Iron sulfide oxidation as influenced by calcium carbonate application

Two overburden materials, with different FeS2 contents (1.9 and 4.1%) and low acid neutralization potential, were limed with CaCO3 at rates of 0, 25, 50, 75, 100, and 125% based on the amount of CaCO3 needed to provide an acid-base account deficit (A/Ba) of zero (A/Ba = neutralization potential--potential acidity--exchangeable acidity). The limed overburden materials were inoculated with Thiobacillus ferrooxidans and leached weekly with deionized water. Residual FeS2 and CaCO3 were determined in samples over a 378-d period. Oxidation followed zero-order kinetics with respect to FeS2 concentration at pH values greater than 4 and first-order kinetics at pH values less than 4. Zero-order oxidation rates ranged from 0.01 to 0.46 micromol g(-1) d(-1) in the overburden with 1.9% FeS2 and from 0.01 to 0.22 micromol g(-1) d(-1) in the overburden with 4.1% FeS2. Oxidation following the first-order rate law had a first-order rate constant of 0.03 d(-1) in the 1.9% FeS2 overburden and 0.01 d(-1) in the 4.1% FeS2 overburden. The calculated half-life was 23 d for the 1.9% FeS2 overburden and 69 d for the 4.1% FeS2 overburden. Additions of CaCO3 affected FeS2 oxidation by controlling the pH of the system. Liming to greater than 50% of the acid-base account deficit did not significantly affect the zero-order oxidation rate. Dissolution of the applied CaCO3 was found to be faster than the oxidation of FeS2 at pH values greater than 4. It was projected that at lime rates up to 125%, the CaCO3 would dissolve and leach out of the system before all the FeS2 oxidized, leaving the potential for acid minesoil formation.     

Factors affecting the ratio of cation exchange capacity to clay content in lignite overburden

Unusually high cation exchange capacity (CEC) values relative to clay content are frequently reported for lignite overburden and minesoils. The CEC to percent clay ratio is commonly greater than one and would require that the average charge of the clay fraction be greater than 100 cmol(c) kg(-1). A comparison of methods for particle-size distribution suggests that the major reason lignite overburden samples have CEC to percent clay ratios greater than one is incomplete dispersion of aggregates of clay minerals or shale fragments. Preliminary investigations revealed the presence of shale fragments, smectite, and partially weathered mica in the silt fraction. Methods commonly used in soil textural analysis underestimated clay content by approximately 24%. The silt fraction may, therefore, provide a "hidden" source of CEC. Another important factor influencing the CEC to percent clay ratio was the presence of organic materials (lignite) in the samples. Lignite may make a significant contribution to CEC in overburden materials. In a study designed to estimate the pH-dependent charge of both the mineral and organic fractions, the CEC of overburden organic constituents was determined to be approximately 158 cmol(c) kg(-1) at pH 8.2. The high CEC to percent clay ratio in lignite overburden and minesoils may be resolved by adjusting methods for clay determination to optimize dispersion and by accounting for CEC due to organic materials. An alternative approach is to use existing methodology and use correction factors to account for incomplete dispersion of clay minerals and the charge contributions of organic materials.     

Comparative uptake of plutonium from soils by Brassica juncea and Helianthus annuus

Plutonium uptake by Brassica juncea (Indian mustard) and Helianthus annuus (sunflower) from soils with varying chemical composition and contaminated with Pu complexes (Pu-nitrate [239Pu(NO3)4], Pu-citrate [239Pu(C6H5O7)], and Pu-diethylenetriaminepentaacetic acid (Pu-DTPA [239Pu-C14H23O10N3]) was investigated. Sequential extraction of soils incubated with applied Pu was used to determine the distribution of Pu in the various soil fractions. The initial Pu activity levels in soils were 44.40-231.25 Bq g(-1) as Pu-nitrate Pu-citrate, or Pu-DTPA. A difference in Pu uptake between treatments of Pu-nitrate and Pu-citrate without chelating agent was observed only with Indian mustard in acidic Crowley soil. The uptake of Pu by plants was increased with increasing DTPA rates, however, the Pu concentration of plants was not proportionally increased with increasing application rate of Pu to soil. Plutonium uptake from Pu-DTPA was significantly higher from the acid Crowley soil than from the calcareous Weswood soil. The uptake of Pu from the soils was higher in Indian mustard than in sunflower. Sequential extraction of Pu showed that the ion-exchangeable Pu fraction in soils was dramatically increased with DTPA treatment and decreased with time of incubation. Extractability of Pu in all fractions was not different when Pu-nitrate and Pu-citrate were applied to the same soil. More Pu was associated with the residual Pu fraction without DTPA application. Consistent trends with time of incubation for other fractions were not apparent. The ion-exchangeable fraction, assumed as plant-available Pu, was significantly higher in acid soil compared with calcareous soil with or without DTPA treatment. When the calcareous soil was treated with DTPA, the ion-exchangeable Pu was comparatively less influenced. This fraction in the soil was more affected with time of incubation. The lowest extractable Pu was from a pH 6.55 Crockett soil that contained the highest clay compared to the other two soils. Extractable soil Pu was largely affected by soil pH and the amounts of clay, salt, metal oxide, and carbonate.     

Uptake and translocation of plutonium in two plant species using hydroponics

This study presents determinations of the uptake and translocation of Pu in Indian mustard (Brassica juncea) and sunflower (Helianthus annuus) from Pu contaminated solution media. The initial activity levels of Pu were 18.50 and 37.00 Bq ml(-1), for Pu-nitrate [239Pu(NO3)4] and for Pu-citrate [239Pu(C6H5O7)+] in nutrient solution. Plutonium-diethylenetriaminepentaacetic acid (DTPA: [239Pu-C14H23O10N3] solution was prepared by adding 0, 5, 10, and 50 microg of DTPA ml(-1) with 239Pu(NO3)4 in nutrient solution. Concentration ratios (CR, Pu concentration in dry plant material/Pu concentration in nutrient solution) and transport indices (Tl, Pu content in the shoot/Pu content in the whole plant) were calculated to evaluate Pu uptake and translocation. All experiments were conducted in hydroponic solution in an environmental growth chamber. Plutonium concentration in the plant tissue was increased with increased Pu contamination. Plant tissue Pu concentration for Pu-nitrate and Pu-citrate application was not correlated and may be dependent on plant species. For plants receiving Pu-DTPA, the Pu concentration was increased in the shoots but decreased in the roots resulting in a negative correlation between the Pu concentrations in the plant shoots and roots. The Pu concentration in shoots of Indian mustard was increased for application rates up to 10 microg DTPA ml(-1) and up to 5 microg DTPA ml(-1) for sunflower. Similar trends were observed for the CR of plants compared to the Pu concentration in the shoots and roots, whereas the Tl was increased with increasing DTPA concentration. Plutonium in shoots of Indian mustard was up to 10 times higher than that in shoots of sunflower. The Pu concentration in the apparent free space (AFS) of plant root tissue of sunflower was more affected by concentration of DTPA than that of Indian mustard.     

Neutralization potential determination of siderite (FeCO3) using selected oxidants

Siderite (FeCO3) is commonly found in coal overburden and, when present, can cause interference in the determination of neutralization potential (NP). Under acidic testing conditions, FeCO3 reacts to neutralize acid, which contributes to the NP. However, continued weathering of FeCO3 (oxidation of Fe2+ and hydrolysis of Fe3+) produces a neutral to slightly acidic solution. The effects of hydrogen peroxide (H2O2), potassium permanganate (KMnO4), and O2 on the laboratory measurement of NP of siderite samples taken from overburden were examined. All oxidation treatments lowered the NP values of the siderite samples as compared with the standard USEPA method. However, oxidation with H2O2 produced variable results depending on the amount of H2O2 added. Neutralization potential values obtained after oxidation treatments were highly correlated with Mn concentration. Reaction products (i.e., 2-line ferrihydrite) of siderite samples with H2O2 and KMnO4 were not representative of natural siderite weathering. Oxidation with O2 produced the lowest NP values for siderite samples. The reaction products produced by oxidation with O2 most closely represent those intermediate products formed when siderite is exposed to atmospheric weathering conditions. Oxidation with O2 also proved to be the most reproducible method for accurately assessing NP when siderite is present in overburden samples.