Formation of estrogenic products from environmental phthalate esters under light exposure

Phthalate esters (PEs) have been suspected to be environmental endocrine disruptors and the detailed mechanism remains unclear. The activities of these chemicals can be enhanced through chemical modification under the environmental conditions. We demonstrate that PEs acquire unequivocal estrogenic activity by light exposure. Through UV exposure of an aqueous PE solution, one active photoproduct, identified as 4-hydroxyPE (PE-4OH) based on its characteristic UV and mass spectra, was detected in an estrogen receptor alpha-dependent transactivation assay. PE-4OH was effectively generated by UV 290 nm. The PE-4OH production accompanied H2O2 generation in a UV dose-dependent manner. Both PE and UV irradiation were indispensable in the generation of H2O2. Addition of H2O2 to the PE solution increased PE-4OH production under UV irradiation. The PE-4OH production was also observed in the PE reaction with the Fenton reagent generating hydroxyl radical without UV irradiation. The proposed mechanism for PE-4OH production based on these results is such that by PE-mediated photosensitization H2O2 is generated from O2 and H+ and decomposed to hydroxyl radical, thus oxidizing the PE benzene ring. The PEs-4OH are remarkably active estrogenic products of PEs and would be involved in ER-mediated endocrine disruption.     

Dechlorination/hydrogenation and destruction reactions of PCDDs in OCDD-added fly ash heated under vacuum

Octachlorodibenzo-p-dioxin (OCDD)-added, pretreated fly ash was heated under vacuum at sample temperatures ranging from T(s)=450 to 650 K. The fly ash and liquid nitrogen-cooled trap samples were analyzed for DD/DF through OCDD/DF. The total amounts of DD through OCDD decrease with increasing T(s), which indicates that dechlorination/hydrogenation (DCH) reactions are not the only reaction channels. Reduction of toxic equivalent (TEQ) for PCDDs by more than 99% was achieved in the fly ash by the vacuum heat treatment at T(s)=650 K for 4 h. The total amount of PCDDs and DD detected in the liquid nitrogen-cooled trap relative to that of added OCDD was about 17%, i.e., PCDDs and DD which were adsorbed to the fly ash surfaces can evaporate into the gaseous phase. The difference between the evaporation behavior of PCDDs in the present and the previous studies is discussed in the light of their states of existence.     

Monitoring OH-PCBs in PCB transport worker’s urine as a non-invasive exposure assessment tool

In this study, we analyzed hydroxylated polychlorinated biphenyls (OH-PCBs) in urine of both PCB transport workers and PCB researchers. A method to monitor OH-PCB in urine was developed. Urine was solid-phase extracted with 0.1% ammonia/ methanol (v/v) and glucuronic acid/sulfate conjugates and then decomposed using β-glucuronidase/arylsulfatase. After alkaline digestion/derivatization, the concentration of OH-PCBs was determined by HRGC/HRMS-SIM. In the first sampling campaign, the worker’s OH-PCB levels increased several fold after the PCB waste transportation work, indicating exposure to PCBs. The concentration of OH-PCBs in PCB transport workers’ urine (0.55~11 μg/g creatinine (Cre)) was higher than in PCB researchers’ urine (< 0.20 μg/g Cre). However, also a slight increase of OH-PCBs was observed in the researchers doing the air sampling at PCB storage area. In the second sampling, after recommended PCB exposure reduction measures had been enacted, the worker’s PCB levels did not increase during handling of PCB equipment. This suggests that applied safety measures improved the situation. Hydroxylated trichlorobiphenyls (OH-TrCBs) were identified as a major homolog of OH-PCBs in urine. Also, hydroxylated tetrachlorobiphenyls (OH-TeCBs) to hydroxylated hexachlorobiphenyls (OH-HxCBs) were detected. For the sum of ten selected major indicators, a strong correlation to total OH-PCBs were found and these can possibly be used as non-invasive biomarkers of PCB exposure in workers managing PCB capacitors and transformer oils. We suggest that monitoring of OH-PCBs in PCB management projects could be considered a non-invasive way to detect exposure. It could also be used as a tool to assess and improve PCB management. This is highly relevant considering the fact that in the next 10 years, approx. 14 million tons of PCB waste need to be managed. Also, the selected populations could be screened to assess whether exposure at work, school, or home has taken place.     

Comparison of sludge characteristics and PCR-DGGE based microbial diversity of nanofiltration and microfiltration membrane bioreactors

The objective of this study was to compare the sludge characteristics and microbial community diversity between the submerged nanofiltration membrane bioreactor (NF MBR) and microfiltration membrane bioreactor (MF MBR) treating the same municipal wastewater. The influence of a higher concentration of organic matter and salt was investigated. The results of water qualities showed that the dissolved organic carbon (DOC), total phosphorus (T-P) and salt concentrations of the supernatant in the NF MBR were three, four and two times as high as those in the MF MBR, respectively. The specific oxygen uptake rate of the NF MBR (2.9+/-0.4 mg O(2)g(-1)MLSSh(-1)) was lower than that of the MF MBR (4.3+/-1.1 mg O(2)g(-1)MLSS h(-1)). Result of extractable extracellular polymeric substances showed that the NF MBR sludge had more protein and less polysaccharide compared to the MF MBR sludge, whereas specific amount of total organic carbon were the same in both MBRs. The median floc diameters of the NF MBR and the MF MBR were 72+/-12 microm and 59+/-12 microm, respectively, which could be attributable to the different polysaccharide concentrations between both MBR mixed liquor. A higher concentration of materials (DOC, T-P and salt) in the bioreactor, determined by the high rejection rate of the NF membrane, did not significantly affect the microbial diversity under similar operation conditions.     

Behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes

We investigated the thermal properties and behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes containing polybrominated flame retardants. The thermal properties of the phenolic laminate wastes were measured with a thermogravimeter and a conduction-type scanning calorimeter (TG-CSC). The weight loss of the wastes on thermal decomposition was mainly in three phases between 40°C and 600°C. The enthalpy (ΔH) of the thermal decomposition was 104 cal/g. The material balance of the decomposition components was measured with batch-type thermal decomposition equipment. The ratios of carbon residue, liquid, and gas on decomposition at 800°C in a vacuum were 37 wt. %, 48 wt. %, and 15 wt. %, respectively. The bromine contents in the carbon residue and liquid were less than 0.02 wt. % and 10 wt. %, respectively. These results are useful both in the carbonization process of these wastes and in the application of carbon residue as carbon materials. Received: August 11, 2000 / Accepted: March 7, 2001     

Improved preparation of recycled polymers in chemical recycling of fiber-reinforced plastics and molding of test product using recycled polymers

We examined an improved preparation method of recycled unsaturated polyester resin from recovered monomeric materials obtained from the depolymerization of fiber-reinforced plastics (FRPs). The formation of unsaturated polyester progressed smoothly in the presence of catalytic amounts of Ca(OAc)₂ and Ti(OBu)₄. The quality of the resin was estimated by the durometer hardness test. The strength test of FRP board prepared from recycled resin showed sufficient hardness for practical use (about 94% of the tensile strength of new resin). We examined the recycled resin by using it to mold successfully an actual test product.     

Efficient chemical recycling of waste fiber-reinforced plastics: use of reduced amounts of dimethylaminopyridine and activated charcoal for the purification of recovered monomer

We have achieved major improvements in the efficient chemical recycling of waste fiber-reinforced plastics (FRPs). The effects of reduction in the amounts of dimethylaminopyridine (DMAP) used for depolymerization were examined. The treatment of waste FRP in the presence of 1 or 2 wt% DMAP resulted in the successful recovery of monomeric materials that could be employed in the polymerization process to produce recycled plastic. The separation of linker units from glass fiber, however, was unsuccessful. The purity of the recovered monomeric material, when treated with activated charcoal, was improved to about 70%. This resulted in effective decoloration of the recovered monomer. Finally, the purified material, after undergoing repolymerization, provided high-quality recycled plastic comparable to new plastics produced from new monomers.     

Toxicological evaluation of the chemical oxidation methods for landfill stabilization

As the stabilization criteria for landfill sites, only chemical criteria for the leachate discharges from the landfill sites have been used in Japan and many other countries. Recently, chemical oxidation has been developed as a method for the early-stabilization of landfills. However, by-products that are difficult to detect by chemical analysis can be produced by this method. Therefore, toxicity tests are useful tools for detecting the changes of leachate quality after application of this method. The heat source in the A landfill was analyzed by organic position inquiry technology, and ozone-treated leachate was sprayed back to the heat source in the landfill. Toxicity changes of the leachate after the spray were monitored using Microtoxtrade mark, ToxScreen-II, and DaphTox tests. The hardly-degradable organic matter was efficiently removed and toxicities of the leachate in the heat source decreased after the application. These toxicity results were significantly related to chemical oxygen demand (COD) changes. Thus, it was concluded that the toxicity tests were effective for monitoring the leachate quality after applying the chemical oxidation method for landfill stabilization, and its incorporation to establish the criteria for early-stabilization of landfill sites needs to be considered.     

Formation of recycled plastics from depolymerized monomers derived from waste fiber-reinforced plastics

To develop a new method for the chemical recycling of plastics, we examined the formation of recycled polymers from the recovered monomeric materials of solubilized waste fiber-reinforced plastics (FRP) under supercritical alcoholic conditions. Treatment of waste FRP with supercritical MeOH resulted in the formation of monomeric organic compounds that mainly contained dimethyl phthalate (DMP) and propylene glycol. The presence of these materials was confirmed by gas chromatography and nuclear magnetic resonance analyses and they were mixed with new DMP and glycols in various ratios to form unsaturated polyesters. The polymerization progressed successfully for all mixing ratios of the recovered and new DMP. Hardness tests on these recycled polymers indicated that the polymer made from a 1:1 mixture of recovered and new dimethyl phthalate had almost the same level of hardness as the polymers made from new materials. We also examined the formation of recycled FRP by using glass fibers and monomeric materials recovered through the present depolymerization method. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6