Characteristics of azaarenes and dioxins in gases emitted from waste incinerators

In this study, we propose an analytical method to determine the fourteen of azaarenes present in flue gas samples collected according to Japanese Industrial Standard K 0311, which designates the method for the determination of dioxins in flue gas. Azaarenes can be analyzed using the acidic water phase after shaking extraction with dichloromethane, which is unnecessary for dioxin analysis. Flue gas samples were obtained from 24 waste incinerators in Japan, and azaarenes were detected in all the flue gas samples (0.21–3800 μg/m³ _N). The most abundant of the detected compounds were quinoline and isoquinoline. The concentration of azaarenes had a tendency to increase with that of polychlorinated dibenzo-p-dioxins and dibenzofurans. The isomer distribution of heptachloro-dibenzofurans (HpCDFs) was calculated using the computed Gibbs energy of formation (ΔG _f ) obtained by the semiempirical molecular orbital method at various temperatures. The calculated isomer distribution was fitted to the measured value of HpCDFs. It seems that the temperature obtained from the fitting calculations is an indicator of the cooling capacity of the combustion gas in an incinerator. The computed ΔG _f also explained the measured isomer distributions of azaarenes. It is suggested that the isomer distribution of azaarenes in the combustion process is thermodynamically controlled. This work was presented in part at the International Conference on Combustion, Incineration/Pyrolysis, and Emission Control, 2006, Kyoto     

Seasonal change of PCDDs/PCDFs/DL-PCBs in the water of Ayase River, Japan: pollution sources and their contributions to TEQ

In Japan, Ayase River is one of the most polluted rivers by PCDDs, PCDFs and dioxin-like PCBs, which are referred to as dioxins in this paper. The water samples of the river were collected once per month for a year, and dioxins were analyzed to examine the dioxin sources and their contributions to toxic equivalent (TEQ). The WHO-2006 TEQs ranged from 0.26 to 7.0 pg-TEQ L⁻¹ and the average was 2.7 pg-TEQ L⁻¹; eight of 12 samples exceeded the environmental quality standard in Japan (1.0 pg-TEQ L⁻¹). The TEQ value was high during the irrigation period from May to August. The most part of the dioxins in the river water existed in suspended solids (SS) and it seemed that the river received water with highly-dioxin-contaminated SS in the irrigation period. The homologue profiles of the water samples suggested that the dioxins were influenced by pentachlorophenol (PCP) and chlornitrofen (CNP) formulations which were widely used as herbicides for the paddy fields in Japan. According to TEQ apportionment estimated by using indicative congeners, the TEQ was mainly contributed by PCP. Moreover, it was also shown that the TEQ contributions of PCP and CNP formulations increased along with the increase of the total TEQ and the TEQ contribution was dominated by these herbicides during the irrigation period. Therefore, it was concluded that the herbicides-originated dioxins run off from the paddy fields into the river during the irrigation period and increased the dioxins level in the river water. The result from the principal component analysis was consistent with these conclusions.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice straw smoke and their origins in Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) contained in the smoke generated from rice straw burning in post-harvest paddy fields in Japan were analyzed to determine their congener profiles. Both the apportionment of toxic equivalent (TEQ) by using indicative congeners and the comparison of the homolog profiles showed that the PCDDs/PCDFs/DL-PCBs present in the rice-straw smoke were greatly influenced by those present as impurities in pentachlorophenol (PCP) and chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations that had been widely used as herbicides in paddy fields in Japan. Further, in order to investigate the effects of paddy-field soil on the PCDDs/PCDFs/DL-PCBs present in rice-straw smoke, PCDD/PCDF/DL-PCB homolog profiles of rice straw, rice-straw smoke and paddy-field soil were compared. Rice-straw smoke was generated by burning rice straw on a stainless-steel tray in a laboratory. The results suggested that the herbicides-originated PCDDs/PCDFs/DL-PCBs and the atmospheric PCDDs/PCDFs/DL-PCBs contributed predominantly to the presence of PCDDs/PCDFs/DL-PCBs in the rice-straw smoke while the contribution of PCDDs/PCDFs/DL-PCBs formed during rice straw burning was relatively minimal. The major sources of the PCDDs/PCDFs/DL-PCBs found in the rice-straw smoke were attributed primarily to the paddy-field soil adhered to the rice straw surface and secondarily to the air taken by the rice straw. The principal component analysis supported these conclusions. It is concluded that rice straw burning at paddy fields acts as a driving force in the transfer of PCDDs/PCDFs/DL-PCBs from paddy-field soil to the atmosphere.     

Baseline study of methane emission from open digesting tanks of palm oil mill effluent treatment

Anthropogenic release of greenhouse gases, especially CO₂ and CH₄ has been recognized as one of the main causes of global warming. Several measures under the Kyoto Protocol 1997 have been drawn up to reduce the greenhouse gases emission. One of the measures is Clean Development Mechanisms (CDM) that was created to enable developed countries to cooperate with developing countries in emission reduction activities. In Malaysia, palm oil industry particularly from palm oil mill effluent (POME) anaerobic treatment has been identified as an important source of CH₄. However, there is no study to quantify the actual CH₄ emission from the commercial scale wastewater treatment facility. Hence, this paper shall address the CH₄ emission from the open digesting tanks in Felda Serting Hilir Palm Oil Mill. CH₄ emission pattern was recorded for 52 weeks from 3600 m³ open digesting tanks. The findings indicated that the CH₄ content was between 13.5% and 49.0% which was lower than the value of 65% reported earlier. The biogas flow rate ranged between 0.8 l min⁻¹ m⁻² and 9.8 l min⁻¹ m⁻². Total CH₄ emission per open digesting tank was 518.9 kg day⁻¹. Relationships between CH₄ emission and total carbon removal and POME discharged were also discussed. Fluctuation of biogas production was observed throughout the studies as a result of seasonal oil palm cropping, mill activities, variation of POME quality and quantity discharged from the mill. Thus only through long-term field measurement CH₄ emission can be accurately estimated.     

PCB decomposition and formation in thermal treatment plant equipment

In this study we investigated both the decomposition and unintentional formation of polychlorinated biphenyl congeners during combustion experiments of refuse-derived fuel (RDF) and automobile shredder residue (ASR) at several stages in thermal treatment plant equipment composed of a primary combustion chamber, a secondary combustion chamber, and other equipments for flue gas treatment. In both experiments, the unintentional formation of PCB occurred in the primary combustion chamber at the same time as the decomposition of PCB in input samples. By combusting RDF, non-ortho-PCB predominantly formed, whereas ortho-PCB and symmetric chlorinated biphenyls (e.g., #52/69, #87/108, and #151) tended to be decomposed. ASR formed the higher chlorinated biphenyls more than RDF. These by-products from ASR had no structural relation with ortho-chlorine. Lower chlorinated biphenyls appeared as predominant homologues at the final exit site, while all congeners from lower to higher chlorinated PCB were unintentionally formed as by-products in the primary combustion chamber. This result showed that the flue gas treatment equipments effectively removed higher chlorinated PCB. Input marker congeners of RDF were #11, #39, and #68, while those for ASR were #11, #101, #110/120, and #118. Otherwise, combustion marker congeners of RDF were #13/12, #35, #77, and #126, while those for ASR were #170, #194, #206, and #209. While the concentration of PCB increased significantly in the primary combustion chamber, the value of toxicity equivalency quantity for dioxin-like PCB decreased in the secondary combustion chamber and the flue gas treatment equipments.     

Specialized feeding mechanism in the pelagic copepod genus Heterorhabdus (Calanoida: Heterorhabdidae), with special reference to the mandibular tooth and labral glands

Scanning and transmission electron microscopy and gut-content analysis revealed the fine structure of the mandibular ventralmost tooth and labral glands of the carnivorous copepods Heterorhabdus spp. on the basis of the specimens collected in the waters near Nansei Islands, Southwestern Japan, in November 1993. The ventralmost tooth is hollow with a subterminal pore and a basal opening. The distal region of the tooth is like a hypodermic needle and is strengthened by opal layers. The tip of the tooth including the subterminal pore usually protrudes from between the labrum and the paragnath, while the basal region of the ventralmost tooth and the whole parts of the other teeth are semi-enclosed in the preoral food chamber formed by the labrum and the paragnath. There is a large glandular cell in the basal region of the mandibular gnathobase, but no direct connection exists between the gnathobasal cells and the tubular lumen of the ventralmost tooth. The posterior surface of the labrum carries a lateral pair of large glandular pores, which are located close to, and appear to fit exactly the basal openings of the ventralmost teeth. Each of these glands has two massive secretory cells, and the secretory materials from these cells appear to be mixed before discharge from the pore. A specialized feeding mechanism is proposed, wherein venom or anaesthetic is injected from the labral-gland pores into the tubular lumen of the mandibular ventralmost tooth, and then relcased into the prey from its subterminal pore immediately after capture using the stout maxillae of prey macrozooplankters such as copepodids and polychaetes.     

Relationship between mouthpart structures and in situ feeding habits of species of the family Pontellidae (Copepoda: Calanoida)

Pontellid copepods were collected from the surface waters of a tidal front region in the Bungo Channel (the Inland Sea of Japan) in June 1986 to examine the relationship between the morphology of cephalic appendages and gut contents. In particular, two dominant species,Labidocera japonica Mori andPontellopsis yamadae Mori, were compared in detail. Large setae on the second maxillae ofL. japonica possessed two rows of setules at right angles to each seta along its inner margin except a terminal part which was serrated, whereas the inner margin of those setae ofP. yamadae was entirely serrated. Judging from the structure of the mouthparts, especially the second maxillae, the former species seems to employ both suspension and raptorial feeding modes, in contrast to the latter, which may use only the raptorial mode of feeding. InP. yamadae, the first maxilla and the maxilliped are also modified for carnivory. Gut content analysis supported the morphological evidence for feeding differences, and revealed thatP. yamadae is a carnivore preying mainly on copepodids whileL. japonica feeds omnivorously on copepod nauplii and phytoplankton particles. Since the mouthpart structures of congeners are quite similar to each other, the feeding behavior and habits might also be similar. Within the family Pontellidae, the generaAnomalocera, Calanopia, Epilabidocera, andPontella have mouthpart structures similar to those ofLabidocera, whereas the genusPontellina resemblesPontellopsis. Morphological similarities would suggest that the first group of genera employs both suspension and raptorial feeding modes, and thatPontellina is a carnivore likePontellopsis.     

Congener profiles of PCB and a proposed new set of indicator congeners

In this study, a new method for calculating total PCB and toxic equivalents (TEQ) of coplanar PCB (Co-PCB) was proposed, called the 'PCB dual method'. This method analysed various kinds of technical PCB, samples contaminated by technical PCB and byproduct PCB. In the PCB dual method, a data set of 15 indicator congeners was utilized for the calculations, having IUPAC nos. #3, #8, #28, #52, #77, #101, #105, #118, #126, #138, #153, #180, #194, #206 and #209. The 15 congener set was chosen from the major congeners, determined by HRGC/HRMS analysis, in 18 technical PCB, Kanechlor, Aroclor, Clophen and Chlorofen, and 20 other samples, such as indoor air, flue gases, emission gases, municipal solid waste (MSW), ash and sealant. To obtain total PCB and TEQ of Co-PCB, the intermediate sum for the concentration of the 15 congeners was multiplied by each multiplication factor. As a result, we obtained the average factor used to calculate total PCB in technical PCB and other samples. For technical PCB, the factor was 3.01, while for indoor air samples, flue and emission gases, MSW, ash and sealants, the factors were 3.92, 4.16, 3.68, 4.52 and 4.77, respectively. Moreover, the factor used to calculate the TEQ of Co-PCB in Kanechlor and other source samples were also obtained. The factors for Kanechlor, indoor air samples and emission gases from a cement plant were in the order of 10(-5), while the factor for flue gases in a MSW incinerator was in the order of 10(-3). These data were valuable for the rough estimation of the TEQ of Co-PCB without separation from other PCB before individual measurements.     

Production and characterization of KOH-activated carbon derived from polychlorinated biphenyl residue generated by the sodium dispersion process

Polychlorinated biphenyl (PCB) residues from the sodium dispersion (SD) process were employed as the raw materials for the production of activated carbon using KOH activation. The pore properties, such as the specific surface area and pore size distribution, were characterized using the Barrett–Joyner–Halenda method and the Horvath–Kawazoe method based on the N₂ adsorption isotherm at 77 K. The activated carbon produced showed similar adsorption capacities and specific surface areas to the commercially available product. The effects of the activation conditions on the porosity of the activated carbon produced were studied. The most significant factor affecting the specific surface proved to be the activation temperature. The activated carbon produced from PCB residues from the high-temperature (423–443 K) SD process had a binary pore size distribution well developed in the 4 nm region and in the micropore region. The pore structure of the carbon produced from PCB residues from the low-temperature (333–393 K) SD process had a wide range of micropores and mesopores.     

Reduction of Methane Released from Palm Oil Mill Lagoon in Malaysia and Its Countermeasures

Palm oil industry in Malaysia is one of the potential candidates for the CDM project because large amount of methane is emitted from the lagoons and open digesting tank of the wastewater treatment system. Therefore the first objective of the project is to investigate the actual GHG emission from the lagoons and open digesting tank in palm oil mills in order to establish the baseline for CDM project. Results indicated that methane contribution to biogas released from the open digesting tank and lagoon systems were 35% and 45%, respectively. These values are much lower than the reported value of 65% obtained by complete anaerobic condition of lab-scale experiments. Based on actual methane release measurement and information gathered from palm oil mill about wastewater treatment, significant amount of methane emission to the atmosphere can be reduced with the installation of new closed digesting tank system converted from the open digesting tank such as just by covering it with applying CDM. It is estimated that a total of RM2.6 million could be obtained from the selling of electricity generated from biogas generation and Certified Emission Reduction(CER). This revised version was published online in August 2006 with corrections to the Cover Date.