Supercritical water gasification of sewage sludge using bench-scale batch reactor: advantages and drawbacks

Sewage sludge, a byproduct of municipal wastewater treatment, was gasified by supercritical water using a bench-scale batch reactor. Configuration of bench-scale batch reactor and operation procedures are discussed in detail. Experience and challenges that arose during the experiment are also shared. Using the bench-scale reactor under the condition of 600 °C, 23 MPa, and a reaction time of 60 min without catalyst presence, a total gas yield of 9.8 mol/(kg-sewage sludge) was obtained. Furthermore, investigations on operational parameters were conducted. Extension of reaction time up to 60 min increased the gasification, reaching a plateau thereafter. Investigation on pressure indicated the superiority of supercritical pressure. The addition of Ni as a catalyst also promoted gasification, although inorganic salts and char seemed to cover the catalyst surface. With regard to the prospect of future operation at a municipal waste water treatment plant, the effect of operational parameters on heavy metal concentration in the liquid phase is also discussed.     

Quantitative analysis of microbial biomass yield in aerobic bioreactor

We have studied the integrated model of reaction rate equations with thermal energy balance in aerobic bioreactor for food waste decomposition and showed that the integrated model has the capability both of monitoring microbial activity in real time and of analyzing biodegradation kinetics and thermal-hydrodynamic properties. On the other hand, concerning microbial metabolism, it was known that balancing catabolic reactions with anabolic reactions in terms of energy and electron flow provides stoichiometric metabolic reactions and enables the estimation of microbial biomass yield (stoichiometric reaction model). We have studied a method for estimating real-time microbial biomass yield in the bioreactor during food waste decomposition by combining the integrated model with the stoichiometric reaction model. As a result, it was found that the time course of microbial biomass yield in the bioreactor during decomposition can be evaluated using the operational data of the bioreactor (weight of input food waste and bed temperature) by the combined model. The combined model can be applied to manage a food waste decomposition not only for controlling system operation to keep microbial activity stable, but also for producing value–added products such as compost on optimum condition.     

Correlation of low-volatile organic chlorine (LVOCl) and PCDD/Fs in various municipal waste incinerators (MWIs)

Medium- and low-volatile organic chlorine (M/LVOCl) and PCDD/Fs in flue gas from various municipal waste incinerators (MWIs) were monitored. The sample for M/LVOCl was collected in an adsorption tube which was thermally desorbed and the amount of chlorine was measured by atomic emission spectrometry (AES) detection using radiofrequency helium plasma. The helium plasma excited chlorine having an optical emission line of 837.6 nm was monitored. The MVOCl and LVOCl were organic chlorine groups whose boiling points (bp) ranged from 70-120 degrees C and 170-270 degrees C, respectively. The compounds having bp 120-170 degrees C were distributed in two tubes. LVOCl correlated well with PCDD/Fs (ng/Nm3, r=0.81) in a wide range of 0.01-100 ng/Nm3 of PCDD/Fs, while the correlation of LVOCl vs. TEQ was less related (r=0.69). These results agreed with the fact that LVOCl monitored the amount of organic chlorine without molecular structure information, which is critical to toxicity. Since the bp of LVOCl was not identical with that of PCDD/Fs, the regression was effected by the conditions of the gas treatment devices. Because most data of 2001 were collected just after the installation of PCDD/Fs in MWIs, the regression of 2001 was slightly different from that of 2002-2003. Eliminating these initial unsteady data, the regression of LVOCl vs. PCDD/Fs became better, giving r= 0.86. Besides having PCDD/Fs as surrogates, M/LVOCl is valuable as a versatile element-selective organic chlorine monitor to improve thermal process control.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in paddy soils and river sediments in Akita, Japan

Paddy soils and sediments from the Yoneshirogawa, Omonogawa, and Koyoshigawa River Basins in Akita were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The levels and compositions in those samples including soils from non-agricultural areas (non-agricultural soils) were investigated using isomer-specific analysis to determine characteristic sources. The PCDD/PCDF compositions in the samples were compared with respect to possible sources. The PCDD/PCDF concentrations in paddy soils were much higher than those in the non-agricultural soils and much higher than those found in other parts of Japan. Although PCDD/PCDFs were ubiquitous in sediments from river sources to mouths of the respective river basins, those concentrations were much lower than those from paddy soils and non-agricultural soils, and from other parts of Japan. Comparison of PCDD/PCDF homologues and isomer compositions for samples indicated that compositions of paddy soils and sediments, except for those from river sources, had similar characteristics to PCDD/PCDFs originating from impurities in herbicides, 2,4,6-trichlorophenyl 4-nitrophenyl ether (CNP) and pentachlorophenol (PCP), and that compositions of river-source sediments and non-agricultural soils resembled those of atmospheric depositions. Results of statistical analyses suggest that PCDD/PCDF contamination of paddy soils and sediments is attributable mainly to three sources: CNP, PCP, and atmospheric deposition. Results of this study also demonstrate that CNP and PCP are not only important contaminants of local areas of Japan, but that they exist throughout Akita, in northern Japan. We therefore conclude that PCDD/PCDF pollution caused by those compounds has a widespread influence on paddy soils and river sediments in Japan.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.     

Chemical and mineralogical evaluation of slag products derived from the pyrolysis/melting treatment of MSW

This paper provides the results of studies on the characteristics of novel material derived from pyrolysis/melting treatment of municipal solid waste in Japan. Slag products from pyrolysis/melting plants were sampled for the purpose of detailed phase analysis and characterization of heavy metal-containing phases using optical microscopy, electron probe microanalysis (EPMA), XRF and XRD. The study revealed that the slag material contains glass (over 95%), oxide and silicate minerals (spinel, melilite, pseudowollastonite), as well as individual metallic inclusions as the major constituents. A distinct chemical diversity was discovered in the interstitial glass in terms of silica content defined as low and high silica glass end members. Elevated concentrations of Zn, Cr, Cu, Pb and Ba were recorded in the bulk composition. Cu, Pb and Ba behave as incompatible elements since they have been markedly characterized as part of polymetallic alloys and insignificantly sulfides in the form of spherical metallic inclusions associated with tracer amounts of other elements such as Sb, Sn, Ni, Zn, Al, P and Si. In contrast, an appreciable amount of Zn is retained by zinc-rich end members of spinel and partially by melilite and silica glass. Chromium exhibits similar behavior, and is considerably held by Cr-rich spinel. The intense incorporation of Zn and Cr into spinel indicates the very effective enrichment of these two elements into phases more environmentally resistant than glass. There was no evidence, however, that Cu and Pb enter into the structure of the crystalline silicates or oxides that may lead to their easier leachability upon exposure to the environment.     

Influence of arsenic stress on synthesis and localization of low-molecular-weight thiols in Pteris vittata

The roles of low-molecular-weight thiols (LMWTs), such as glutathione and phytochelatins, in arsenic (As) tolerance and hyperaccumulation in Pteris vittata an As-hyperaccumulator fern remain to be better understood. This study aimed to thoroughly characterize LMWT synthesis in P. vittata to understand the roles played by LMWTs in As tolerance and hyperaccumulation. LMWT synthesis in P. vittata was induced directly by As, and not by As-mediated oxidative stress. Expression of PvECS2, one of the putative genes of γ-glutamylcysteine synthetase (γECS), increases in P. vittata shoots at 48 h after the onset of As exposure, almost corresponding to the increase in the concentrations of γ-glutamylcysteine and glutathione. Furthermore, localization of As showed similar trends to those of LMWTs in fronds at both whole-frond and cellular levels. This study thus indicates the specific contribution of LMWTs to As tolerance in P. vittata. γECS may be responsible for the As-induced enhancement of LMWT synthesis.     

Detection of dicofol and related pesticides in human breast milk from China, Korea and Japan

Previously, we demonstrated that the concentrations of DDTs were greater in breast milk collected from Chinese mothers than from Japanese and Korean mothers. To investigate dicofol as a possible source of the DDTs in human breast milk, we collected breast milk samples from 2007 to 2009 in China (Beijing), Korea (Seoul, Busan) and Japan (Sendai, Takarazuka and Takayama). Using these breast milk samples, we quantified the concentrations of dichlorobenzophenone, a pyrolysis product of dicofol (simply referred to as dicofol hereafter), dichlorodiphenyltrichloroethane and its metabolites (DDTs) using GC-MS. Overall, 12 of 14 pooled breast milk samples from 210 mothers contained detectable levels of dicofol (>0.1 ng g⁻¹ lipid). The geometric mean concentration of dicofol in the Japanese breast milk samples was 0.3 ng g⁻¹ lipid and significantly lower than that in Chinese (9.6 ng g⁻¹ lipid) or Korean breast milk samples (1.9 ng g⁻¹ lipid) (p < 0.05 for each). Furthermore, the ΣDDT levels in breast milk from China were 10-fold higher than those from Korea and Japan. The present results strongly suggest the presence of extensive emission sources of both dicofol and DDTs in China. However, exposure to dicofol cannot explain the large exposure of Chinese mothers to DDTs because of the trace levels of dicofol in the ΣDDTs. In the present study, dicofol was confirmed to be detectable in human breast milk. This is the first report to identify dicofol in human samples.