C. M. Kao

Application of persulfate to remediate petroleum hydrocarbon-contaminated soil: Feasibility and comparison with common oxidants

In this study, batch experiments were conducted to evaluate the feasibility of petroleum-hydrocarbon contaminated soil remediation using persulfate oxidation. Various controlling factors including different persulfate and ferrous ion concentrations, different oxidants (persulfate, hydrogen peroxide, and permanganate), and different contaminants (diesel and fuel oil) were considered. Results show that persulfate oxidation is capable of treating diesel and fuel oil contaminated soil. Higher persulfate and ferrous ion concentrations resulted in higher diesel degrading rates within the applied persulfate/ferrous ion molar ratios. A two-stage diesel degradation was observed in the batch experiments. In addition, treatment of diesel-contaminated soil using in situ metal mineral activation under ambient temperature (e.g., 25°C) may be a feasible option for site remediation. Results also reveal that persulfate anions could persist in the system for more than five months. Thus, sequential injections of ferrous ion to generate sulfate free radicals might be a feasible way to enhance contaminant oxidation. Diesel oxidation efficiency and rates by the three oxidants followed the sequence of hydrogen peroxide>permanganate>persulfate in the limited timeframes. Results of this study indicate that the application of persulfate oxidation is a feasible method to treat soil contaminated by diesel and fuel oil.

Biotransformation of cyanide to methane and ammonia by Klebsiella oxytoca

Klebsiella oxytoca, isolated from cyanide-containing industrial wastewater, was shown to be able to biodegrade cyanide to non-toxic endproducts using cyanide as the sole nitrogen source. In this study, ammonia was one of the detected endproduct of cyanide biodegradation by the concentrated resting cells of K. oxytoca. Moreover, cyanide has been shown to be biotransformed to methane through the actions of concentrated resting cells. Biodegradation of cyanide by cell-free extracts was not observed, which might be due to the inactivation of nitrogenase (an oxygen-labial enzyme) caused by the oxygen exposure after cell disruption. Results show that the cyanide consumption by resting cells of K. oxytoca was induced when the pretreatment of these cells with cyanide was conducted. However, the cyanide-degrading capability of resting cells pretreated with ammonia was inhibited. The inhibition of cyanide degradation by resting cells of K. oxytoca was affected by the ammonia concentration. This might result from the suppression of nitrogenase activity of K. oxytoca by ammonia since nitrogenase was suggested to be the sole cyanide-degrading enzyme during the cyanide degradation process. Results from this study also show that the processes of cyanide biodegradation and ammonia production by resting cells occurred simultaneously. This suggests that the utilization of cyanide as nitrogen source by K. oxytoca might proceed using ammonia as an assimilatory substrate.

Remediation of PCE-contaminated aquifer by an in situ two-layer biobarrier: laboratory batch and column studies

The industrial solvent tetrachloroethylene (PCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop an in situ two-layer biobarrier system consisting of an organic-releasing material layer followed by an oxygen-releasing material layer. The organic-releasing material, which contained sludge cakes from a domestic wastewater treatment plant, is able to release biodegradable organics continuously. The oxygen-releasing material, which contained calcium peroxide, is able to release oxygen continuously upon contact with water. The first organic-releasing material layer was to supply organics (primary substrates) to reductively dechlorinate PCE in situ. The second oxygen-releasing material layer was to release oxygen to aerobic biodegrade or cometabolize PCE degradation byproducts from the first anaerobic layer. Batch experiments were conducted to design and identify the components of the organic and oxygen-releasing materials, and evaluate the organic substrate (presented as chemical oxygen demand (COD) equivalent) and oxygen release rates from the organic-releasing material and oxygen-releasing materials, respectively. The observed oxygen and COD release rates were approximately 0.0368 and 0.0416 mg/d/g of material, respectively. A laboratory-scale column experiment was then conducted to evaluate the feasibility of this proposed system for the bioremediation of PCE-contaminated groundwater. This system was performed using a series of continuous-flow glass columns including a soil column, an organic-releasing material column, two consecutive soil columns, and an oxygen-releasing material column, followed by two other consecutive soil columns. Anaerobic acclimated sludges were inoculated in the first four columns, and aerobic acclimated sludges were inoculated in the last three columns to provide microbial consortia for contaminant biodegradation. Simulated PCE-contaminated groundwater with a flow rate of 0.25 L/d was pumped into this system. Effluent samples from each column were analyzed for PCE and its degradation byproducts. Results show that up to 99% of PCE removal efficiency was obtained in this passive system. Thus, the biobarrier treatment scheme has the potential to be developed into an environmentally and economically acceptable remediation technology for the in situ treatment of PCE-contaminated aquifer.

Effects of soil pH, temperature and water content on the growth of Burkholderia pseudomallei.

Optimum conditions were determined for the growth ofBurkholderia pseudomallei in natural soils or waters. It grows better in paddy soil, crop-covered and fallow field than in fresh and salty water. Although the optimal temperature and pH for the growth were 37 or 42 °C, and 6.5 or 7.5 in an environmental-mimicking soil medium, this bacterium can still grow at 4 °C, which was suggested to be related with the occurrence of melioidosis in some cold areas. In soil media with water content <15.B. pseudomallei did not grow until 60 d of incubation, suggesting that water contents of soils in which it dwelled would be one important factor in determining the growth rate.

Assessment of toxicity of polycyclic aromatic hydrocarbons in sediments of Kaohsiung Harbor, Taiwan

Polycyclic aromatic hydrocarbon (PAH) contamination and toxicity levels in the surface sediments of Kaohsiung Harbor, Taiwan were evaluated using sediment quality guidelines (SQGs) and toxic equivalent factors. Eighty surface sediment samples were collected from twenty locations in Kaohsiung Harbor for PAH analysis using gas chromatography/mass spectrometry (GC/MS). Concentrations of total PAHs varies from 34.0 to 16,700 ng/g with a mean concentration of 1490±2689 ng/g. The spatial distribution of PAHs reveals that PAH concentration is relatively higher in the river mouth regions, especially in the Salt River mouth where it gradually diminishes toward the harbor region. Distributions of PAHs, during both the wet and dry seasons, show that PAHs are more easily disbursed in the receiving sea water thereby leading to a wider range of chemical distribution. Hence, most of the chemicals accumulate in the harbor water channel. Diagnostic ratios show that the possible source of PAHs in the southern industrial area of the harbor could be coal combustion while in the other zones it could be petroleum combustion and/or a mixed sources. The toxic equivalent concentrations (TEQ(carc)) of PAHs varied from 3.9 to 1970 ng TEQ/g. The higher total TEQ(carc) values were found in the southern industrial area of the harbor. As compared with US sediment quality guidelines, the observed levels of PAHs in the industrial zone exceeded the effects range low (ERL), which will eventually cause acute biological damage. Based on the analyses using the SQGs, surface sediments from Kaohsiung Harbor were moderately contaminated and most samples have a low probability of toxicity pollution, except for the Salt River mouth situated in the south Kaohsiung Harbor area. This area has a medium to high probability of toxicity pollution.

Evaluation of natural attenuation rate at a gasoline spill site

Contamination of groundwater by gasoline and other petroleum-derived hydrocarbons released from underground storage tanks (USTs) is a serious and widespread environmental problem. Natural attenuation is a passive remedial approach that depends upon natural processes to degrade and dissipate contaminants in soil and groundwater. Currently, in situ column technique, microcosm, and computer modeling have been applied for the natural attenuation rate calculation. However, the subsurface heterogeneity reduces the applicability of these techniques. In this study, a mass flux approach was used to calculate the contaminant mass reduction and field-scale decay rate at a gasoline spill site. The mass flux technique is a simplified mass balance procedure, which is accomplished using the differences in total contaminant mass flux across two cross-sections of the contaminant plume. The mass flux calculation shows that up to 87% of the dissolved total benzene, toluene, ethylbenzene, and xylene (BTEX) isomers removal was observed via natural attenuation at this site. The efficiency of natural biodegradation was evaluated by the in situ tracer method, and the first-order decay model was applied for the natural attenuation/biodegradation rate calculation. Results reveal that natural biodegradation was the major cause of the BTEX mass reduction among the natural attenuation processes, and approximately 88% of the BTEX removal was due to the natural biodegradation process. The calculated total BTEX first-order attenuation and biodegradation rates were 0.036 and 0.025% per day, respectively. Results suggest that the natural attenuation mechanisms can effectively contain the plume, and the mass flux method is useful in assessing the occurrence and efficiency of the natural attenuation process.

Treatment of petroleum-hydrocarbon contaminated soils using hydrogen peroxide oxidation catalyzed by waste basic oxygen furnace slag

The contamination of subsurface soils with petroleum hydrocarbons is a widespread environmental problem. The objective of this study was to evaluate the potential of applying waste basic oxygen furnace slag (BOF slag) as the catalyst to enhance the Fenton-like oxidation to remediate fuel oil or diesel contaminated soils. The studied controlling factors that affect the removal efficiency of petroleum hydrocarbons included concentrations of H(2)O(2), BOF slag dosages, types of petroleum hydrocarbons (e.g., fuel oil and diesel), and types of iron mineral. Experimental results indicate that oxidation of petroleum hydrocarbon via the Fenton-like process can be enhanced with the addition of BOF slag. Results from the X-ray powder diffraction analysis reveal that the major iron type of BOF slag/sandy loam system was iron mineral (e.g., alpha-Fe(2)O(3) and alpha-FeOOH). Approximately 76% and 96% of fuel oil and diesel removal were observed (initial total petroleum hydrocarbon (TPH) concentration=10,000 mg kg(-1)), respectively, with the addition of 15% of H(2)O(2) and 100 g kg(-1) of BOF slag after 40 h of reaction. Because BOF slag contains extractable irons such as amorphous iron and soluble iron, it can act as an iron sink to supply iron continuously for Fenton-like oxidation. Results demonstrate that Fenton-like oxidation catalyzed by BOF slag is a potential method to be able to remediate petroleum-hydrocarbon contaminated soils efficiently and effectively.

Application of real-time PCR, DGGE fingerprinting, and culture-based method to evaluate the effectiveness of intrinsic bioremediation on the control of petroleum-hydrocarbon plume.

Real-time polymerase chain reaction (PCR), denaturing gradient gel electrophoresis (DGGE), and the culture-based method were applied in the intrinsic bioremediation study at a petroleum-hydrocarbon contaminated site. The genes of phenol hydroxylase (PHE), ring-hydroxylating toluene monooxygenase (RMO), naphthalene dioxygenase (NAH), toluene monooxygenase (TOL), toluene dioxygenase (TOD), and biphenyl dioxygenase (BPH4) were quantified by real-time PCR. Results show that PHE gene was detected in groundwater contaminated with benzene, toluene, ethylbenzene, xylene isomers (BTEX) and methyl tert-butyl ether (MTBE), and this indicates that intrinsic bioremediation occurred at this contaminated site. Results from DGGE analyses reveal that the petroleum-hydrocarbon plume caused the variation in microbial communities. In this study, MTBE degraders including Pseudomonas sp. NKNU01, Bacillus sp. NKNU01, Klebsiella sp. NKNU01, Enterobacter sp. NKNU01, and Enterobacter sp. NKNU02 were isolated from the contaminated groundwater using the cultured-based method. Results from MTBE biodegradation experiment show that the isolated bacteria were affected by propane. This indicates that propane may influence the metabolic pathway of MTBE by these bacteria. Knowledge and comprehension obtained from this study will be helpful in evaluating the occurrence and effectiveness of intrinsic bioremediation on the remediation of petroleum-hydrocarbon contaminated groundwater.

Evaluation of TCDD biodegradability under different redox conditions

Polychlorinated dibenzo-p-dioxins have been generated as unwanted by-products in many industrial processes. Although their widespread distribution in different environmental compartments has been recognized, little is known about their fate in the ultimate environment sinks. The highly stable dioxin isomer 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been called the most toxic compound known to man. In this laboratory microcosm study, TCDD bioavailability was evaluated under five reduction/oxidation (redox) conditions including aerobic biodegradation, aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Activated sludge and aquifer sediments from a TCDD and a pentachlorophenol (PCP) contaminated site were used as the inocula. Acetate, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in cometabolism and reductive dechlorination microcosms. After a 90-day incubation period, microcosms constructed under reductive dechlorination conditions were the only treatment showing promising remediation results. The highest TCDD degradation rate [up to 86% of TCDD removal (with an initial concentration of 96 microg/kg of soil)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cakes as the primary substrates. Except for reductive dechlorination microcosms, no significant TCDD removal was observed in the microcosms prepared under other conditions. Thus, application of an effective primary substrate to enhance the reductive dechlorination process is a feasible method for TCDD bioremediation. Bioremediation expense can be significantly reduced by the supplement of some less expensive alternative substrates (e.g., sludge cakes, cane molasses). Results would be useful in designing a scale-up in situ or on-site bioremediation system such as bioslurry reactor for field application.

Biodegradation of propionitrile by Klebsiella oxytoca immobilized in alginate and cellulose triacetate gel

A microbial process for the degradation of propionitrile by Klebsiella oxytoca was studied. The microorganism, K. oxytoca, was isolated from the discharged wastewater of metal plating factory in southern Taiwan and adapted for propionitrile biodegradation. The free and immobilized cells of K. oxytoca were then examined for their capabilities on degrading propionitrile under various conditions. Alginate (AL) and cellulose triacetate (CT) techniques were applied for the preparation of immobilized cells. The efficiency and produced metabolic intermediates and end-products of propionitrile degradation were monitored in bath and continuous bioreactor experiments. Results reveal that up to 100 and 150 mM of propionitrile could be removed completely by the free and immobilized cell systems, respectively. Furthermore, both immobilized cell systems show higher removal efficiencies in wider ranges of temperature (20-40 degrees C) and pH (6-8) compared with the free cell system. Results also indicate that immobilized cell system could support a higher cell density to enhance the removal efficiency of propionitrile. Immobilized cells were reused in five consecutive degradation experiments, and up to 99% of propionitrile degradation was observed in each batch test. This suggests that the activity of immobilized cells can be maintained and reused throughout different propionitrile degradation processes. A two-step pathway was observed for the biodegradation of propionitrile. Propionamide was first produced followed by propionic acid and ammonia. Results suggest that nitrile hydratase and amidase were involved in the degradation pathways of K. oxytoca. In the continuous bioreactor, both immobilized cells were capable of removing 150 mM of propionitriles completely within 16h, and the maximum propionitriles removal rates using AL and CT immobilized beads were 5.04 and 4.98 mM h(-1), respectively. Comparing the removal rates obtained from batch experiments with immobilized cells (AL and CT were 1.57 and 2.18 mM h(-1) at 150 mM of propionitrile, respectively), the continuous-flow bioreactor show higher potential for practical application.