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Dedicated to Prof. Dr. Ulrich Förstner on his 65th birthday

DOI: http://dx.doi.org/10.1065/jss2005.01.126

Goal, Scope and Background. Goethite (α-FeOOH) as the most frequently occurring iron oxide in the environment plays a significant role in the binding of inorganic pollutants. Accordingly, synthetic goethite is used for the purification of contaminated water. Goethite crystals can be prepared in different shape as porous and non-porous forms. The mineral can also be modified by partial substitution of structural Fe+3 for different foreign elements. The biggest possible substituent known so far is Cd+2 which causes a strong expansion of the unit-cell parameters. An incorporation of Pb+4 generates a permanent positive charge. Goethites with these morphological and structural modifications were selected for sorption experiments with Co2+, Ni2+, Zn2+, Cd2+, Pb2+, and arsenate. It was intended to demonstrate the potential of mineral modification for improving sorption properties.

Methods. Batch sorption studies were carried out combining each mineral with a single element at different pH and reaction times. Cations were investigated at a single initial concentration only while arsenate was tested over a range of concentrations in order to establish sorption isotherms. The sorption step was followed by an extraction step to characterize time dependent immobilization reactions.

Results and Discussion. A time dependent increase of trace metal and arsenate sorption is attributed to a migration of ions into pores of star-shaped goethite and to a binding by specific sorption sites at the surface. The migration into pores is related to the size of adsorbing cations. The almost identical sorption behaviour of Ni2+ and Co2+ on pure goethite is contrasted by a strong preference of Co over Ni on Cd-goethite. Expansion of the unit-cell dimensions in Cd+2 substituted goethite generates highly specific binding sites at the surface. These are accessible to Co and Zn only. A permanent positive charge in Pb+4 substituted goethite reduces the binding of cations and doubles the sorption capacity for arsenate. Pb-goethite also contains a limited portion of highly specific sites which can only be accessed by Zn2+. Immobilization takes place even after a short contact time of 16 hours. This process results in a growing fraction of non-extractable metals and arsenate with reaction time.

Conclusions. Pores and foreign elements in the goethite structure greatly affect the reactivity of the mineral and the ability to immobilize inorganic pollutants. A possible mechanisms for the preferred sorption of Co and Zn by Cd-goethite is seen in the ability of these metal ions to adopt a smaller size: Co by oxidation of Co2+ to Co3+ and Zn by tetrahedral coordination of Zn2+. This kind of binding can be viewed as structural incorporation. The binding properties of modified goethites can well be characterized by sorption tests including an array of elements with different ionic size and charge.

Recommendation and Outlook. There is considerable potential for designing goethite modifications with improved surface reactivity for specific purposes such as water purification and possibly catalysis of reactions.