Behavior of PAHs from sewage sludge incinerators in Korea

Although production of sewage sludge increases every year, its proper treatment has only been recently raised as a new issue, as current landfill and ocean dumping arrangements are expected to become increasingly difficult to manage in the future. The Korean Ministry of Environment plans to diversify its processing facilities and expand its processing systems by 2011, with the purpose of processing all sludge produced in Korea. According to this plan, incineration (including incineration of municipal wastes) will process 30% of the entire sewage sludge throughout the country in 2011. This study reviews the characteristics of PAH, which is one of the organic substances found in sewage sludge during the incinerating process. The total amount of PAH produced from sewage sludge incineration was found to be 6.103 mg/kg on average, and investigation performed on 16 PAHs of inlets and outlets of the air control devices at five full-scale incineration facilities showed that concentrations of the PAHs on the inlet and on the outlet ranged from 3.926 to 925.748 microg/m(3) and from 1.153 to 189.449 microg/m(3), respectively. In the case of the incineration facility fed with municipal waste (95%) and sewage sludge (5%), the total of the PAH emissions concentration was higher than that found at the incineration facilities used exclusively to treat sewage. The combustion of waste vinyl and plastics contained in municipal waste fed into the facility might contribute to the high levels of PAHs in the stack gas. However more investigation is needed on the production mechanism of PAHs at different operating conditions of the incineration facilities, such as the types of waste, and other relevant factors.     

Gene expression analysis and classification of mode of toxicity of polycyclic aromatic hydrocarbons (PAHs) in Escherichia coli

Escherichia coli is known to respond to certain toxic chemicals through an increased expression of various stress genes. In this study, therefore, the expression of recA, katG, fabA and grpE genes was used as a representative for DNA, oxidative, membrane and protein damage, respectively, after E. coli was exposed to different polycyclic aromatic hydrocarbons (PAHs), i.e., phenanthrene, naphthalene and benzo[a]pyrene. To accomplish this, the expression levels of these four genes were quantified using a real-time RT-PCR analysis when E. coli cultures were under stressful conditions, such as those caused by an exposure to mitomycin C, hydrogen peroxide and phenol. It was found that the primary toxic effect of each chemical is clearly seen when the expression levels of the different genes are compared. Tests with the PAHs showed naphthalene and benzo[a]pyrene to be genotoxic, while phenanthrene had no clear effect on the expression of any of these genes. Based on these results, the effects due to these toxic chemicals and the extent of each stress can be evaluated with ease using the expression levels of different stress responsive genes.     

Investigation of the generation of hydroxyl radicals and their oxidative role in the presence of heterogeneous copper catalysts

The presence and impact of hydroxyl radicals generated via the catalytic decomposition of H(2)O(2) over heterogeneous copper catalysts were investigated by using two detection methods, an electron spin resonance-spin trapping method and a chemical probe method. Detection of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct signal and formation of 4-chlorocatechol during the oxidation of a 4-chlorophenol substrate demonstrated that the three heterogeneous copper catalysts employed here (CuO, Cu/Al(2)O(3) and CuO.ZnO/Al(2)O(3)) were capable of generating hydroxyl radicals in combination with H(2)O(2). The oxidative mechanism of the hydroxyl radical in the presence of heterogeneous copper catalysts is discussed with regard to the further oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct and hydroxylated products of 4-chlorophenol oxidation. Interestingly, integration of the 5,5-dimethyl-1-pyrroline-N-oxide-OH adduct signal could not be used to reliably measure the total amount of hydroxyl radicals generated as a result of oxidative attack on the adduct. This may be as a result of locally higher hydroxyl radical concentrations in the presence of a heterogeneous catalyst leading to further unwanted oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH.     

Distribution of dioxins, furans, and dioxin-like PCBs in solid products generated by pyrolysis and melting of automobile shredder residues

Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls (PCBs) in char and slag produced from automobile shredder residue by pyrolysis and melting process were analyzed to measure changes in the characteristics and distribution of their congeners caused by thermal treatment. In particular, a large quantity of dioxin-like PCBs occurred in low-chlorinated congeners. The concentration of PCDDs/PCDFs in char was 0.542 microg/kg, with mostly PCDFs dominant and its toxicity equivalent concentration (TEQ) was about 70ngTEQ/kg. The concentration and toxicity equivalent concentration of dioxin-like PCBs in char were 0.869 microg/kg and 1.60ngTEQ/kg, respectively. Melted char slag was produced using various cooling methods: water quenching, air cooling, and slow cooling. The concentrations of PCDDs/PCDFs in slag produced by the methods were 1.51, 1.38, and 2.43ngTEQ/kg, respectively; those of dioxin-like PCBs were close to 0.01ngTEQ/kg. The congener distributions varied only slightly among the cooling methods. Applying melting procedure to char reduced PCDD/PCDF concentration by 95.3%, and the corresponding TEQ concentration was reduced by 97.9%. We thus conclude that melting process is an efficient way to reduce the concentrations of PCDDs/PCDFs in solids produced by pyrolysis.     

The characteristics of wet air oxidation of phenol over CuOx/Al2O3 catalysts: effect of copper loading

The nature of active copper species is well-known to vary with copper loading, i.e., isolated Cu(2+) to bulk CuO. In this work, however, the effect of copper loading on the activity and the selectivity was investigated for the wet oxidation of phenol over CuO(x)/Al(2)O(3) catalysts. The activity and the mineralization selectivity of the catalysts increased with copper loading up to 7wt% and remained almost the same at a higher loading. The optimum copper loading was about 7wt% for the wet oxidation of phenol over CuO(x)/Al(2)O(3) catalysts in this work. The nature of copper species with different loading was characterized with TPR, XRD, and XANES. The chemical states of copper in the CuO(x)/Al(2)O(3) catalysts were confirmed as varying with copper loading: isolated Cu(2+) ions for 1wt%; highly dispersed Cu(2+) cluster for 5wt% and 7wt%, and bulk CuO for 10-25wt%. The stability of the CuO(x)/Al(2)O(3) catalysts with different copper loading was also studied with respect to carbonaceous deposits and copper leaching.     

A sensitive and reliable quantification method for Bisphenol A based on modified competitive ELISA method

Bisphenol A (BPA), generally known as bisphenols, has been identified as a potential estrogenic substance. BPA must be conjugated to carrier protein and BSA was commonly used. 4,4-Bis(4-hydroxyphenyl) valeric acid (BHPVA) has a bisphenolic structure and a long carbon chain with a reactive carboxyl group on the end. In this study, BHPVA-BSA was used to produce polyclonal antibody against bisphenolic structure, and a modified competitive ELISA method for quantification of BPA was developed. This system was based on BHPVA-BSA for polyclonal antibody production against bisphenolic structure, and BHPVA-HRP for determination of BPA substituting detection antibody in competitive reaction. Recovery was assessed at 10 different concentrations (2-1000 ng/ml) of BHPVA, and the recovery range was from 96.3% to 107.2%. The variation was from 6.2% to 9.8% for intra assay and from 10.1% to 12.6% for inter assay. The quadratic was used to establish the curve regression. The range was found to be between 2 and 1000 ng/ml. This modified competitive ELISA method has proven to be a very useful tool for quantification of BPA without the unexpected interaction of BSA and anti-BSA polyclonal antibody.     

Desorption Kinetics of Benzene in a Sandy Soil in the Presence of Powdered Activated Carbon

Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption–desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q _irr) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption–desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q _irr) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4–40 times) rate constant for rapid process (k ₁) than that for slow process (k ₂), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.     

Development of clean technology in alcohol fermentation industry

A zero-discharge system for the alcohol fermentation industry was developed by recycling distillery waste (stillage). Stillage was able to be recycled as cooking water for the next fermentation after treating it with appropriate separation processes. Ultrafiltration with a ceramic membrane played a key role in the separation processes. When the permeate from the ultrafiltration of stillage was recycled to the cooking step, the total fermentation time was prolonged from 60 to 70–80 h, but the average ethanol production yield (8.8%) was similar to that in the conventional process (9.0%). In contrast, direct recycle of stillage without membrane filtration showed negative effects on both fermentation time and alcohol yield as recycling was repeated. This new process was confirmed to have stable operation over eight recycles. This new clean technology for the ethanol production industry makes it possible to eliminate the stillage treatment steps using the conventional biological treatment processes such as anaerobic digestion and activated sludge steps currently being operated in industry.