Abiotic degradation of four phthalic acid esters in aqueous phase under natural sunlight irradiation

Abiotic degradability of four phthalic acid esters （PAEs） in the aquatic phase was evaluated over a wide pH range 5-9. The PAE solutions in glass test tubes were placed either in the dark and under the natural sunlight irradiation for evaluating the degradation rate via hydrolysis or photolysis plus hydrolysis, respectively, at ambient temperature for 140 d from autumn to winter in Osaka, Japan. The efficiency of abiotic degradation of the PAEs with relatively short alkyl chains, such as butylbenzyl phthalate （BBP） and di-nbutyl phthalate （DBP）, at neutral pH was significantly lower than that in the acidic or alkaline condition. Photolysis was considered to contribute mainly to the total abiotic degradation at all pH. Neither hydrolysis nor photolysis of di-ethylhexyl phthalate （DEHP） proceeded significantly at any pH, especially hydrolysis at neutral pH was negligible. On the other hand, the degradation rate of di- isononyl phthalate （DINP） catalyzed mainly by photolysis was much higher than those of the other PAEs, and was almost completely removed during the experimental period at pH 5 and 9. As a whole, according to the half-life （t1/2） obtained in the experiments, the abiotic degradability of the PAEs was in the sequence： DINP （32-140 d） 〉 DBP （50-360 d）, BBP （58-480 d） 〉 DEHP （390-1600 d） under sunlight irradiation （via photolysis plus hydrolysis）. Although the abiotic degradation rates for BBP, DBP, and DEHP are much lower than the biodegradation rates reported, the photolysis rate for DINP is comparable to its biodegradation rate in the acidic or alkaline condition.

Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge

Nonylphenol(NP), nonylphenoxy acetic acid(NP1EC), nonylphenol monoethoxy acetic acid(NP2EC), nonylphenol monoethoxylate(NP1EO) and nonylphenol diethoxylate(NP2EO) are biodegradation end products(BEPs) of nonionic surfactant nonylphenolpolyethoxylates (NPnEO). In this research, sorption of these compounds onto model activated sludge was characterized. Sorption equilibrium experiments showed that NP, NP1EO and NP2EO reached equilibrium in about 12 h, while equilibrium of NP1EC and NP2EC were reached earlier, in about 4 h. In sorption isotherm experiments, obtained equilibrium data at 28℃ fitted well to Freundlich sorption model for all investigated compounds. For NP1EC, in addition to Freundlich, equilibrium data also fitted well to Langmuir model. Linear sorption model was also tried, and equilibrium data of all NP, NP1EO, NP2EO and NP2EC except NP1EC fitted well to this model. Calculated Freundlich coefficient(K F) and linear sorption coefficient(K D) showed that sorption capacity of the investigated compounds were in order NP>NP2EO>NP1EO>NP1EC≈NP2EC. For NP, NP1EO and NP2EO, high values of calculated K F and K D indicated an easy uptake of these compounds from aqueous phase onto activated sludge. Whereas, NP1EC and NP2EC with low values of K F and K D absorbed weakly to activated sludge and tended to preferably remain in aqueous phase.

Accelerated degradation of a variety of aromatic compounds by Spirodela polyrrhiza-bacterial associations and contribution of root exudates released from S. polyrrhiza

Removal experiments of phenol, aniline, 2,4-dichlorophenol, nonylphenol and bisphenol A （BPA） using Spirodela polyrrhiza- bacterial associations revealed that all compounds but BPA underwent accelerated removal. The mechanisms differed depending on the substrates. It was found that S. polyrrhiza has a great ability to release phenolic compound-rich root exudates, and the exudates seem to stimulate bacterial degradation of a variety of aromatic compounds.

Biodegradability of four phthalic acid esters under anaerobic condition assessed using natural sediment

Biodegradability of di-n-butyl phthalate （DBP）, butylbenzyl phthalate （BBP）, di-ethylhexyl phthalate （DEHP）, and di-isononyl phthalate （DINP） under an anaerobic condition was evaluated using three natural sediment microcosms obtained from ponds in Osaka, which had not been significantly polluted by the chemicals. The degradabilities of the four phthalic acid esters（PAEs） were analyzed by a first-order kinetic model with a lag phase and ranked as DBP〉BBP〉〉DEHP〉DINP. The PAEs with shorter alkyl-chains, DBP and BBP, were degraded with quite short lag phases near to zero and short half-lives of a few days. The PAEs with longer alkyl-chains, DEHP and DINP, were degraded with lag phases of 5-30 d and the quite long half-lives of a couple of hundred days. Although no data was available on the anaerobic biodegradability of D1NP before this study, it was clarified that DINP can be degraded with slow degradation rates. The fact that all the three intact sediments were capable of biodegradation of the PAEs suggests that potential of anaerobic biodegradation of PAEs is widespread in the aquatic environment.

Optimal turning method of composting regarding hygienic safety

The new turning method was proposed and verified its effectiveness to pathogens by laboratory scale experiments. Considering the results obtained from the previous studies, it could be said that turning of a composting pile was essential in terms of hygienic aspects but the number of turning should be minimized. Effectiveness of inactivation was estimated for each composting run. From this estimation, turning by layers, which is different from conventional turning that mixes compost pile entirely, was proposed and investigated its performance by experiments. Composting operations with static pile method, complete mix(conventional) turning method, and proposed turning(layer turning) method were done and their effectiveness on inactivation of indicator microorganism was evaluated and compared. As results, the conventional turning method was not a proper method in terms of pathogen inactivation, whereas, the proposed turning method showed an excellent performance and should be employed in a composting operation.

A reactor system combining reductive dechlorination with co-metabolic oxidation for complete degradation of tetrachloro-entylene

A laboratory sequential anaerobic aerobic bioreactor system, which consisted of an anaerobic fixed film reactor and two aerobic chemostats, was set up to degrade tetrachloroethylene (PCE) without accumulating highly toxic degradation intermediates. A soil enrichment culture, which could reductively dechlorinate 900 μM (ca. 150 mg/L) of PCE stoichiometrically into cis 1,2 dichloroethylene ( cis DCE), was attached to ceramic media in the anaerobic fixed film reactor. A phenol degrading strain, Alcaligenes sp. R5, which can efficiently degrade cis DCE by co metabolic oxidation, was used as inoculum for the aerobic chemostats consisted of a transformation reactor and a growth reactor. The anaerobic fixed film bioreactor showed more than 99 % of PCE transformation into cis DCE in the range of influent PCE concentration from 5 μM to 35 μM at hydraulic retention time of 48h. On the other hand, efficient degradation of the resultant cis DCE by strain R5 in the following aerobic system could not be achieved due to oxygen limitation. However, 54% of the maximum cis DCE degradation was obtained when 10 μmol of hydrogen peroxide (H 2O 2) was supplemented to the transformation reactor as an additional oxygen source. Further studies are needed to achieve more efficient co metabolic degradation of cis DCE in the aerobic reactor.

Comparative evaluation of processes for heavy metal removal from municipal solid waste incineration fly ash

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Biodegradation of synthetic surfactants by river microorganisms

Four kinds of widely used synthetic surfactants and polyethylene glycol (PEG) which corresponds to the hydrophilic moieties of polyoxyethylene-type nonionic surfactants were subjected to a complete biodegradation test using microorganisms from relatively unpolluted river waters (the TOC-Handai method). Sodium dodecyl sulfate (SDS), alcohol ethoxylate (AE) and PEG were mineralized by most of the microorganisms used as inocula, irrespective of differences in their degradation rates, which is in agreement with their biodegradabilities confirmed so far by other tests.These degradable surfactants were, however, not completely degraded by some river microorganisms. Among the surfactants tested, SDS was degraded most rapidly by microorganisms of each river in the same manner but the degradation rates of AE and PEG differed considerably according to the inoculum sampling station. Sodium linear alkylbenzensulfonate (LAS) and nonylphenol ethoxylate (NPE). which are known to be recalcitrant molecules, were not degraded completely by microorganisms of any of the river waters within the testing period; degradation of the former rarely proceeded , while that of the latter ceased leaving the well-known intermediates. The residual metabolites of NPE generated by biodegradation, which were analyzed by high-performance liquid chromatography and gas chromatography/mass spectrometry, revealed that this surfactant was transformed to carboxylated metabolites, nonylphenoxy acetic acid (NP1EC)and [(nonylphenoxy)ethoxy] acetic acid (NP2EC) exclusively.

Screening of agonistic activities against four nuclear receptors in wastewater treatment plants in Japan using a yeast two-hybrid assay

To assess the potential endocrine disruptive effects through multiple nuclear receptors （NRs）, especially non-steroidal NRs, in municipal wastewater, we examined the agonistic activities on four NRs （estrogen receptor α, thyroid hormone receptor α, retinoic acid receptor ct and retinoid X receptor α） of untreated and treated wastewater from municipal wastewater treatment plants （WWTPs） in Japan using a yeast two-hybrid assay. Investigation of the influent and effluent of seven WWTPs revealed that agonistic activities against steroidal and non-steroidal NRs were always detected in the influents and partially remained in the effluents. Further investigation of four WWTPs employing conventional activated sludge, pseudo-anoxic-oxic, anoxic-oxic and anaerobic-anoxic-oxic processes revealed that the ability to reduce the agonistic activity against each of the four NRs varies depending on the treatment process. These results indicated that municipal wastewater in Japan commonly contains endocrine disrupting chemicals that exert agonistic activities on steroidal and non-steroidal NRs, and that some of these chemicals are released into the natural aquatic environment. Although the results obtained in yeast assays suggested that measured levels of non-steroidal NR agonists in the effluent of WWTPs were not likely to cause any biological effect, further study is required to assess their possible risks in detail.

Bacterial community succession during the enrichment of chemolithoautotrophic arsenite oxidizing bacteria at high arsenic concentrations

To generate cost-effective technologies for the removal of arsenic from water, we developed an enrichment culture of chemolithoau- totrophic arsenite oxidizing bacteria （CAOs） that could effectively oxidize widely ranging concentrations of As（III） to As（V）. In addition, we attempted to elucidate the enrichment process and characterize the microbial composition of the enrichment culture. A CAOs enrichment culture capable of stably oxidizing As（III） to As（V） was successfully constructed through repeated batch cultivation for more than 700 days, during which time the initial As（iiI） concentrations were increased in a stepwise manner from 1 to 10-12 mmol/L. As（III） oxidation activity of the enrichment culture gradually improved, and 10-12 mmol/L As（III） was almost completely oxidized within four days. Terminal restriction fragment length polymorphism analysis showed that the dominant bacteria in the enrichment culture varied drastically during the enrichment process depending on the As（III） concentration. Isolation and characterization of bacteria in the enrichment culture revealed that the presence of multiple CAOs with various As（Ⅲ） oxidation abilities enabled the culture to adapt to a wide range of As（Ⅲ） concentrations. The CAOs enrichment culture constructed here may be useful for pretreatment of water from which arsenic is being removed.

Characterization of the genes involved in nitrogen cycling in wastewater treatment plants using DNA microarray and most probable number-PCR

To improve nitrogen removal performance of wastewater treatment plants （WWTPs）, it is essential to understand the behavior of nitrogen cycling communities, which comprise various microorganisms. This study characterized the quantity and diversity of nitrogen cycling genes in various processes of municipal WWTPs by employing two molecular-based methods：most probable number-polymerase chain reaction （MPN-PCR） and DNA microarray. MPN-PCR analysis revealed that gene quantities were not statistically different among processes, suggesting that conventional actwated sludge processes （CAS） are similar to nitrogen removal processes in their ability to retain an adequate population of nitrogen cycling microorganisms. Furthermore, most processes in the WWTPs that were researched shared a pattern：the nitS and the bacterial amoA genes were more abundant than the nirK and archaeal amoA genes, respectivelv. DNA microarray analysis revealed that several kinds of nitrification and denitrification genes were detected in both CAS and anaerobic-oxic processes （AO）, whereas limited genes were detected in nitrogen removal processes. Results of this study suggest that CAS maintains a diverse community of nitrogen cycling microorganisms; moreover, the microbial communities in nitrogen removal processes may be specific.