Leaching characteristics of stabilized/solidified fly ash generated from ash-melting plant

This study was designed to elucidate the leaching characteristics of stabilized/solidified (S/S) fly ash generated by ash-melting. For this study, pH-dependent leaching tests, sequential extraction procedures, and column leaching tests were carried out. The pH-dependent leaching test results for Pb, Cu, and Zn showed that the heavy metal concentrations in the high-pH range were lower than the predicted values for hydroxide and carbonate. During sequential extraction, Cu and Pb were principally distributed in the S/S ashes' organic matter fraction in the chelating agent, suggesting that metals bind to the chelating agent. The percentage of the water-soluble fraction for Pb and Cu was low (<0.2 %). The fly ashes treated with a chelating agent and cement had low leachability potential for metals in the high-pH range. Column tests for S/S fly ashes showed that two leaching stages were distinguishable: one for short time, corresponding to faster metal leaching, and another for the leaching rate. Kinetic speciation was then applied to data obtained from column leaching tests. The first-order reaction/diffusion model showed a better fit for Ca, Pb, and Cu, suggesting that the initial dissolution of soluble compounds, such as metal chloride, was controlled by the first-order reaction (surface wash off). Subsequently, insoluble compounds such as hydroxide or carbonate might penetrate into the porous matrix by diffusion.     

Investigation of 1,4-dioxane originating from incineration residues produced by incineration of municipal solid waste

As a groundwater contaminant, 1,4-dioxane is of considerable concern because of its toxicity, refractory nature to degradation, and rapid migration within an aquifer. Although landfill leachate has been reported to contain significant levels of 1,4-dioxane, the origin of 1,4-dioxane in leachate has not been clarified until now. In this study, the origins of 1,4-dioxane in landfill leachate were investigated at 38 landfill sites and three incineration plants in Japan. Extremely high levels of 1,4-dioxane 89 and 340 microg l(-1), were detected in leachate from two of the landfill sites sampled. Assessments of leachate and measurement of 1,4-dioxane in incineration residues revealed the most likely source of 1,4-dioxane in the leachate to be the fly ash produced by municipal solid waste incinerators. Effective removal of 1,4-dioxane in leachate from fly ash was achieved using heating dechlorination systems. Rapid leaching of 1,4-dioxane observed from fly ash in a sequential batch extraction indicated that the incorporation of a waste washing process could also be effective for the removal of 1,4-dioxane in fly ash.     

Evaluation of an electrolysis apparatus for inactivating antineoplastics in clinical wastewater

We recently reported a system for inactivating antineoplastics in which sodium hypochlorite is supplied by the electrolysis of sodium chloride solution. In this study, we designed an electrolysis apparatus for inactivating the cytotoxicity of antineoplastics in clinical wastewater using the system. The apparatus consists of an electrolysis cell with platinum-iridium electrodes, a pool tank, a circulating system for wastewater, a safety system for explosive gas and overflow, and an exhaust duct. The free chlorine concentration increased linearly up to 6500 mg l(-1), and pH also increased to 9.0-10.0 within 2h, when 0.9% sodium chloride solution was electrolyzed. We examined its efficacy with model and clinical wastewaters. The reciprocal of dilution factor for disappearance of cytotoxicity using Molt-4 cells was compared before and after electrolysis. In the model wastewater, that was 9.10 x 10(4) before electrolysis, and 3.56 x 10(2) after 2h of electrolysis. In the clinical wastewater (n=26), that was 6.90 x 10(3)-1.02 x 10(6) before electrolysis, and 1.08 x 10(2)-1.45 x 10(4) after 2h of electrolysis. Poisonous and explosive gases released by the electrolysis were measured; however, they were found to be negligible in terms of safety. The environmental load was evaluated by carbon dioxide generation as an index and it was found that the carbon dioxide generated by the electrolysis method was 1/70 lower than that by the dilution method with tap water. Moreover, the cost of the electrolysis method was 1/170 lower than that of the dilution method. This method was found to be both effective and economically valuable.     

In situ assay with the midge Kiefferulus calligaster for contamination evaluation in aquatic agro-systems in central Thailand

The aims of this study were to verify the suitability of in situ tests using the tropical midge Kiefferulus calligaster and to evaluate the most sensitive endpoint for the assessment of aquatic pesticide contamination. In situ tests were carried out in freshwater drainage channels (farm channels) that supply vegetable crops and receive considerable pesticide spray drift, and at channels outside farms (main channels). Moreover a pesticide-free farm was used as reference site. The endpoints analysed were: survival of the larvae, body length increment, capsule width increment, cholinesterase activity and glutathione S-transferase activity. Seasonal change was investigated as rainy season and dry season. Deleterious effects were observed at some farms especially during the rainy season when farmers apply heavier doses of pesticides. However, high mortality rates observed in main channels suggest that these water bodies are also affected by other impacts besides pesticide use. This work shows the potential of the in situ assay with K. calligaster as a tool for the environmental quality assessment of tropical aquatic ecosystems.     

Fe(III) promoted LAS (linear alkylbenzenesulfonate) removal from waters

The mechanisms of the interactions between Fe(III) aquacomplexes and surfactants were investigated; three alkylbenzenzsulfonates, two surfactants (octylbenzenesulfonate (OBS) and dodecylbenzenesulfonate (DBS)), and a shorter derivative (ethylbenzenesulfonate (EBS)) were studied. The results with OBS show evidence for three different ways in which Fe(III) interferes with the surfactant: the widely described flocculation process, complexation of Fe(OH)2+ (aquacomplexes) by the surfactant, and a redox reaction. The formation of a weak complex is maximum for a ratio of three between the monomeric aquacomplex [FeOH(H2O)5]2+ and OBS. In the presence of oxygen, an intramolecular redox reaction occurs inside the complex. The interaction between commercial DBS and Fe(III) was also investigated. Immediate precipitation occurred, mainly involving derivatives of higher molecular weights that are contained in the DBS samples. The constituents with the shortest alkyl chain were not affected by the presence of Fe(III) as it was also observed with EBS.     

Separation and characterization of the colored material from sugarcane molasses

The colored material (X) was effectively separated from sugarcane molasses using reversed-phase chromatography. Characterization of the molecular structure of sample X was performed using infrared absorption (IR) spectrometry, mass spectrometry (MS), and dynamic light scattering (DLS). The IR spectrum was similar to that of commercial humic acid, and the MS analysis showed that the sample possessed relatively small heterogeneous molecules with molecular masses around 234, 446, 657, 868, and 1079 Da. On the other hand, X sample showed an inhibitory activity toward the cysteine proteinase papain. Furthermore, the inhibitory (G-1) and weak inhibitory (G-2) fractions were separated from sample X using gel permeation chromatography. Samples G-1 and G-2 inhibited papain partial-noncompetitively and had the inhibition constants of 5.01 x 10(-5) and 1.08 x 10(-3)M, respectively. Interestingly, in the DLS experiment, the Stokes radius of sample G-1 was approximately 2 nm, about twice one of sample G-2.     

Analysis of biomagnification of persistent organic pollutants in the aquatic food web of the Mekong Delta, South Vietnam using stable carbon and nitrogen isotopes

The present study elucidated the biomagnification profiles of persistent organic pollutants (POPs) through a tropical aquatic food web of Vietnam based on trophic characterization using stable nitrogen analysis. Various biological samples collected from the main stream of the Mekong Delta were provided for the analysis for both POPs, and stable nitrogen and carbon isotope ratios. Of the POPs analyzed, dichlorodiphenyltrichloroethane and its metabolites (DDTs) were the predominant contaminants with concentrations ranging from 0.058 to 12 ng/g wet weight, followed by polychlorinated biphenyls (PCBs) at 0.017-8.9 ng/g, chlordane compounds (CHLs) at 0.0043-0.76 ng/g, tris-4-chlorophenyl methane (TCPMe) at N.D.-0.26 ng/g, hexachlorocyclohexane isomers (HCHs) at N.D.-0.20 ng/g and hexachlorobenzene (HCB) at 0.0021-0.096 ng/g. Significant positive increases of concentrations in DDTs, CHLs, and TCPMe against the stable nitrogen ratio (delta(15)N) were detected, while, concentrations of HCHs and HCB showed no significant increase. The slopes of the regression equations between the log-transformed concentrations of these POPs and delta(15)N were used as indices of biomagnification. The slopes of the POPs for which positive biomagnification was detected ranged from 0.149 to 0.177 on a wet weight basis. The slopes of DDTs and CHLs were less than those reported for a marine food web of the Arctic Ocean, indicating that less biomagnification had occurred in the tropical food web. Of the isomers of CHLs, unlike the studies of the Arctic Ocean, oxychlordane did not undergo significant biomagnification through the food web of the Mekong Delta. This difference is considered to be due to a lack of marine mammals, which might metabolize cis- and trans-chlordane to oxychlordane, in the Mekong Delta ecosystem. The biomagnification profile of TCPMe is reported for the first time in the present study.     

Spatial trends of polyfluorinated compounds in guillemot (Uria aalge) eggs from North-Western Europe

Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.     

Haematological and biochemical effects of polyphenolics in animal models

Polyphenols of natural and synthetic origin are exploited in tanning sector to convert putrescible skin/hide to non-putrescible leather. However, only 30-40% of the inputs have been taken up for processing, the remaining is released as unspent. The existing conventional wastewater treatment systems are inefficient in removing or degrading these unspent polyphenols and thus detrimental to ecosystem. The present study demonstrates the evaluation of impact of both synthetic and natural polyphenols on biochemical and haematological properties of blood and serum in animal models. The results reveal that concentrations of polyphenols play a major role. At higher concentrations, irrespective of their nature, there was a marked change in the lipid profile (81% reduction), followed by insignificant change in glucose levels, RBC and WBC counts and other haematological parameters. At lower concentrations, no significant changes in the above said properties were observed.     

Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.