Abstract  The concentrations and removal efficiencies of various kinds of micropollutants were investigated and the relationships between the input sources of industrial wastewater and occurrence patterns of each micropollutant were identified at nine on-site industrial wastewater treatment plants (WWTPs). The distribution pattern of each compound varied according to the WWTP type and several micropollutants were significantly related with specific industries: chlorinated phenols (ClPhs) with paper and metal industries, polycyclic aromatic hydrocarbons (PAHs) with petrogenic- and pyrogenic-related industries, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with the paper industry, and chlorinated benzenes (ClBzs) with dye-related industries. The activated sludge (AS) process was very efficient in the removal of ClPhs and PAHs, and the filtration process in the removal of PCDD/Fs and 1,4-dioxane. Generally, the removal efficiencies of each micropollutant varied according to the WWTP type.

Abstract  1,4-Dioxane (dioxane), a probable human carcinogen, is used as a solvent stabilizer for 1,1,1-trichloroethane (TCA) and other chlorinated solvents. Consequently, TCA and its abiotic breakdown product 1,1-dichloroethene (DCE) are common co-contaminants of dioxane in groundwater. The aerobic degradation of dioxane by microorganisms has been demonstrated in laboratory studies, but the potential effects of environmentally relevant chlorinated solvent co-contaminants on dioxane biodegradation have not yet been investigated. This work evaluated the effects of TCA and DCE on the transformation of dioxane by dioxane-metabolizing strain Pseudonocardia dioxanivorans CB1190, dioxane co-metabolizing strain Pseudonomas mendocina KR1, as well as Escherichia coli expressing the toluene monooxygenase of strain KR1. In all experiments, both TCA and DCE inhibited the degradation of dioxane at the tested concentrations. The inhibition was not competitive and was reversible for strain CB1190, which did not transform the chlorinated solvents. For both strain KR1 and toluene monooxygenase-expressing E. coli, inhibition of dioxane degradation by chlorinated solvents was competitive and irreversible, and the chlorinated solvents were degraded concurrently with dioxane. These data suggest that the strategies for biostimulation or bioaugmentation of dioxane will need to consider the presence of chlorinated solvents during site remediation.

Abstract  In order to improve the bonding between halloysite nanotubes (HNTs) and poly(L-lactide) (PLLA), and hence to increase the mechanical properties of HNTs/PLLA nano-composite, HNTs were surface-grafted with PLLA under microwave irradiation and then blended with PLLA matrix. The optimal conditions for grafting polymerization are: irradiation time of 30 min, microwave power of 30 W and reaction temperature of 130 degrees C. The structure and properties of the surface-grafted HNTs (g-HNTs) were characterized by Fourier transformation infrared (FTIR), thermal gravimetric analysis (TGA), X-ray diffraction (XRD) and dynamic light scattering (DLS). Nano-composites of g-HNTs/PLLA and non-grafted HNTs/PLLA were subsequently evaluated in terms of crystallinity, dispersion, interfacial interaction, mechanical performance and cytocompatibility by polarized optical microscopy (POM), field scanning electron microscope (FESM), tensile testing and cell culture experiment. Results show that the grafted PLLA chains on the surfaces of HNTs, as inter-tying molecules, played an important role in improving the adhesive strength between the nanotubes and the polymer matrix. The enhanced interaction among g-HNTs and PLLA matrix resulted in a better tensile strength and modulus compared to the pristine PLLA and HNTs/PLLA. Cell culture results indicated that g-HNTs promoted both adhesion and proliferation of M3T3 fibroblasts on the g-HNTs/PLLA composite film.

Abstract  Palladium-catalyzed cascade C-H alkenylation and arylation provides convenient access to polycyclic aromatic compounds. Treatment of 3-bromoaniline derivatives bearing a bromocinnamyl group on the nitrogen atom with a catalytic amount of [Pd(OAc)(2)] and PCy(3)·HBF(4) in the presence of Cs(2)CO(3) in dioxane affords naphthalene-fused indole derivatives in good yields. This double cyclization reaction is also applicable to heterocyclic substrates, giving fused indoles containing a heteroaromatic ring such as dibenzofuran, dibenzothiophene, carbazole, indole, or benzofuran through heterocyclic C-H arylation. When using a 2,6-unsubstituted aniline derivative, the first C-H arylation preferentially proceeds at the more hindered position of the aniline ring.

Abstract  A new one-pot synthesis of 9-(pyridin-2-yl)-9H-carbazoles through the simultaneous C-H activation and palladium(II)-catalyzed cross-coupling of N-phenylpyridin-2-amines with potassium aryltrifluoroborates is presented. Silver acetate and 1,4-dioxane proved to be the best oxidant and solvent, respectively. The product yields fluctuated from modest to excellent and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The kinetic isotope effects (k(H)/k(D)) for the first and second C-H activation/C-C or C-N formation steps were measured as 2.14 and 1.18, respectively. Finally, a rational catalytic mechanism is presented based on all experimental evidence.

Abstract  The photophysics of thioflavin T (ThT) were observed in different non-aqueous reverse micelles by using steady state absorption and emission spectroscopy and time resolved fluorescence spectroscopy. We have used glycerol, ethylene glycol, dimethyl formamide, methanol and acetonitrile as polar solvents to form reverse micelles. In all reverse micelles with increase in w (w = [polar solvent]/[AOT]) the fluorescence quantum yield decreased in a regular way. The time resolved fluorescence study of ThT in different reverse micelles shows the similar trend as like above. We had plotted a calibration curve using the fluorescence quantum yield of ThT in glycerol-methanol mixtures vs. viscosity and from that curve we found that ThT faced a greater microviscosity in glycerol pool of AOT/isooctane/glycerol reverse micelles than in the pure glycerol, even at the highest w value. In all reverse micelles the emission quantum yield of ThT was retarded several times compared to neat solvents. We have found that the fluorescence quantum yield of ThT decreased with gradual increase in polarity by studying the emission properties of ThT in dioxane-water mixtures of different polarity.

Abstract  A comprehensive orthogonal two-dimensional liquid chromatography (2D-LC) based on the modification of mobile phases was developed with a sample loop-valve interface. To improve the compatibility of mobile phases and analysis speed, some special solvents were chosen as the mobile phases, and the column temperature was elevated to decrease the viscosity of mobile phases of reversed-phase liquid chromatography (RPLC). Based on this principle, the first dimension was normal-phase liquid chromatography (NPLC) with a SiO2 column, and the second dimension was reversed-phase liquid chromatography containing two tandem C18 columns. 1,4-Dioxane was used in the NPLC mobile phase, and isopropyl alcohol was employed in the RPLC mobile phase. Moreover, the elevated column temperature enabled the reduction of the backpressure and using tandem C18 columns to improve the resolving power in RPLC. The new comprehensive 2D-LC system and applied strategy offered a novel idea for construction of 2D-LC system. A traditional Chinese medicine, Zhengtian pill, was used as the test sample to evaluate the constructed 2D-LC system. 876 peaks were detected, and the peak capacity reached 1740.

Abstract  A pulse radiolysis technique was used to measure the UV absorption spectra of c-C4H7O2 and (c-C4H7O2)O2 radicals over the range 220–320 nm, (c-C4H7O2)250 nm=(5.9±0.6)×10-18 and [(c-C4H7O2)O2 ]240nm=(4.8×0.8)×10-18 cm2 molecule-1. The observed self-reaction rate constants for the c-C4H7O2 and (c-C4H7O2)O2 radicals, defined as -d[c-C4H7O2]/dt= 2k4[c- C4H7O2]2 and -d[(c-C4H7O2)O2 ]/dt=2k5obs[(c-C4 H7O2)O2]2 were k4=(3.3±0.4)×10-11 and k5obs=(7.3±1.2)×10-1 2 cm3 molecule-1 s-1. The rate constants for reactions of (c-C4H7O2)O2 radicals with NO and NO2 were k6 (1.2±0.3)×10-11 and k7=(1.3±0.3)×10-11 cm3 molecule-1 s-1, respectively. The rate constants for the reaction of F atoms with 1,4-dioxane and the reaction of c-C4H7O2 radicals with O2, were k3=(2.4±0.7)×10-10 and k2=(8.8±0.9)×10-12 cm3 molecule-1 s-1, respectively. A relative rate technique was used to measure the rate constant for the reaction of Cl atoms with 1,4-dioxane, k17=(2.0±0.3)×10-10 cm3 molecule-1 s-1. A long-pathlength FTIR spectrometer coupled to a smog chamber system was used to show that the sole atmospheric fate of the alkoxy radical (c-C4H7O2)O is decomposition via C–C bond scission leading to the formation of H(O)COCH2CH2OC(O)H (ethylene glycol diformate).

Abstract  Karbe and Kerlin have questioned the classification of spongiosis hepatis as a preneoplastic lesion or even a benign neoplasm, designated as spongiotic pericytoma, and have proposed to use the term cystic degeneration for this lesion in rats and fish. However, the reclassification of spongiosis as cystic degeneration is unwarranted for several reasons. In the rat, spongiosis hepatis represents a specific pathomorphologic entity, originating from the perisinusoidal (Ito) cells; it may occur spontaneously in aged animals but its number and size increases significantly after exposure to various (hepato)carcinogens. Comparative morphological, immunohistochemical, and autoradiographic studies in rats exposed to N-nitrosomorpholine revealed that spongiosis hepatis is an integral part of larger proliferative Ito-cell aggregates showing an autonomous, progressive growth. The classification of spongiosis hepatis as a benign neoplasm is based on these findings that endorse and extend previous considerations on the preneoplastic or neoplastic nature of this lesion. Irrespective of the classification of spongiosis hepatis as a benign neoplastic or a preneoplastic lesion, there is compelling evidence for its reliability as a sensitive marker for (hepato)carcinogenic effects in rats and fish. The data collected by Karbe and Kerlin support rather than contradict the reliability of spongiosis hepatis as an effect marker for carcinogens.

Abstract  BARBER(1 934) reported the death of five factory workers, who were employed in processes involving the use of dioxan. The principal lesions found at autopsy were a central zonal necrosis of the liver and a symmetrical necrosis of the cortex of the kidneys. The similarity of the renal condition to that found in the cortical necrosis of pregnancy first prompted the present investigation.

Abstract  Subchronic oral toxicity of 1,4-dioxane was examined by administering 1,4-dioxane in drinking water at 6 different concentrations of 0 (control), 640, 1,600, 4,000, 10,000 or 25,000 ppm (wt/wt) to F344 rats and BDF1mice of both sexes for 13 weeks. Food and water consumption and terminal body weight were decreased dose-dependently in rats and mice. A dose-dependent increase in the relative weights of kidney and lung was noted in rats and mice, while the relative liver weight was increased only in rats. Increases in plasma levels of aspartate aminotransferase (AST) and alanine aminotransferase (ALT) and a decrease in plasma glucose were noted primarily in the rats and mice dosed 25,000 ppm. Histopathological examination revealed that 1,4-dioxane affected the upper and lower respiratory tracts, liver, kidneys and brain in rats, while only the former two organs were affected in mice. Nuclear enlargement occurred in the respiratory, olfactory, tracheal and bronchial epithelia of the 1,4-dioxane-dosed rats and mice. The 1,4-dioxane-induced hepatic lesions were characterized by centrilobular swelling and necrosis in rats and mice and by glutathione S-transferase placental form (GST-P)-positive altered hepatocellular foci in rats, which are known as preneoplastic lesions. A no-observed-adverse-effect-level (NOAEL) was determined at 640 ppm for both rats and mice, since the nuclear enlargement in the nasal respiratory epithelium and the centrilobular swelling of hepatocytes in rats and the nuclear enlargement in the bronchial epithelium in mice were observed at 1,600 ppm. The NOAEL value corresponded to the estimated 1,4-dioxane intake of 52 mg/kg/day in rats and 170 mg/kg/day in mice.

Abstract  The responsiveness of SENCAR mouse skin to 20 different chemicals with known carcinogenic properties was assessed in initiation/promotion experiments. The purpose of these experiments was to evaluate the extent of false negative responses in mouse skin initiation/promotion protocols and to determine the extent to which early papilloma development can be used to predict the eventual development of malignant tumors. The chemicals were administered as initiators by four different routes: oral, intraperitoneal, subcutaneous, and topical. Following the initiating dose of carcinogen, the animals were subjected to topical applications of 1 microgram 12-O-tetradecanoylphorbol-13-acetate (TPA) 3 times per week for a period of 20 weeks. The yield of papillomas at 24 weeks was selected as a potential predictor of carcinoma yields at 52 weeks following the start of the promotion schedule. Positive responses were observed with only eight of the compounds tested. Where positive results were observed, there was some evidence that the response could depend both qualitatively and quantitatively on the route of administration. However, no route was clearly superior, i.e., different chemicals gave greater responses by different routes. Papilloma yield at 24 weeks following the start of the promotion schedule was clearly related to the development of carcinomas at 52 weeks. No simple linear relationship existed between papilloma yield and carcinoma development, since the number of malignant tumors per papilloma decreased with increasing papilloma yields. The relationship between papilloma and carcinoma yields appeared to be independent of the carcinogen used. These data indicate that there are some limitations in using mouse skin initiation/promotion experiments as the sole basis for identifying substances with carcinogenic activity. However, the test does perform well within certain classes of compounds. Within the limits of these chemical classes, the use of papilloma yield to predict carcinoma yield appears justified.

Abstract  Results from Drosophila mutagenicity tests of 45 chemical compounds assayed for the National Toxicology Program are presented. Nine compounds were judged positive and four equivocal in the sex-linked recessive lethal test. The nine positive compounds were acetin, allyl glycidyl ether, cyclophosphamide, 1,2-dibromo-3-chloropropane, 2,3-dibromo-1-propanol, dimethylcarbamyl chloride, 1,2-epoxy-butane, lasiocarpine, and N-nitrosopiperidine. The results for chloral hydrate, maleic hydrazide, propantheline bromide, and trifluralin were equivocal. Of the nine compounds positive in recessive lethal induction, only two--allyl glycidyl ether and dimethylcarbamyl chloride--failed to induce translocations. The remaining 32 were judged to be nonmutagenic under the conditions used.

Abstract  Twenty-seven chemicals were tested for their mutagenic potential in the L5178Y tk+/tk- mouse lymphoma cell forward mutation assay using procedures based upon those described by McGregor et al. (McGregor DB, Martin R, Cattanach P, Edwards I, McBride D, Caspary WJ (1987): Environ Mol Mutagen 9:143-160). Cultures were exposed to the chemicals for 4 hr, then cultured for 2 days before plating in soft agar with or without trifluorothymidine (TFT), 3 micrograms/ml. The chemicals were tested at least twice. Statistically significant responses were obtained with acid orange 10, aniline, benzaldehyde, o-chloroaniline, chlorodibromomethane, cytembena, 1,2-dibromo-4-(1,2-dibromomethyl) cyclohexane, dieldrin, lithocholic acid, oxytetracycline, phenazopyridine HCl, 1-phenyl-3-methyl-5-pyrazolone, sodium diethyldithiocarbamate, solvent yellow 14, tetraethylthiuram disulfide (disulfiram), 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. Apart from phenazopyridine HCl, acid orange 10, and solvent yellow 14, rat liver S9 mix was not a requirement for the mutagenic activity of these compounds. Chemical not identified as mutagens were N-4-acetylaminofluorene, chlorpheniramine maleate, chloropropamide, 1,4-dioxane, endrin, ethylene glycol, iron dextran, methapyrilene, sodium(2-ethylhexyl)alcohol.

Abstract  To evaluate the applicability of an in vivo-in vitro replicative DNA synthesis (RDS) test using rat hepatocytes, we conducted the RDS test with 22 nongenotoxic (Ames-negative) hepatocarcinogens and 25 noncarcinogens under our standardized conditions and judgement criteria. Compared to controls (RDS incidence of under 1.0%), the RDS test gave positive results for 18 hepatocarcinogens (positive sensitivity: 82%), and negative results for 20 noncarcinogens (negative specificity: 80%), and thus the overall concordance was 81%. These findings strongly suggest that the RDS test is an extremely useful method for early detection of nongenotoxic hepatocarcinogens.

Abstract  Neoplastic and proliferative hepatic lesions observed in 500 male and 499 female DBF1 mice used as untreated controls in the past ten 2-year carcinogenicity studies (each 50 males and 50 females for one study) for industrial chemicals at the Japan Bioassay Research Center. The incidences of altered cell foci (ACF) were 11.6% in males and 2.8% in females and those of each type of ACF were as follows; basophilic, eosinophilic, clear, vacuolated, and mixed cell foci were 4.0%, 1.2%, 4.6%, 0.2%, and 1.6% in male mice, respectively, and 1.2%, 0%, 0.8%, 0.4%, and 0.4% in females, hepatocellular adenoma (HCA) was 15% in males (minimum 4%, maximum 30%), and 4.4% in females (minimum 2%, maximum 8%), hepatocellular carcinoma (HCC) was 22.8% (minimum 2%, maximum 36%) in males and 2.0% (minimum 0%, maximum 4%) in females, vascular tumors were 6.6% (minimum 0%, maximum 6%) in male mice and 15.0% (minimum 6%, maximum 20%) in females. Compared with the data in rats, incidences of HCA and HCC in BDF1 mice were remarkably higher, however, the incidence of ACF in BDF1 mice was lower than those of rats. The different incidence of ACF noted in rats and in mice may suggest the different implications of ACF as the preneoplastic role in hepatocarcinogenesis.

Abstract  The authors explored the tissue and intracellular distribution in the body of xenobiotics (aniline-1-14C hydroclorate, dioxane-1,4-14C, toluol-1-14C, phenol-1-14C and 1,2-14C ethylene glycol) following their administration in single doses to white rats. The distribution of the tested substances in the body was correlated with their toxic effects. An analysis of distribution coefficients revealed a multifactorial nature of the distribution in the body of xenobiotics--environmental pollutants. A key role in the distribution of xenobiotics in the body is attributed to histohematic barriers which provide for the selective accumulation of xenobiotics in tissues by utilizing existing modes of active and passive membrane transport. The polytropic nature of the biological effects typical of most chemical environmental pollutants is accounted for by their multireceptor interactions in the body as well as by membrane damage resulting in the distortion of genetic information and, consequently, disorganization of metabolic processes.

Abstract  The ability of the rodent carcinogens 1,4-dioxane (DX) and thiourea (TU) to induce meiotic non-disjunction (ND) was assessed in 3- and 6-day-old Drosophila melanogaster females. The chemicals were administered orally and three 24 h and one 48 h broods were obtained after mating, to sample oocytes treated in increasingly earlier stages of development. The broods represent mainly mature oocytes (brood I), nearly mature oocytes (brood II), early oocytes (brood III) and very early oocytes (brood IV). The toxicity of DX increased with dose (1% (not toxic), 1.5, 2, 3, 3.5%) as well as a reduction in fecundity which was moderate. Induction of ND in mature oocytes was positive with 2, 3 and 3.5% concentrations and was not related to dose. In immature oocytes it was also positive though already at the lowest concentration tested (1%), suggesting a sensitivity higher than that of mature oocytes. TU at 0.10-10%, did not affect viability, but since fecundity was seriously impaired at high doses, ND was not assessed beyond the 1.5% concentration. TU also induced ND in mature and in immature oocytes; neither a threshold nor a dose effect was detected. The response of mature oocytes was lower than that of immature oocytes. TU induced increases of ND in the earliest cells tested in a more consistent fashion than DX. The data clearly show that both chemicals induced ND in mature oocytes and in the three subsets in which immature oocytes were fractionated. Though toxicity may play a significant unspecific role in the induction of chromosome malsegregation by DX and TU, the induction of ND at low doses, moderately toxic to the oocytes, suggests that the interaction with specific targets contributed to the results obtained.

Abstract  The spermicidal surfactant nonoxynol-9 (Igepal CO-630, GAF Corp.) and a potential impurity, 1,4-dioxane, were tested in the in vitro cell transformation assay using BALB/3T3 cells. Two treatment periods, 48 hr and 13 days, were used. Nonoxynol-9, tested at levels up to 10 micrograms/ml, did not induce transformation, whereas dioxane was very active in the induction of type III foci in the cultured BALB/3T3 cells.

Abstract  The disposal of organic chemicals in trenches at a waste disposal site near Ottawa, Ontario, Canada, has resulted in the contamination of the underlying aquifer. The organic residues measured in groundwater samples are reported and the mechanisms of contaminant transport in the aquifer discussed. Groundwater samples from monitoring wells and multilevel samplers were analyzed by gas chromatography-mass spectrometry. Ultratrace quantities of chlorinated dibenzodioxins and furans were found in groundwaters directly beneath the trenches. A wide variety of compounds were identified and quantitated in samples from the aquifer. The compound of greatest concern was 1,4-doixane, because of its toxicity and mobility, while that present in greatest concentration was a Freon, F113, which appeared to be very persistent, although three transformation products were identified.

Abstract  Nearly 500 long-term rodent carcinogenicity studies carried out by the National Cancer Institute and the National Toxicology Program were examined, and 12 chemicals were identified that produced nasal tumors: allyl glycidol ether, p-cresidine, 1,2-dibromo-3-chloropropane, 1,2-dibromoethane, 2,3-dibromo-1-propanol, dimethylvinyl chloride, 1,4-dioxane, 1,2-epoxybutane, iodinated glycerol, procarbazine, propylene oxide, and 2,6-xylidine. All 12 of these chemicals produced nasal tumors in rats, and 5 also produced nasal tumors in mice. Most of the nasal carcinogens (1) produced tumor increases in both sexes, (2) produced tumors at other sites as well, (3) had significantly reduced survival at doses that were carcinogenic, and (4) were genotoxic. Only 5 of the 12 nasal carcinogens were administered by inhalation. A variety of different types of nasal cavity tumors were produced, and specific tumor rates are given for those chemicals causing multiple tumor types. Increased incidences of nasal neoplasms were often accompanied by suppurative/acute inflammation, epithelial/focal hyperplasia and squamous metaplasia. However, high incidences of these nonneoplastic nasal lesions were also frequently seen in inhalation studies showing no evidence of nasal carcinogenicity, suggesting that in general nasal carcinogenesis is not associated with the magnitude of chronic toxicity observed at this site.

Abstract  Molecular capsules based solely on the interaction of halogen bonding (XB) are presented along with their host-guest binding properties in solution. The first example of a well-defined four-point XB supramolecular system is realized by decorating resorcin[4]arene cavitands with polarized halogen atoms for dimerization with tetra(4-pyridyl) resorcin[4]arene cavitands. NMR binding data for the F, Cl, Br, and I cavitands as the XB donor show association constants (Ka ) of up to 5370 M(-1) (ΔG283 K =-4.85 kcal mol(-1) , for I), even in XB-competitive solvent, such as deuterated benzene/acetone/methanol (70:30:1) at 283 K, where comparable monodentate model systems show no association. The XB capsular geometry is evidenced by two-dimensional HOESY NMR, and the thermodynamic profile shows that capsule formation is enthalpically driven. Either 1,4-dioxane or 1,4-dithiane are encapsulated within each of the two separate cavities within the XB capsule, with of up to Ka =9.0 10(8)  M(-2) (ΔG283 K =-11.6 kcal mol(-1) ).

Abstract  The title compound, C(15)H(16)O(4), was prepared by the reaction of 2,2-dimethyl-1,3-dioxane-4,6-dione and 3,4-dimethyl-benzaldehyde in ethanol. The 1,3-dioxane ring exhibits an envelope conformation. In the crystal, mol-ecules are linked by weak inter-molecular C-H⋯O hydrogen bonds, forming chains parallel to the b axis.