The role of metals in dioxin formation from combustion of newspapers and polyvinyl chloride in an incinerator

Newspapers impregnated with NaCl mixed with various chloride metals (CuCl2, MgCl2, MnCl2, FeCl3, NiCl2, and CoCl2) and electric wire coated with polyvinyl chloride (PVC) were combusted in a well-controlled incinerator. Exhaust gas samples collected at the outlet of the incinerator were analyzed for dioxins (PCDDs, PCDFs, and coplanar PCBs) by gas chromatography/mass spectrometry. The amount of total dioxins formed from newspaper samples ranged from 34.2 ng/g (with NaCl+CoCl2) to 67.0 ng/g (with NaCl+CuCl2). PCDFs composed 88-94% of the total dioxins formed in the exhaust gases. The highest levels of PCDF isomers obtained were Cl3-CDF from the sample with NaCl+CuCl2 (14.8 ng/g), Cl2-CDF from the sample with NaCl+MgCl2 (12.3 ng/g), and Cl(1)-CDF from samples with NaCl+MnCl2 (12.6 ng/g), with NaCl+FeCl3 (11.8 ng/g), and with NaCl+NiCl2 (13.3 ng/g), and with NaCl+CoCl2 (8.62 ng/g). The total of Cl4-8-CDDs comprised 76-88% of the total Cl1-8-CDDs. In particular, Cl7-CDDs had the highest levels except for the sample with NaCl+NiCl2. Total dioxins formed from samples of electric wire coated with PVC and PVC alone were 38.3 ng/g and 112 ng/g, respectively, suggesting that the presence of copper reduced dioxin formation.     

Global pollution monitoring of polychlorinated dibenzo-p-dioxins (PCDDs), furans (PCDFs) and coplanar polychlorinated biphenyls (coplanar PCBs) using skipjack tuna as bioindicator

In order to elucidate the global distribution of dioxins and related compounds, such as PCDDs, PCDFs and coplanar PCBs, levels of these compounds were determined in the muscle of skipjack tuna (Katsuwonus pelamis) collected from the offshore waters and open seas near Japan, Taiwan, Philippines, Indonesia, Seychelles and Brazil, and the Japan Sea, the East China Sea, the South China Sea, the Indian Ocean and the North Pacific Ocean. PCDDs, PCDFs and coplanar PCBs were detected in almost all the specimens collected from all the locations surveyed, indicating widespread contamination by these compounds in the marine environment. Higher concentrations of dioxins and coplanar PCBs were detected in the samples from temperate Asian regions, plausibly due to larger usage and anthropogenic generation in highly industrialized countries around the East China Sea and the South China Sea, such as Japan, Korea, Taiwan, Hong Kong and coastal China.     

Adsorption and removal of oxo-anions of arsenic and selenium on the zirconium(IV) loaded polymer resin functionalized with diethylenetriamine-N,N,N',N'-polyacetic acid

A polymer adsorbent in which a Zr(IV)-edta complex analogue is immobilized has been prepared and applied to the removal of oxo-anions of As(III), As(V) and Se(IV). Effective retention of these anions has been demonstrated with the proposed polymer complex system. The adsorption mechanism of oxo-anions onto the Zr(IV)-chelated polymer complex has been investigated using Zr(IV)-edta as the model compound. The formation of mixed complexes with oxo-anions has been exemplified by the isolation of the carbonato complex K2[Zr(CO3)edta].3H2O, the structure of which has been confirmed by X-ray crystallography. NMR study suggests that oxo-anions that form weak or moderate conjugate acids, including those of As(III), As(V) and Se(IV), can form mixed complexes with Zr(IV)-edta using the unsaturated coordination site. However, oxo-anions of strong conjugate acids did not show any appreciable interaction with this complex. According to these observations, retention of oxo-anions on the Zr(IV)-chelated polymer complex has been interpreted by a ligand substitution reaction. The adsorption characteristics of As(III), As(V) and Se(IV) on the Zr(IV)-loaded resin have been examined with respect to the equilibrium adsorption, percentage extraction and the effect of co-existing ions. The adsorption and desorption cycles of the oxo-anions have been demonstrated using a column packed with the proposed resin without any loss of column performance, which indicates the possibility for repeated use.     

Novel malonate-type copolymers containing vinyl alcohol blocks as biodegradable segments and their builder performance in detergent formulations

Poly[(disodium methylene malonate)-co-(vinyl alcohol)] [P(DSMM-VA)] and poly[(disodium ethoxymethylene malonate)-co-(vinyl alcohol)] [P(DSEMM-VA)] containing a poly(vinyl alcohol) (PVA) block as a biodegradable segment were prepared and their biodegradability and functionality were evaluated and compared with those of the corresponding fumarate and maleate copolymers. It was found that the 1,1-dicarboxylate-type copolymers, P(DSMM-VA) and P(DSEMM-VA), showed better biodegradability than the corresponding 1,2-dicarboxylate-type copolymers, P(DSF-VA) and P(DSM-VA). This improved biodegradability of P(DSMM-VA) and P(DSEMM-VA) is probably attributable to their more expanded polymer chain in aqueous solution, which will be more accessible to the degrading enzymes. The minimum chain length of the PVA-block, which acts as a biodegradable segment in the polymer chain, is estimated to be 2–3 and 3–4 monomer units for P(DSMM-VA) and P(DSEMM-VA), respectively. On the other hand, the minimum PVA block is about 5 and 7 monomer units for the fumarate and maleate copolymers, respectively. It was confirmed that P(DSMM-VA) showed excellent builder performance compared to the corresponding fumarate copolymer.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

A model of deforestation by human population interactions

A differential equation was employed in modelling deforestation by human population interactions to yield an explicit mathematical model. The theoretical relation and many possible models were applied to the grid cell data in Hiroshima Prefecture, and relative appropriateness of each model was evaluated by Akaike's information criterion (AIC) using raw data. Intensive further verification was executed bythe bootstrap method. It was demonstrated that the theoretical relation was in the best agreement among many other models in comparison.     

Low-temperature adaptation of deep-sea bacteria isolated from the Japan Trench

Montastraea annularis, M. faveolata, and M.␣franksi are three recently separated species that together dominate reefs of the tropical western Atlantic. Despite morphological, life-history, ecological and genetic differences, the legitimacy of their status as separate species has been questioned. This controversy stems from both the scarcity of unambiguous, diagnostic differences among them, and from the possibility of extensive hybridization associated with their approximately synchronous reproduction in sympatry. Here we report on fertilization trials and the timing of spawning, both of which suggest that the potential for hybridization may be limited. Crosses between M. faveolata (the most genetically distinctive taxon) and the other two species were largely unsuccessful, as were selfed matings for all three species. M. annularis and M. franksi showed no evidence of fertilization barriers, but the timing of spawning typically differed between them by 1 to 2 h. We also found that spawning times in the field of M. annularis and M. faveolata were non-overlapping in 1995, and that the timing of spawning in M. annularis could be experimentally shifted forward by simulating earlier than natural sunsets. These findings from Panamá and Honduras, particularly given their consistency with comparable observations and experiments elsewhere, provide evidence of reproductive isolation and support the separate species status of these three taxa. Some hybridization may occur under natural conditions at these sites, particularly between M. annularis and M.␣franksi. Rampant genetic interchange among these taxa in Central America seems unlikely, however, in the light of the concordant associations between morphology, reproductive biology and other characters which are observed. Received: 22 July 1996 / Accepted: 2 October 1996     

Body temperature independence of solar radiation in free-ranging loggerhead turtles,Caretta caretta,during internesting periods

Body temperatures, ambient water temperatures, light intensities and vertical positions (depth) of eight loggerhead turtles, Caretta caretta, were monitored by small recorders during internesting periods from 1991 through 1993 off Wakayama Prefecture, Japan. Body temperatures of eight loggerhead turtles were higher than ambient water temperatures through-out their internesting periods. Light intensities were compared with body temperatures and no evidence was obtained to suggest that the raised body temperatures were caused by the direct influence of solar radiation. Body temperatures were kept higher than water temperatures in cloudy weather or even at night. Mean thermal differences between body and water temperatures were significantly different among individuals, and larger turtles had a greater mean thermal difference. Elevations in body temperatures of adult loggerhead turtles can reasonably be assumed to result from the accumulation of metabolically produced heat. Surfacing times (spent at depths shallower than 2 m) of seven turtles were only 10.3 to 38.9% of their internesting periods, with the exception of one turtle who spent 66.3% of her time at the surface. Loggerhead turtles did not seem to bask positively at the sea surface to absorb radiative heat.     

Characteristics of carbonaceous aerosols in Beijing, China

Carbonaceous aerosols and PM10 were monitored from September 8 to November 30, 2002, in a semi-urban site (Tsinghua University) in Beijing. Daily concentrations of OC and EC ranged from 7.1 to 65.9 microgCm(-3) and from 1.3 to 26.1 microgCm(-3), with the overall average concentrations of 21.2 microgCm(-3) and 7.3 microgCm(-3), respectively. The diurnal variation of carbonaceous concentrations on 2 h basis presented two-peak trend, which was attributed to the cooperative effect of local meteorological conditions and anthropogenic sources such as traffic exhaust and human outdoor activities. Daily average OC/EC ratio varied between 1.5 and 5.3 with an average of 3.0. Strong correlation between OC and EC (R2=0.8) indicated that their main sources were common. The frequency of OC/EC ratio presented Gaussian normal distribution trend in fall, of which the peak value appeared in the range of 2.8-5. In winter, it presented bi-peak mode, with the first peak near 1.4-1.6, and the second between 2.8 and 5. The high value (2.8-5) implied the SOC formation in both seasons, and the low one probably suggested the primary OC/EC ratio from coal burning in winter. Averagely, PM10 and carbonaceous species exhibited higher concentrations in Wednesday than in other weekdays, which could be ascribed to the low wind speed (1.6 ms(-1)) and high humidity (62.9%). OC was the abundant component accounting for 76% of TC. OC and EC contributed 15% and 5% to PM10, respectively. The estimation on a minimum OC/EC ratio (1.5) basis showed that SOC accounted more than 50% for the total organic carbon. Even in winter, the SOC contribution to OC was also significant, as high as 40%.     

Synthesis and characterization of m- and p-methylbenzyl-mercapturic acids derived from m- and p-xylenes

Chemical synthesis and physical properties of two mercapturic acids suggested as urinary metabolites of m- and p-xylenes ace described. These compounds may be used for the identification and quantivative determination by high-performance liquid chromatography of the corresponding mercapturic acids in urine.     

Influence of residual carbon on the decomposition process of PCDD/Fs in MSWI fly ash

In heating treatment of fly ash to reduce PCDD/Fs, cooling process is important to inhibit de novo formation of PCDD/Fs. In this study, assuming that residual carbon is the dominant factor of de novo synthesis, the relation between PCDD/Fs and residual carbon was examined. Firstly, by using MSWI fly ash which was treated in an actually operated facility, both the content of PCDD/Fs and residual carbon were decreased as heating temperature increased. At temperatures higher than 400 degrees C, the reduction rate of residual carbon was higher than 20% and more than 95% of PCDD/Fs was decomposed. In order to simulate a heating treatment process, fly ash was heated at different temperatures and gas atmospheres, oxygen or nitrogen. Heated fly ash was placed for 2 h at 300 degrees C in oxygen to promote de novo synthesis, or cooled immediately. As a result, good correlation between PCDD/Fs and residual carbon was found, therefore it was shown experimentally that residual carbon was the main factor for PCDD/Fs formation by de novo synthesis in fly ash.