Kinetic analysis of data obtained from studies on microbial degradation of cement waste forms, using shrinking core models.

Model equations based on analytical solutions of two shrinking core models (acid dissolution or shrinking unreacted core (SUC) model, and bulk diffusion model), were used to analyze the kinetics of microbial degradation of cement waste forms. Two current approaches of waste form microbial stability evaluation (Nuclear Regulatory Commission (NRC) method and refined biofilm formation) were used to generate the data. Good linear correlations with R(2)>0.95 were obtained for the leaching data from both the NRC and biofilm approaches, using the model equation based on the bulk diffusion concept. Analyses using the model equation based on the acid dissolution model generally gave poor correlations except when data obtained from biofilm formation method was normalized.

Enhanced biodegradation of methylhydrazine and hydrazine contaminated NASA wastewater in fixed-film bioreactor.

The aerobic biodegradation of National Aeronautics and Space Administration (NASA) wastewater that contains mixtures of highly concentrated methylhydrazine/hydrazine, citric acid and their reaction product was studied on a laboratory-scale fixed film trickle-bed reactor. The degrading organisms, Achromobacter sp., Rhodococcus B30 and Rhodococcus J10, were immobilized on coarse sand grains used as support-media in the columns. Under continuous flow operation, Rhodococcus sp. degraded the methylhydrazine content of the wastewater from a concentration of 10 to 2.5 mg/mL within 12 days and the hydrazine from approximately 0.8 to 0.1 mg/mL in 7 days. The Achromobacter sp. was equally efficient in degrading the organics present in the wastewater, reducing the concentration of the methylhydrazine from 10 to approximately 5 mg/mL within 12 days and that of the hydrazine from approximately 0.8 to 0.2 mg/mL in 7 days. The pseudo first-order rate constants of 0.137 day(-1) and 0.232 day(-1) were obtained for the removal of methylhydrazine and hydrazine, respectively, in wastewater in the reactor column. In the batch cultures, rate constants for the degradation were 0.046 and 0.079 day(-1) for methylhydrazine and hydrazine respectively. These results demonstrate that the continuous flow bioreactor afford greater degradation efficiencies than those obtained when the wastewater was incubated with the microbes in growth-limited batch experiments. They also show that wastewater containing hydrazine is more amenable to microbial degradation than one that is predominant in methylhydrazine, in spite of the longer lag period observed for hydrazine containing wastewater. The influence of substrate concentration and recycle rate on the degradation efficiency is reported. The major advantages of the trickle-bed reactor over the batch system include very high substrate volumetric rate of turnover, higher rates of degradation and tolerance of the 100% concentrated NASA wastewater. The results of the present laboratory scale study will be of great importance in the design and operation of an industrial immobilized biofilm reactor for the treatment of methylhydrazine and hydrazine contaminated NASA wastewater.

Stability evaluation of a cement based waste form to microbially induced degradation.

In this study the current Nuclear Regulatory Commission (NRC) protocol is used to evaluate the stability of Tuskegee cement/cobalt chloride waste form in the presence of Thiobacillus thiooxidans (T. thiooxidans). A critical examination of this protocol and identified limitations are reported also. Tuskegee cement/cobalt chloride waste forms were shown to exhibit considerable instability to microbial degradation as indicated by significant physical deterioration, and increased leaching of calcium and cobalt on exposure to T. thiooxidans. The instability was aggravated with higher levels of cobalt chloride content of the waste forms. The degradative capability of T. thiooxidans closely followed its ability to significantly decrease the pH of its environment. Inherent limitations in the NRC protocol were observed which could lead to serious result interpretation errors. The use of a T. thiooxidans culture that is significantly lower in pH in comparison to the control medium could lead to an overestimation of the degradative effect of T. thiooxidans, while the use of a culture that is substrate limited could result in an underestimation of T. thiooxidans capability.

A refinement of the biofilm formation method for waste forms stability evaluation.

A refinement of the biofilm formation method for waste form stability evaluation was carried out in this study. Refinement of the biofilm formation method became necessary because of the reduced contrast in degradation between control and experimental samples. The reduction in contrast was occasioned by the long duration of exposure (12 days) of the control samples to sterile medium of low pH in the first stage. Results of evaluation carried out reveal that the duration of the first stage of the biofilm formation method can be reduced to 24 h, with substantial increase in the contrast between degradations experienced by control and experimental samples. Reduction of the first stage can be done without compromising the efficiency of the inoculation process, which the longer duration of the first stage was originally intended to ensure. A doubt as to actual formation of biofilms on experimental samples, resulting from the use of non-sterile tubings and glass wares in the second stage, was also addressed in this study. Results reveal that substantial attachment of microbes occur on the surfaces of experimental samples in the first stage, thus any supply of microbes via the tubings and glass wares in the second stage is only additional and inconsequential.

Development of a biofilm formation method for waste forms stability evaluation.

The development of an accurate assessment protocol is critical for the prediction of long-term performance of waste disposal systems under field conditions. In this study, the development of a biofilm formation method for the evaluation of waste forms stability to microbially induced degradation (MID) is reported. The development process involved significant modifications to the existing Nuclear Regulatory Commission (NRC) approach. In the biofilm formation method, the control media and fermenter broths are designed to be of similar pH to avoid overestimation of the microbe's capability to degrade the waste forms. In the NRC approach, the pH values are different. The existing one-stage process of the NRC approach is also replaced with a two-stage process in the biofilm formation method. This is to ensure full evaluation of the microbe's involvement in waste forms degradation. The first stage of the two-stage process is for biofilm formation and the second is for biofilm evaluation. The use of a two-stage process eliminates the possibility of substrate limitation, resulting in values of degradation indices that are about two times higher than those obtained using the single-stage NRC approach. Two waste forms (100% Tuskegee cement and 21% cobalt chloride/79% cement) were used in the development of the biofilm formation method. Both waste forms showed evidence of biofilm formation. The formation of biofilm on the cobalt-containing waste form indicates a lack of anti-microbial capability of cobalt.

Batch culture biodegradation of methylhydrazine contaminated NASA wastewater.

The batch culture degradation of NASA wastewater containing mixtures of citric acid, methylhydrazine, and their reaction product was studied. The organic contaminants present in the NASA wastewater were degraded by Achromobacter sp., Rhodococcus B30 and Rhodococcus J10. While the Achromobacter sp. showed a preference for the degradation of the citric acid, the Rhodococcus species were most effective in reducing the methylhydrazine and the reaction product. Removals of more than 50% were observed for citric acid, methylhydrazine and the reaction product when the NASA wastewater was inoculated with the microbes in batch cultures. Simulation and chemical characterization of citric acid and hydrazine mixtures show that the interaction is partly of a chemical nature and leads to the formation of a conjugated UV/Visible absorbing compound. An 'azo' carbonyl derivative of the citric acid, consistent with the spectral data obtained from the investigation, has been proposed as the possible product.