Arsenic (V) adsorption on iron oxide implications for soil remedeation and water purification

University dissertation from Luleå tekniska universitet

Abstract: Addition of iron oxide based adsorbents to arsenic contaminated soils has been proposed as a mean to reduce the mobility of arsenic in the soil. However, the conditions in the soil such as pH value, the presence of phosphate after addition of fertilizer to the soil or the presence of Zn (II) as a co-contaminant may affect the adsorption of arsenate on the iron oxide and may therefore have implications for the mobility of arsenic in the remediated soil. In the present work, a new flow method was developed to study the adsorption of arsenate on synthetic iron oxide with high surface area (ferrihydrite) in situ by means of Attenuated Total Reflection – Fourier Transform Infrared (ATR – FTIR) spectroscopy and the method was used for studying how the adsorption of arsenate was affected by the pH/pD value, the presence of phosphate and Zn (II) in the system. The highest adsorption of arsenate was found at pD 4 and decreased as the pD value increased. The arsenate complexes formed on ferrihydrite appeared to be very stable at pD 4, while the stability decreased as the pD value increased. Arsenate showed a higher adsorption affinity than phosphate on ferrihydrite under the conditions studied. However, phosphate was able to replace about 10 % of pre-adsorbed arsenate on ferrihydrite at pD 4 and about 20 % of the pre-adsorbed arsenate at pD 8.5 in equimolar concentrations of phosphate and arsenate. Phosphate replaced 30 % of pre-adsorbed arsenate at pD 4 and up to 50 % of pre-adsorbed arsenate at pD 8.5 when the concentration of phosphate in the system was 5 times higher than that of arsenate. Batch adsorption experiments indicated an enhancement in the arsenate removal from a ferrihydrite suspension in the presence of Zn (II) at pH 8 in accordance with previous reports. However, no adsorption of arsenate on ferrihydrite in the presence of high concentrations of Zn (II) in the system was observed by infrared spectroscopy. Instead, precipitation of zinc hydroxide carbonate followed by arsenate adsorption on the zinc precipitate was found to be the most likely explanation of these results. Although iron oxides are selective towards arsenate, high specific surface areas are required to achieve sufficiently high adsorption capacity. A method of increasing the specific surface area of coarse hematite particles to obtain a good adsorbent was also developed in the present work. The method comprises an acid treatment to produce iron ions followed by hydrolysis to precipitate an iron oxy-hydroxide coating on the hematite particles. While the arsenate adsorption capacity of the original coarse hematite particles was found to be negligible, the sintered coarse hematite particles showed good potential as an adsorbent for arsenate with an adsorption capacity of about 0.65 mg[As]/g. The method developed for studying adsorption on iron oxides by in situ ATR - FTIR spectroscopy was further developed for studying the adsorption of flotation collectors on iron oxides. Iron ore is often separated from gangue minerals by means of reverse flotation in which a surfactant should selectively adsorb on the gangue mineral rendering it hydrophobic. However, unwanted adsorption of the surfactants on the iron oxide has been reported to affect the production of iron ore pellets. A method was developed to study the adsorption of the surfactant Atrac 1563 on synthetic hematite in situ by means of ATR - FTIR spectroscopy. The adsorption of Atrac 1563 on hematite at pH 8.5 was found to mostly occur via interactions between the polar ester and ethoxy groups of the surfactant and the hematite surface.

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