Effects of photoirradiation on the adsorption of dissolved organic matter to goethite

The effects of photoirradiation of dissolved organic matter (DOM) on its subsequent adsorption to the Fe(III)oxyhydroxide mineral goethite were investigated at 22°C in 0.10 mol L⁻¹ NaClO₄ solutions at pH 3.5 and 5.5, Photoirradiation of DOM decreased the abundance of high molecular-weight components and formed new lower molecular-weight components, including low molecular weight carboxylic acids (i.e., formic, malonic, and acetic acids). Adsorption of non-irradiated DOM decreased from pH 3.5 to 5.5 and was dominated by the intermediate molecular weight (1251-3750 Da) fraction, although the 451-1250 and 3751-11350 Da fractions also contributed to adsorption at pH 3.5. Irradiation resulted in a substantial decrease in DOM adsorption affinity at pH 3.5, primarily due to loss of components in the 1251-3750 and 3751-11350 Da fractions. Irradiation resulted in only a small decrease in DOM adsorption affinity at pH 5.5; the loss of components in the 3751-11350 Da fraction upon irradiation had little effect on adsorption because they played little or no role in the non-irradiated sample at this pH. Irradiation of DOM also affected its interactions with Fe in solution and the solution iron(II)/iron(III) speciation. The combined effects of irradiation followed by adsorption produced DOM that was lower in molecular weight and had a decreased UV-Vis absorptivity than either process, alone. Together, these two processes are likely to have important environmental consequences in terms of UV penetration of surface waters, contaminant mobility, and DOM bioavailability.