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.     

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.     

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     

Woody biomass and RPF gasification using reforming catalyst and calcium oxide

This study focused on steam gasification and reforming of waste biomass using a reforming catalyst. The purpose of the study was to evaluate the durability of a commercial Ni reforming catalyst and the effect of CaO on the reforming behavior, and to clarify detailed factors of catalytic performance, as well as the effect of operating parameters on the characteristics of produced gas composition. Moreover, catalyst regeneration was carried out and the behavior of catalytic activity based on gas composition was investigated. Using a fluidized bed gasifier and a fixed bed reformer, gasification and reforming of waste biomass were carried out. Commercial Ni-based catalyst and calcined limestone (CaO) were applied to the reforming reaction. Temperature of the gasifier and reformer was almost 1023 K. Ratio of steam to carbon in the feedstock [mol mol⁻¹] and equivalence ratio (i.e., ratio of actual to theoretical amount of oxygen) [-] were set at about 2 and 0.3, respectively. The feed rate of the feedstock into the bench-scale gasifier was almost 15 kg h⁻¹. The results of waste biomass gasification confirmed the improvement in H₂ composition by the CO₂ absorption reaction using the reforming catalyst and CaO. In addition, CaO proved to be especially effective in decreasing the tar concentration in the case of woody biomass gasification. Catalytic activity was maintained by means of catalyst regeneration processing by hydrogen reduction after air oxidation when woody biomass was used as feedstock.     

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.     

Absorption of atmospheric phenol by various tree species and their tolerance to phenol

To assess the effect of tree planting on atmospheric phenol, a study was made on the absorption of phenol by various tree species and the tolerance of these species to phenol. The absorption rates ranged from 21.3 (camellia) to 129 ng dm^‐2h^‐1 ppb^‐1 (Japanese elm) at 1000 μmol of photons m^‐2 s^‐1, and the absorption rate increased in the following order: coniferous tree species ? evergreen broad‐leaved tree species < deciduous broad‐leaved tree species. When the light intensity was varied, a linear relationship between the phenol absorption rate and the transpiration rate was observed for three tree species. In comparison with the absorption rate estimated from a simplified gas diffusive resistance model, we conclude that phenol is absorbed through the stomata and is metabolized fairly rapidly within the leaf tissue, although the absorption rate is less than the estimated potential absorption rate. At phenol concentrations below 200 ppb, the tree can absorb atmospheric phenol for at least 8 h without any visible foliar injury. Trees in general could act as an important sink for atmospheric phenol at phenol concentrations less than 200 ppb, a concentration about twenty times higher than normal ambient levels.     

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.     

Obligate commensalism of <Emphasis Type="Italic">Curvemysella paula</Emphasis> (Bivalvia: Galeommatidae) with hermit crabs

Curvemysella paula is a markedly crescent-shaped bivalve that lives inside snail shells occupied by hermit crabs. Here, we describe the unique symbiotic life, growth pattern, and reproductive biology of this bivalve, based on specimens collected from the shallow, muddy bottom of the Seto Inland Sea, Japan. C. paula was found attached to columellae in the siphonal canal, mainly of nassariid snail shells occupied by two types of hermit crabs: Diogenes edwardsii (Diogenidae) and Spiropagurus spiriger (Paguridae). The crescent-shaped shell of C. paula is an adaptation to symbiotic life in the narrow interspace between the snail shell and the hermit-crab abdomen. C. paula is a protandric hermaphrodite. In our samples, each host snail shell harbored one (or rarely a few) large female and several males. All the female bivalves settled on the host shells with their anterior end facing outward and benefited from currents created by the hermit crab when feeding. In the muddy bottom, snail shells are a limited resource for both the hermit crabs and symbiotic bivalves. The bivalves benefit from the mobility of the hermit crabs, which prevent the shells from becoming buried in the mud. C. paula represents the only example of obligate commensalism with hermit crabs found in Bivalvia.     

Apportionment of TEQs from four major dioxin sources in Japan on the basis of five indicative congeners

The major sources of dioxins (polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs)) in the environment in Japan have been considered to be combustion by-products, pentachlorophenol (PCP) formulations, chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations, and PCB products. Data on PCDDs, PCDFs and DL-PCBs from the four sources were analyzed, and indicative congeners whose concentrations were highly correlated with WHO-2006 toxic equivalencies (TEQs) were identified for each source sample. The indicative congeners for combustion by-products, PCP formulations, and CNP formulations were 2,3,4,7,8-pentachlorodibenzofuran, 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin, and 1,2,3,7,8-pentachlorodibenzo-p-dioxin, respectively; for PCB products, the indicative congeners were IUPAC Nos. #126- and #105-pentachlorobiphenyls. Moreover, using the data on PCDDs, PCDFs and DL-PCBs, we developed a set of equations for estimating the apportionment of TEQs from the four sources by using only the concentrations of the above-mentioned five indicative congeners. The equations were used along with the analysis results of different types of environmental samples collected from Japan, to determine the TEQ contributions of the four sources. The obtained values of TEQ contributions seemed to be reasonable. The estimation method was developed by using the data on major dioxin sources in Japan, and therefore, it is generally adaptable to environmental samples from any part of Japan. The method may be usable for regions outside Japan if source identification is carried out and the estimation equations are modified appropriately.     

Deposition of 137Cs in Rokkasho, Japan and its relation to Asian dust

Biweekly atmospheric depositions of (137)Cs were measured in Rokkasho, Aomori, Japan from March 2000 to March 2006 to study recent (137)Cs deposition. Although the deposition level was generally lower than the detectable limit, deposition samples collected in spring occasionally had measurable levels of (137)Cs. The annual (137)Cs deposition from 2001 to 2005 was 0.04-0.69 Bq m(-2) with a mean value of 0.27 Bq m(-2). Depositions of insoluble Al, Fe and Ti were strongly correlated with the (137)Cs deposition, suggesting that suspension of soil particles was the main source of the recent (137)Cs deposition. Asian dust events were coincident with some of the significant (137)Cs depositions in spring. It was found that the ratios of (137)Cs/Al and Fe/Al could be used as indices for discriminating Asian dust from suspension of the local surface soil. Backward trajectory analysis suggested southern Mongolian and northeastern China regions as sources of the significant (137)Cs depositions.