, Kheoruenromne I, Suddhiprakarn A, Gilkes RJ (2006) Properties of iron oxides in red Oxisols and red Ultisols as affected by rainfall and soil parent material. Australian Journal of Soil Research 44, 63–70.
Properties of iron oxides in red Oxisols and red Ultisols as affected by rainfall and soil parent material.CrossRef | 1:CAS:528:DC%2BD28XhtlWjsr4%3D&md5=dee4905e10a23142d467c60ca681ff0cCAS | open url image1

Trolard F, Bourrie G, Jeanroy E, Herbillon AJ, Martin H (1995) Trace metals in natural iron oxides from laterites: a study using selective kinetic extraction. Geochimica et Cosmochimica Acta 59, 1285–1297.
Trace metals in natural iron oxides from laterites: a study using selective kinetic extraction.CrossRef | 1:CAS:528:DyaK2MXltVGlsrk%3D&md5=e173ad273fb9afc167d8f5eb33849ab0CAS | open url image1

Wells MA, Gilkes RJ, Fitzpatrick RW (2001) Properties and acid dissolution of metal-substituted hematites. Clays and Clay Minerals 49, 60–72.
Properties and acid dissolution of metal-substituted hematites.CrossRef | 1:CAS:528:DC%2BD3MXhs12rsbY%3D&md5=416f6a6773aa9da936fe60e5116e3a1eCAS | open url image1

Wells MA, Fitzpatrick RW, Gilkes RJ (2006) Thermal and mineral properties of A1-, Cr-, Mn-, Ni- and Ti-substituted goethite. Clays and Clay Minerals 54, 176–194.
Thermal and mineral properties of A1-, Cr-, Mn-, Ni- and Ti-substituted goethite.CrossRef | 1:CAS:528:DC%2BD28Xkslygsbg%3D&md5=911e6c39b8845bc8cd671ad68b3a1c64CAS | open url image1

Wiriyakitnateekul W, Suddhiprakarn A, Kheoruenromne I, Gilkes RJ (2005) Extractable iron and aluminum predict the P sorption capacity of Thai soils. Australian Journal of Soil Research 43, 757–766.
Extractable iron and aluminum predict the P sorption capacity of Thai soils.CrossRef | 1:CAS:528:DC%2BD2MXhtVamt77P&md5=bb91d635c2f1158b034008943dab1b9eCAS | open url image1

Wiriyakitnateekul W, Suddhiprakarn A, Kheoruenromne I, Smirk MN, Gilkes RJ (2007) Iron oxides in tropical soils on various parent materials. Clay Minerals 42, 437–451.
Iron oxides in tropical soils on various parent materials.CrossRef | 1:CAS:528:DC%2BD1cXjsFOrt7k%3D&md5=00d2715f16c9eb45d1f1c45736815ba4CAS | open url image1

Wisawapipat W, Kheoruenromne I, Suddhiprakarn A, Gilkes RJ (2009) Phosphate sorption and desorption by Thai upland soils. Geoderma 153, 408–415.
Phosphate sorption and desorption by Thai upland soils.CrossRef | 1:CAS:528:DC%2BD1MXht1Gnt7vJ&md5=cd2143f0e031ea9b901ba9822e157ba2CAS | open url image1


Full Text PDF (1.54 MB) Export Citation