Processes of Iron and Manganese Retention in Laboratory Peat Microcosms Subjected to Acid Mine Drainage

Despite increasing use of constructed wetlands for treatment of metal-enriched acid coal mine drainage (AMD), the biotic and abiotic mechanisms of metal retention in such wetlands are poorly understood. The present study was conducted to evaluate the processes responsible for Fe and Mn retention in peat and the effects of microbial activity, pH, temperature, and metal concentration in AMD on these processes. Experimental units consisted in 30 g (wet wt.) of fresh Sphagnum peat, which was repeatedly flushed with synthetic AMD at pH 3.5. Of the four major processes of metal cation retention in peat (cation exchange, complexation with peat organics, precipitation as oxides, and precipitation as sulfides), Fe oxidation and Fe binding on peat organics were predominant, with Fe oxides and organically bound Fe making up, respectively, 62 and 22% of the total Fe in the peat at the end of the experiment. Whereas Fe complexation was a finite process, reaching saturation at 12 mg Fe g⁻¹ dry peat, Fe-oxide concentration in peat increased steadily throughout the experiment. At pH 3.5, Fe-oxide precipitation was depressed by the addition of an antiseptic (formaldehyde) to AMD, suggesting that the process was microbially mediated. Iron oxide precipitation was higher at pH 5.5 than 3.5 and less depressed at pH 5.5 than 3.5 by the presence of formaldehyde in AMD. The efficiency of peat to remove Fe from AMD was diminished at low temperature (<15°C) and high Fe concentration in AMD (>100 mg L⁻¹). Manganese retention in peat was small compared with that of Fe, and Mn was retained in peat almost exclusively as exchangeable Mn²⁺. Retention of Fe²⁺ in peat was not affected by the presence of Mn²⁺ in AMD. Iron oxides that had accumulated in peat subjected to AMD were not readily resolubilized by any of three processes investigated: photoreduction, microbial Fe(III) reduction under reducing conditions, and exposure to simulated acid precipitation. These findings suggest that constructed wetlands may be an appropriate technology to remove Fe from AMD with low soluble Fe concentration, but are inadequate for treating drainage waters rich in soluble Mn. This work was supported by a ant from the USEPA R-812379-01-0.