Laboratory investigations of the effects of nitrification-induced acidification on Cr cycling in vadose zone material partially derived from ultramafic rocks.

Sacramento Valley (California, USA) soils and sediments have high concentrations of Cr(III) because they are partially derived from ultramafic material. Some Cr(III) is oxidized to more toxic and mobile Cr(VI) by soil Mn oxides. Valley soils typically have neutral to alkaline pH at which Cr(III) is highly immobile. Much of the valley is under cultivation and is both fertilized and irrigated. A series of laboratory incubation experiments were conducted to assess how cultivation might impact Cr cycling in shallow vadose zone material from the valley. The first experiments employed low (7.1 mmol N per kg soil) and high (35 mmol Nkg(-1)) concentrations of applied (NH(4))(2)SO(4). Initially, Cr(VI) concentrations were up to 45 and 60% greater than controls in low and high incubations, respectively. After microbially-mediated oxidation of all NH(4)(+), Cr(VI) concentrations dropped below control values. Increased nitrifying bacterial populations (estimated by measurement of phospholipid fatty acids) may have increased the Cr(VI) reduction capacity of the vadose zone material resulting in the observed decreases in Cr(VI). Another series of incubations employed vadose zone material from a different location to which low (45 meq kg(-1)) and high (128 meq kg(-1)) amounts of NH(4)Cl, KCl, and CaCl(2) were applied. All treatments, except high concentration KCl, resulted in mean soil Cr(VI) concentrations that were greater than the control. High concentrations of water-leachable Ba(2+) (mean 38 μmol kg(-1)) in this treatment may have limited Cr(VI) solubility. A final set of incubations were amended with low (7.1 mmol Nkg(-1)) and high (35 mmol Nkg(-1)) concentrations of commercial liquid ammonium polyphosphate (APP) fertilizer which contained high concentrations of Cr(III). Soil Cr(VI) in the low APP incubations increased to a concentration of 1.8 μmol kg(-1) (5× control) over 109 days suggesting that Cr(III) added with the APP fertilizer was more reactive than naturally-occurring soil Cr(III).