Byung J. Kim

Effects of Ozonation on the Biodegradability of Substituted Phenols

Abstract The aerobic biodegradability of unoxidised and ozonated chloro-, nitro-, and amino-phenols was investigated using batch bioassays with unacclimated biomass. Chloro- and nitro-phenols exhibited biorecalcitrant behavior at 200 mg/liter as COD, yet were more readily degraded at 30 mg/liter as COD. Ozonation of chloro- and nitro-phenols significantly enhanced their biodegradability. While unoxidized aminophenols were readily degradable, ozonation significantly decreased their biodegradability. Quantitative structure activity relationships (QSARs) using Hammett constants were developed for biodegradability of unoxidized substituted phenols. For the eight substituted phenols studied, ozonation significantly decreased the Microtox toxicity of each, with EC50 values increasing from 0.7 to 1.6 orders-of-magnitude.

Enhancing Fenton oxidation of TNT and RDX through pretreatment with zero-valent iron

The effect of reductive treatment with elemental iron on the rate and extent of TOC removal by Fenton oxidation was studied for the explosives 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) using a completely stirred tank reactor (CSTR). The results support the hypothesis that TNT and RDX are reduced with elemental iron to products that are oxidized more rapidly and completely by Fentons reagent. Iron pretreatment enhanced the extent of total organic carbon (TOC) removal by approximately 20% and 60% for TNT and RDX, respectively. Complete TOC removal was achieved for TNT and RDX solutions with iron pretreatment under optimal conditions. On the other hand, without iron pretreatment, complete TOC removal of TNT and RDX solutions was not achieved even with much higher H(2)O(2) and Fe(2+) concentrations. Nitrogen was recovered as NH(4)(+) and NO(3)(-) when Fe(0)-treated TNT and RDX solutions were subjected to Fenton oxidation. The bench-scale iron treatment-Fenton oxidation integrated system showed more than 95% TOC removal for TNT and RDX solutions under optimal conditions. These results suggest that the reduction products of TNT and RDX are more rapidly and completely degraded by Fenton oxidation and that a sequential iron treatment-Fenton oxidation process may be a viable technology for pink water treatment.

Effect of substrate Henry's constant on biofilter performance

Abstract Butanol, ether, toluene, and hexane, which have Henrys constants ranging from 0.0005 to 53, were used to investigate the effects of substrate solubility or availability on the removal of volatile organic compounds (VOCs) in trickle-bed biofilters. Results from this study suggest that, although removal of a VOC generally increases with a decrease in its Henrys constant, an optimal Henrys constant range for biofiltration may exist. For the treatment of VOCs with high Henrys constant values, such as hexane and toluene, the transfer of VOCs between the vapor and liquid phases or between the vapor phase and the biofilm is a rate-determining step. However, oxygen (O2) transfer may become a rate-limiting step in treating VOCs with low Henrys constants, such as butanol, especially at high organic loadings. The results demonstrated that in a gas-phase aerobic biofilter, nitrate can serve both as a growth-controlling nutrient and as an electron acceptor in a biofilm for the respiration of VOCs with low Henrys constants. Microbial communities within the biofilters were examined using denaturing gradient gel electrophoresis to provide a more complete picture of the effect of O2 limitation and denitrification on biofilter performance.

The roles of intermediates in biodegradation of benzene, toluene, and p-xylene by Pseudomonas putida F1.

Several types of biodegradation experiments with benzene, toluene, or p-xylene show accumulation of intermediates by Pseudomonas putida F1. Under aerobic conditions, the major intermediates identified for benzene, toluene, and p-xylene are catechol, 3-methylcatechol, and 3,6-dimethylcatechol, respectively. Oxidations of catechol and 3-methylcatechol are linked to biomass synthesis. When oxygen is limited in the system, phenol (from benzene) and m-cresol and o-cresol (from toluene) accumulate.

Biotransformation of explosive-grade nitrocellulose under denitrifying and sulfidogenic conditions

Waste nitrocellulose (NC) is regulated as a hazardous material. The objective of this study was to determine if NC exposed to denitrifying and sulfidogenic conditions would undergo sufficient removal of the nitro groups to yield a material that is no longer explosive. Enrichment cultures were established with methanol as the electron donor for nitrate-reducing conditions and lactate for sulfate-reducing conditions. NC was added to the cultures at 10 g/l. A statistically significant decrease in the nitrogen (N) content of NC occurred in both enrichment cultures, from approximately 13.1-13.2% in virgin NC to 12.2-12.4%. This was accompanied by an increase in nitrogen gas formation. The presence of a primary substrate (methanol and lactate) was necessary to affect this change; NC itself did not serve as an electron donor. In cultures that were carrying out denitrification but were then depleted of nitrate, with methanol still present, a slightly greater removal of nitro groups from NC occurred along with additional formation of nitrogen gas. NC did not have an inhibitory affect on the denitrification process but it did significantly slow the rate of lactate consumption and sulfate reduction. Fourier Transform Infrared Spectroscopy (FTIR) results indicated that NC exposed to denitrifying conditions was enriched in hydroxyl groups, consistent with removal of some of the nitro groups by hydrolysis of the nitrate esters. NC exposed to nitrate- and sulfate-reducing conditions and virgin NC were also compared based on their explosive properties using a small-scale burning test. The biologically treated NC exhibited somewhat less reactivity, but was still rated as explosive. The decrease in%N, increase in N2, and FTIR results demonstrated that NC does undergo biotransformation in the presence of nitrate- and sulfate-reducing enrichment cultures, but the extent of denitration does not appear to be adequate to yield a nonhazardous product.

The effect of nitrate on VOC removal in trickle bed biofilters

Abstract In response to the growing concern over volatile organic compounds (VOCs), biofiltration is becoming an established economical air pollution control technology for removing VOCs from waste air streams. Current research efforts are concentrating on improving control over key parameters that affect the performance of gas phase biofilters. This study utilized diethyl ether as a substrate, nitrate as the sole nutrient nitrogen source within two co-currently operated trickle-bed biofilters, for over 200 days. The two pelletized medium biofilters were operated at a low empty bed contact time of 25 s, inlet gas flow rates of 8.64 m 3 /day, nutrient liquid flow rates of 1 liter/day, and COD loading rates of 1.8 and 3.6 kg/m 3 per day, respectively. Operational parameters including contaminant concentration in the gas phase, nutrient nitrate concentration in the aqueous phase, and the frequency of biomass removal were considered. Special attention was given to the effect and the role of nitrate on VOC removal. Throughout the experiment, nitrate persisted in the liquid effluent and the ether removal efficiencies improved with increasing influent nitrate concentration, which suggest that the nitrate diffusion into the biofilms is rate determining. By increasing the concentration of oxygen in the feed to this biofilter from 21% (ambient air) to 50 and 100%, while maintaining an influent ether concentration of 133 ppmv and a feed nitrate concentration of 67 mg-N/liter, the performance of the biofilter was not significantly affected. These results suggest that nitrogen was rate limiting as a growth nutrient rather than as an electron acceptor for the respiration of ether. The results also indicated that removal of excess biomass is necessary to maintain long-term performance. However, the required frequency of biomass removal depends on operating parameters such as loading.

Effect of gas empty bed contact time on performances of various types of rotating drum biofilters for removal of VOCs

The effects of gas empty bed contact time (EBCT), biofilter configuration, and types of volatile organic compounds (VOCs) were evaluated to assess the performance of rotating drum biofilters (RDBs), especially at low EBCT values. Three types of pilot-scale RDBs, a single-layer RDB, a multi-layer RDB, and a hybrid RDB, were examined at various gas EBCTs but at a constant VOC loading rate. Diethyl ether, toluene, and hexane were used separately as model VOC. When EBCT increased from 5.0 to 60s at a constant VOC loading rate of 2.0kgCOD/(m(3)day), ether removal efficiency increased from 73.1% to 97.6%, from 81.6% to 99.9%, and from 84.0% to 99.9% for the single-layer RDB, the multi-layer RDB, and the hybrid RDB, respectively, and toluene removal efficiency increased from 76.4% to 99.9% and from 84.8% to 99.9% for the multi-layer RDB and the hybrid RDB, respectively. When hexane was used as the model VOC at a constant loading rate of 0.25kgCOD/(m(3)day), hexane removal efficiency increased from 31.1% to 57.0% and from 29.5% to 50.0% for the multi-layer RDB and hybrid RDB, respectively. The single-layer, multi-layer, and hybrid RDBs exhibited, respectively, the lowest, middle, and highest removal efficiencies, when operated under similar operational loading conditions. Hexane exhibited the lowest removal efficiency, while diethyl ether displayed the highest removal efficiency. The data collected at the various EBCT values correlated reasonably well with a saturation model. The sensitivity of removal efficiency to EBCT varied significantly with EBCT values, VOC properties, and biofilter configurations. Process selection and design for RDB processes should consider these factors.

A two-step model for the kinetics of BTX degradation and intermediate formation by Pseudomonas putida F1

A two-step model is developed for the aerobic biodegradation of benzene,toluene, and p-xylene (BTX) by Pseudomonas putida F1. The model contains three unique features. First, an initial dioxygenation step transforms BTX into their catechol intermediates, but does not support biomassgrowth. Second, the benzene or toluene intermediates are mineralized, which supports biomass synthesis. Third, BTX exhibit competitive inhibition on each others transformation, while toluene and benzenenoncompetitively inhibit the mineralization of their catechol intermediate. A suite of batch and chemostat experiments is used to systematically measure the kinetic parameters for the two-step transformations and the substrate interactions.

Reductive transformation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine, octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine, and methylenedinitramine with elemental iron

Reductive (pre)treatment with elemental iron is a potentially useful method for degrading nitramine explosives in water and soil. In the present study, we examined the kinetics, products, and mechanisms of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) degradation with elemental iron. Both RDX and HMX were transformed with iron to formaldehyde, NH4+, N2O, and soluble products. The yields of formaldehyde were relatively constant (71% +/- 5%), whereas the yields of NH4+ and N2O varied, depending on the nitramine and the mechanism. The reactions most likely were controlled by a surface process rather than by external mass transfer. Methylenedinitramine (MDNA) was an intermediate of both RDX and HMX and was transformed quantitatively to formaldehyde with iron. However, product distributions and kinetic modeling results suggest that MDNA represented a minor reaction path and accounted for only 30% of the RDX reacted and 14% of the formaldehyde produced. Additional experiments showed that RDX reduction with elemental iron could be mediated by graphite and Fe2+ sorbed to magnetite, as demonstrated previously for nitroaromatics and nitrate esters. Methylenedinitramine was degraded primarily through reduction in the presence of elemental iron, because its hydrolysis was slow compared to its reactions with elemental iron and surface-bound Fe2+. Our results show that in a cast iron-water system, RDX may be transformed via multiple mechanisms involving different reaction paths and reaction sites.

Mathematical model for the biodegradation of VOCs in trickle bed biofilters

The objective of this work is to develop a fundamental mathematical model that describes the biodegradation of volatile organic compounds (VOCs) in gas phase trickle-bed biofilters, and to estimate the unknown model parameters. The mathematical model considers a three-phase system (biofilm, water, and gas phase), non-uniform bacterial population, and one limiting substrate. Two pilot-scale trickle-bed biofilters were operated to remove the VOC diethyl ether from a waste gas stream. Experimental results from this system were used to estimate the unknown parameters of the steady-state model: the maximum rate of substrate utilization μ m X f / Y , the Monod constant, K s , and the ether biofilm/water diffusivity ratio, r d . While the value of μ m X f / Y was uniquely determined, the values of K s and r d were highly correlated. High values of the Monod constant and the ether diffusivity in the biofilm gave similar predictions to those corresponding to low values of both parameters. Batch studies were used to estimate the value of K s without mass transfer limitations showing that K s < 1 mg/L=2.6 mg COD/L. Using this information and biofilter operating data the true values of K s and r d were determined.