Identification of chemical substances in industrial wastes and their pyrolytic decomposition products

In order to quantify the sources of chemical pollutants in the leachate from reclaimed wastes, chemical substances in 11 different types of industrial wastes were identified. Their elution behaviors were also investigated. Alkanes (5.3-890 ng g(-1)), benzenes (8.1-110 ng g(-1)), polyaromatic hydrocarbons (PAHs) (3.2-560 ng g(-1)), alcohols, steroids, phenol (7.1 ng g(-1)), ketones, furans (190-210 ng g(-1)), phthalates (8.9-560 ng g(-1)), benzoquinones, dibenzothiophene (190 ng g(-1)), benthiocarb (4.2 ng g(-1)), sulfur, nitrile compounds, amino compounds, amido compounds, pyridines, quinolines (1.8-15 ng g(-1)), isoquinolines, carbazoles, acridines, chlordenes (1.5-1.6 ng g(-1)) and nonachlors (1.1-1.6 ng g(-1)) were detected in 9 types of industrial wastes. The chemical substances detected in waste at the highest concentrations were alkanes, PAHs and phthalates. Water supply sludge, dust and brick garbage contained many kinds of chemical substances. The elution behaviors of specific chemical substances, COD and nutrients varied by characteristic and production process of each waste. Over 100 different compounds were detected in pyrolysis products including carbohydrate, carotynoid, amino acids, proteins, humic acids, lignin and combustion products.     

Distribution of copper,silver and gold during thermal treatment with brominated flame retardants

The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition.In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue.     

The effects of pH on fluoxetine in Japanese medaka (Oryzias latipes): acute toxicity in fish larvae and bioaccumulation in juvenile fish

Recent detection of fluoxetine in the aquatic environment and fish suggests a possibly high accumulation of fluoxetine; however, no report is available on the bioaccumulation of fluoxetine in aquatic organisms. Since bioaccumulation of fluoxetine was probably dependent on pH near the pK(a) value of 10.1, experiments were conducted approximately at pH 7, 8, and 9. Distribution coefficients between 1-octanol and water (D(ow)), and those between synthetic membrane vesicles (liposomes) and water (D(lip-wat)) were determined at pH 7, 8, and 9. The D(ow) and D(lip-wat) values increased significantly with increasing pH. Acute toxicity tests were performed using Japanese medaka (Oryzias latipes) prior to the bioaccumulation test, and 96-h LC(50) values were 5.5, 1.3, and 0.20mgl(-1) at pH 7, 8, and 9, respectively. In the bioaccumulation test, concentrations of fluoxetine and its major metabolite, norfluoxetine, in the fish body and liver were measured. The bioconcentration factors (BCF) of fluoxetine for Japanese medaka were 8.8, 3.0x10, and 2.6x10(2) in the body and 3.3x10(2), 5.8x10(2), and 3.1x10(3) in the liver at pH 7, 8, and 9, respectively. The BCF values were lower at pH 7 and higher at pH 9 mainly because of the increase in nonionized species with significantly higher hydrophobicity than the ionized species at pH values closer to pK(a). A similar trend was obtained for the concentration of norfluoxetine in the fish but the pseudo-BCF values (the ratio of the norfluoxetine concentration in the fish and the fluoxetine concentration in test water) were higher than the BCF value of fluoxetine at all pH conditions.     

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) (R_L/S) increased with pH due to the flooded incubation. The R_L/S for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.     

Removal of bisphenol a in soil by cyclodextrin derivatives

The apparent aqueous solubility of the endocrine disruptor in hydroxypropyl‐cyclodextrin (HP‐CD) solutions was investigated for evaluating the remediation of soil contamination and ground water pollution. The apparent solubility of bisphenol A (BPA) in water was significantly increased in HP‐CD solutions. The solubilization effect of HP‐CD's is caused by the formation of inclusion complexes of BPA and cyclodextrin. The relative aqueous‐phase concentration of BPA linearly increased with increasing HP‐CD concentration. The solubility of BPA increased in the order of the addition of HP‐a‐CD, HP‐7‐CD, and HP‐ß‐CD. However, it did not depend upon the degree of hydroxypropylation substitution. It is concluded that HP‐CD may be utilized for the remediation of soil contamination.     

Spatiotemporal variability in recruitment around Iriomote Island, Ryukyu Archipelago, Japan: implications for dispersal of spawning corals

Spatiotemporal recruitment patterns of scleractinian corals were investigated around Iriomote Island, Ryukyu Archipelago, Japan, in relation to adult coral cover in 2005 and 2006. Although almost all corals were broadcasting spawners, the relationship between recruitment and adult coral cover differed among coral families (Acroporidae, Poritidae, and Pocilloporidae), likely due to differences in embryonic development time. For spawning pocilloporid corals, whose larvae develop relatively more rapidly, recruitment was higher at sites where adult coral cover was higher. In contrast, recruitment was not related to adult coral cover in acroporid and poritid corals, whose embryonic development times were relatively slow. Moreover, recruitment of acroporid corals varied between years, and recruitment was greater at leeward compared to windward reefs for a few days after spawning. These results suggest that embryonic development time and wind-driven surface currents affect larval dispersal and subsequent recruitment patterns at a local scale. Based on embryonic development time, some spawning corals are more likely to have higher rates of self-seeding than others. Our results predict that among spawning corals, local populations of acroporid and poritid corals, whose larvae potentially disperse over long distances and recruit in neighboring reefs, are more resilient to local disturbances than those of pocilloporid corals, whose recruitment relies upon local stock.     

Variability in nursery function of tropical seagrass beds during fish ontogeny: timing of ontogenetic habitat shift

Seagrass beds are often considered to be important nurseries for coral reef fish, yet the effectiveness of these nursery functions (refuge and food availability) at different juvenile stages is poorly understood. To understand how the demands of juvenile fish on seagrass nursery functions determines the timing of ontogenetic habitat shifts from seagrass beds to coral reefs, we conducted visual transect survey and field tethering and caging experiments on three different sizes of the coral reef fish Pacific yellowtail emperor (Lethrinus atkinsoni) during its juvenile tenure in seagrass beds at Ishigaki Island, southern Japan. The study showed that although the number of individual L. atkinsoni juveniles decreased by >90 % during their stay in the seagrass nursery, the shelter and/or food availability functions of the nursery, at least for a juvenile size of approximately 5 cm total length (TL), provided the best survival and growth option. The timing of ontogenetic migration to coral reefs of larger fish (>8 cm TL) was attributed to foraging efficiency for larger food items in different habitats. Overall, the function of the seagrass bed nursery changed with juvenile body size, with marginally higher survival and significantly greater growth rates during early juvenile stages in seagrass beds compared to coral reefs. This would contribute to the enhancement in the number of individuals eventually recruited to adult populations.     

Update of daily intake of PCDDs, PCDFs, and dioxin-like PCBs from food in Japan

Total diet study (TDS) samples of 14 food groups from 16 locations in Japan, collected in 1999 and 2000, were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) to estimate the update of daily intake of these contaminants from food. The mean daily intake of toxic equivalency (TEQ) for an adult weighing 50 kg, calculated at non-detected isomer concentrations equal to zero (ND=0), was estimated to be 2.25 pg TEQ/kg b.w./day. When non-detected isomer concentrations are assumed to be equal to half of the limits of detection (ND=1/2 LOD), the mean daily intake was estimated to be 3.22 pg TEQ/kg b.w./day. These values were below the tolerable daily intake (TDI) of 4 pg TEQ/kg b.w. for PCDD/Fs and dioxin-like PCBs set in Japan. In both the estimates, the mean daily intakes were highest from fish and shellfish (76.9% at ND=0 and 53.9% at ND=1/2 LOD of the total TEQs), followed by those from meat and eggs (15.5% at ND=0 and 11.7% at ND=1/2 LOD of the total TEQs). Congener specific data revealed that these total TEQ levels were dominated by 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3^′,4,4^′,5-PeCB in each case (71.7% at ND=0 and 63.1% at ND=1/2 LOD of the total TEQs). The dioxin-like PCBs (non-ortho and mono-ortho PCBs) accounted for about 50% of these total TEQs. These data will be very useful in the risk assessment of PCDD/Fs and dioxin-like PCBs from food in Japan.     

Correlation coefficients between the dioxin levels in mother's milk and the distances to the nearest waste incinerator which was the largest source of dioxins from each mother's place of residence in Tokyo, Japan

BACKGROUND: To observe the relationship between the PCDD/F and Co-PCB levels in samples of human breast milk and nearby waste incinerators in Tokyo, Japan. METHODS: Breast milk was taken from 240 mothers residing in Tokyo, Japan to measure and analyze the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs; 14 congeners), polychlorinated dibenzofurans (PCDFs; 15 congeners), and coplanar polychlorinated biphenyls (Co-PCBs; 12 congeners) contained in the fat. Individual milk samples (about 50 ml) were obtained from the mothers 30 days after delivery, between the months of June and September in 1999 and 2000. A map of Tokyo was used to measure the distances between each mother's place of residence and the closest public and industrial waste incinerators. RESULTS: The distances to the nearest waste incinerators bore no apparent correlations with the congeners of PCDD/Fs and Co-PCBs. The distances were also uncorrelated with the mean toxic equivalent quantities (TEQs) of PCDD/Fs (the sum of PCDDs and PCDFs), Co-PCBs, and the total PCDD/Fs and Co-PCBs. CONCLUSIONS: Although waste incinerators were the largest source of dioxins in Japan at the time of the study, the dioxins levels of mother's milk bore no apparent relationships with the distances between the mothers' domiciles and the nearest waste incinerators. In this study, several meaningful factors were not taken into account, namely, the wind direction, the level of dioxin emitted from each incinerator, the level of environmental pollution of dioxins, and the average time the mothers stayed at home each day. A full understanding of these points awaits future studies.