The influence of redox potential and pH on arsenic speciation and solubility was studied in a contaminated soil. Alterations in the oxidation state of arsenic, as influenced by redox potential and pH, greatly affected its solubility in soil. At higher soil redox levels (500-200 mV), arsenic solubility was low and the major part (65-98%) of the arsenic in solution was present as As(V). An alkaline pH, or the reduction of As(V) to As(III), released substantial proportions of arsenic into solution. Under moderately reduced soil conditions (0-100 mV), arsenic solubility was controlled by the dissolution of iron oxyhydroxides. Arsenic was coprecipitated [as As(V)] with iron oxyhydroxides and released upon their solubilization. Upon reduction to -200 mV, the soluble arsenic content increased 13-fold as compared to 500 mV. The observed slow kinetics of the As(V)-As(III) transformation and the high concentrations of Mn present indicate that, under reduced soil conditions, arsenic solubility could be controlled by a Mn3(As04)2 phase.

Arsenic absorption by rice (Oryza sativa, L.) in relation to the chemical form and concentration of arsenic added in nutrient solution was examined. A 4 x 3 x 2 factorial experiment was conducted with treatments consisting of four arsenic chemical forms [arsenite, As(Ill); arsenate, As(V); monomethyl arsenic acid, MMAA; and dimethyl arsenic acid, DMAA], three arsenic concentrations [0.05, 0.2, and 0.8 mg As L-J], and two cultivars [Lemont and Mercury] with a different degree of susceptibility to straighthead, a physiological disease attributed to arsenic toxicity. Two controls, one for each cultivar, were also included. Arsenic phytoavailability and phytotoxicity are determined primarily by the arsenic chemical form present. Application of DMAA increased total dry matter production. While application of As(V) did not affect plant growth, both As(Ill) and MMAA were phytotoxic to rice. Availability of arsenic to rice followed the trend: DMAA < As(V) < MMAA < As(III). Upon absorption, DMAA was readily translocated to the shoot. Arsenic(Ill), As(V), and MMAA accumulated in the roots. With increased arsenic application rates the arsenic shoot/root concentration decreased for the As(Ill) and As(V) treatments. Monomethyl arsenic acid (MMAA), however, was translocated to the shoot upon increased application. The observed differential absorption and translocation of arsenic chemical forms by rice is possibly responsible for the straighthead disorder attributed to arsenic.

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Arsenic absorption by rice (Oryza sativa, L.) in relation to As chemical form present in soil solution was examined. Rice plants were grown in soil suspensions equilibrated under selected conditions of redox and pH, affecting arsenic solubility and speciation. A decrease in pH led to higher dissolved arsenic concentrations. When the soil redox potential dropped below 0 mV, most of the arsenic was present as As(Ill). Under more oxidizing conditions both As(Ill) and As(V) are present. Chemical speciation of As in the watersoluble fraction affected its phytoavailability. Most indigenous arsenic taken up by the plants remained in the root. Plant arsenic availability increased with increasing arsenic concentration in solution (lower soil pH) and with increasing amounts of soluble As(Ill) (lower soil redox). We also studied the uptake of monomethyl arsenic acid (MMAA), a widely used defoliant and herbicide, as affected by soil redox-pH condition. Amended MMAA was approximately two times more phytoavailable than the indigenous inorganic As forms and increased with decreasing pH and redox.

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