Coprecipitation of Arsenate with Metal Oxides. 3. Nature, Mineralogy, and Reactivity of Iron(III)−Aluminum Precipitates

Abstract

Coprecipitation involving arsenic with aluminum or iron has been studied because this technique is considered particularly efficient for removal of this toxic element from polluted waters. Coprecipitation of arsenic with mixed iron−aluminum solutions has received scant attention. In this work we studied (i) the mineralogy, surface properties, and chemical composition of mixed iron−aluminum oxides formed at initial Fe/Al molar ratio of 1.0 in the absence or presence of arsenate [As/Fe+Al molar ratio ( R ) of 0, 0.01, or 0.1] and at pH 4.0, 7.0, and 10.0 and aged for 30 and 210 days at 50 °C and (ii) the removal of arsenate from the coprecipitates after addition of phosphate. The amounts of short-range ordered precipitates (ferrihydrite, aluminous ferrihydrite and/or poorly crystalline boehmite) were greater than those found in iron and aluminum systems (studied in previous works), due to the capacity of both aluminum and arsenate to retard or inhibit the transformation of the initially formed precipitates into well-crystallized oxides (gibbsite, bayerite, and hematite). As a consequence, the surface areas of the iron−aluminum oxides formed in the absence or presence of arsenate were usually much larger than those of aluminum or iron oxides formed under the same conditions. Arsenate was found to be associated mainly into short-range ordered materials. Chemical composition of all samples was affected by pH, initial R, and aging. Phosphate sorption was facilitated by the presence of short-range ordered materials, mainly those richer in aluminum, but was inhibited by arsenate present in the samples. The quantities of arsenate replaced by phosphate, expressed as percentages of its total amount present in the samples, were particularly low, ranging from 10% to 26%. A comparison of the desorption of arsenate by phosphate from aluminum−arsenate and iron−arsenate (studied in previous works) and iron−aluminum−arsenate coprecipitates evidenced that phosphate has a greater capacity to desorb arsenate from aluminum than iron sites.