Abstract  The sensitized-photoreactions of diphenyliodonium salt and four of its technically relevant derivatives bearing lipophilic substituents were investigated by pseudo-steady-state and time-resolved CIDNP experiments. Singlet (naphthalene, diphenylanthracene, dimethylanthracene) and triplet (xanthone, thioxanthone, Michler's ketone) sensitizers were used in a variety of solvents (acetonitrile, dimethyl sulfoxide, dimethylformamide, methanol, chloroform, tetrahydrofurane, diethylene glycol dimethyl ether, dioxane, toluene). Under all conditions, the primary step leading to CIDNP was found to be electron transfer from the excited sensitizer *Sens to the onium cation On(+). All spin-polarization effects could be explained consistently within the framework of radical pair theory (S-T-0-type CIDNP). Pair substitution, i.e., the transformation of the primary radical pairs RP I (On(.)Sens(.+)) into secondary pairs RP 2 (Ph(.)Sens(.+), where Ph. is the phenyl or an aryl radical) plays a key role for the CIDNP effects and even leads to a field dependence of the polarization phases for the system diphenyliodonium cation/naphthalene in dioxane. Decreasing solvent polarity causes an increase of the rate RP 1 --> RP 2. The introduction of a long lipophilic side chain into the onium salt has the same effect, presumably owing to self-solvation.<

Abstract  The physical properties of organized system (bilayers and monolayers at the air water interface) composed of bovine lipid extract surfactant (BLES) were studied using correlated experimental techniques. 6-Dodecanoyl-2-dimethylamino-naphthalene (LAURDAN)-labeled giant unilamelar vesicles (mean diameter approximately 30 microm) composed of BLES were observed at different temperatures using two-photon fluorescence microscopy. As the temperature was decreased, dark domains (gel-like) appeared at physiological temperature (37 degrees C) on the surface of BLES giant unilamelar vesicles. The LAURDAN two-photon fluorescent images show that the gel-like domains span the lipid bilayer. Quantitative analysis of the LAURDAN generalized polarization function suggests the presence of a gel/fluid phase coexistence between 37 degrees C to 20 degrees C with low compositional and energetic differences between the coexisting phases. Interestingly, the microscopic scenario of the phase coexistence observed below 20 degrees C shows different domain's shape compared with that observed between 37 degrees C to 20 degrees C, suggesting the coexistence of two ordered but differently organized lipid phases on the bilayer. Epifluorescence microscopy studies of BLES monomolecular films doped with small amounts of fluorescent lipids showed the appearance and growth of dark domains (liquid condensed) dispersed in a fluorescent phase (liquid expanded) with shapes and sizes similar to those observed in BLES giant unilamelar vesicles. Our study suggests that bovine surfactant lipids can organize into discrete phases in monolayers or bilayers with equivalent temperature dependencies and may occur at physiological temperatures and surface pressures equivalent to those at the lung interface.

Abstract  The solution properties of two water-soluble polymers, poly(acrylic acid) (PAA), covalently labeled with the fluorescent hydrophobic dye naphthalene (Np), have been investigated in water:organic solvent mixtures. The naphthalene chromophores have been randomly attached, onto the polymer, with two different degrees of labeling. Fluorescence measurements (steady-state and time-resolved) have been used to follow the photophysical behavior of the polymers and consequently report on the self-association of the polymers in the mixed organic (methanol or dioxane):aqueous solutions. The emission spectra of the high-labeled Np PAA reveal the presence of monomer and excimer bands whereas with the low-labeled polymer only monomer emission is observed. The excitation spectra collected at the monomer and excimer emission bands show significant differences, depending on the water content of the mixture, which indicate the simultaneous presence of preformed and dynamic dimers as routes to excimer formation. The time-resolved data decay profiles of the high-labeled polymer in the mixtures were always triple exponential whereas in pure methanol and dioxane they follow biexponential laws. The data in the mixtures are consistent with two types of monomers and one excimer. Both monomers are able to give rise to excimer in the excited state, one type involving the movement of long distant Np chromophores and the other involving a local reorientation of adjacent Np chromophores. These correspond to different decay times: (1) a long which corresponds to the long distant approach of non-neighboring Np chromophores forming an excimer and (2) a short corresponding to the fast adjustment of two neighboring Np chromophores in order to have the adequate parallel geometry. An additional decay time corresponding to the excimer decay was found to be present at all wavelengths. All the decay times were dependent on the water content of the mixture. An estimation of the two excimer forming rate constants values is made for the mixed media considered in this work. On the whole, using both steady-state and time-resolved fluorescence parameters, and by comparing data for a polymer with a small number of hydrophobes with a more highly modified one, it is possible in great detail to demonstrate how association is controlled by solvent quality for the hydrophobes and by the distance between hydrophobes.

Abstract  The high aqueous solubility of monoaromatic and some diaromatic oil components may hinder classical growth-based MPN enumeration of bacterial mono- and di-aromatics degraders because these aromatics are toxic in high concentrations. We developed a microplate MPN method for the enumeration of toluene-, xylene-, naphthalene-, biphenyl- and benzothiophene-degraders on the basis of phase-partitioning of substrate between a biologically inert organic phase and an aqueous mineral salt medium. This way, it was possible to maintain non-toxic, aqueous concentrations in the microplate wells. Depletion of aqueous aromatics by growth of the degraders was prevented by the continuous solubilization of aromatics from the silicone phase. The method was validated by MPN enumerating degrader cultures both with phase-partitioned aromatics and with tryptic soy broth as carbon sources. The applicability of the method was demonstrated by MPN-enumerating mono- and di-aromatic degraders in soils of varying hydrocarbon pre-exposure.

Abstract  The US Air Force wrote the specification for the first official hydrocarbon-based jet fuel, JP-4, in 1951. This paper will briefly review the toxicity of the current fuel, JP-8, as compared to JP-4. JP-8 has been found to have low acute toxicity with the adverse effects being slight dermal irritation and weak dermal sensitization in animals. JP-4 also has low acute toxicity with slight dermal irritation as the adverse effect. Respiratory tract sensory irritation was greater in JP-8 than in JP-4. Recent data suggest exposure to jet fuel may contribute to hearing loss. Subchronic studies for 90 days with JP-8 and JP-4 showed little toxicity with the primary effect being male rat specific hydrocarbon nephropathy. A 1-year study was conducted for JP-4. The only tumors seen were associated with the male rat specific hydrocarbon nephropathy. A number of immunosuppressive effects have been seen after exposure to JP-8. Limited neurobehavioral effects have been associated with JP-8. JP-8 is not a developmental toxicant and has little reproductive toxicity. JP-4 has not been tested for immune, neurobehavioral or reproductive endpoints. JP-8 and JP-4 were negative in mutagenicity tests but JP-4 showed an increase in unscheduled DNA synthesis. Currently, JP-8 is being used as the standard for comparison of future fuels, including alternative fuels. Emerging issues of concern with jet fuels include naphthalene content, immunotoxicity and inhalation exposure characterization and modeling of complex mixtures such as jet fuels.

Abstract  This volume of the IARC Monographs considers some traditional herbal medicines, including extracts from certain plants of the genera Aristolochia, Rubia, Morinda and Senecio; some mycotoxins, specifically aflatoxins and fumonisin B1; and two industrial chemicals, naphthalene and styrene. Of these, the Monographs have previously evaluated several of the pyrrolizidine alkaloids that occur in certain species of Senecio, Crotalaria and other plant genera, including riddelliine (IARC, 1976, 1987); various mycotoxins, including the aflatoxins (IARC, 1993a) and the family of mycotoxins to which fumonisin B1 belongs (IARC, 1993b); and styrene (IARC, 1994). These previous evaluations are summarized in Table 1.

Abstract  The three different ligands (Q(2) to Q(4)) based on 2-amino-1,4-naphthoquinone (Q(1)), have been synthesized and explored as neutral ionophores for preparing polyvinyl chloride-based membrane sensors selective to indium (III). The addition of potassium tetrakis(4-chlorophenyl) borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 16 having membrane of ligand (Q(2)) with composition (%, w/w) ionophore Q(2) (3.0%):PVC (30.0%):o-NPOE (63.0%):KTpClPB (4.0%). This sensor exhibits Nernstian response with slope 19.8 mV/decade of activity in the concentration range 2.5 x 10(-7) to 1.0 x 10(-2) M indium (III), performs satisfactorily over wide pH range of (2.5-7.5) with a fast response time (10 s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of acetonitrile, ethanol and methanol. The proposed sensor can be used over a period of 3.5 months without significant drift in potentials. The quantitative application of sensor was also evaluated by comparative analysis of artificially made sea water with AAS.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. RRM BOOK CHAPTER GENOTOXICITY TEST CHEMICAL TRACE ANALYSIS SEQUENTIAL FLUID-FLUID EXTRACTION VOLUME REDUCTION GAS CHROMATOGRAPHY MASS SPECTROMETRY ORGANIC COMPOUND CHLORINATED WATER JOINT SAMPLE PRETREATMENT METHODS AND TECHNIQUES POLLUTION ASSESSMENT CONTROL AND MANAGEMENT ANALYTICAL METHOD

Abstract  The contamination of marine ecosystems by endocrine disrupting compounds (EDCs) is of great concern. Protein expression profile maybe a good method to help us understand the molecular mechanisms of EDCs-toxicity to aquatic organisms. In this study, the abalone (Haliotis diversicolor supertexta), was selected as the target organism. Toxicological effects of two reference endocrine disruptors: diallyl phthalate (DAP, 50microgL(-1)) and bisphenol-A (BPA, 100microgL(-1)) were investigated after a three months static-renewal exposure on abalones using proteomics to analyze their hepatopancreas tissues. Some enzyme activity parameters of hepatopancreas extracts were also performed, including Na(+)-K(+)-ATPase, Ca(2+)-Mg(2+)-ATPase, peroxidase (POD) and malondialdehyde (MDA) production. After analyzing the proteomics profile of hepatopancreas by 2D gel electrophoresis, we found that 24 spots significantly increased or decreased at protein expression level (2-fold difference) in the 2D-maps from the treatment groups. Eighteen out of 24 protein spots were successfully identified by matrix-assisted laser desorption/ionization tandem time-of-flight mass spectrometry (MALDI-TOF-MS). These proteins can be roughly categorized into diverse functional classes such as detoxification, oxidative stress, hormone regulating, cellular metabolism and innate immunity. In addition, the enzymatic results indicated that DAP/BPA exposure affected the oxidative stress status and the cellular homeostasis, which partly corroborated the proteomics' results. Taken together, these data demonstrate that proteomics is a powerful tool to provide valuable insights into possible mechanisms of toxicity of EDCs contaminants in aquatic species. Additionally, the results highlight the potential of abalone as a valuable candidate for investigating EDCs impacts on marine ecosystems.

Abstract  Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental pollutants produced in the combustion of organic matter. PAHs are present in automobile exhaust and tobacco smoke, and they have recently been designated as human carcinogens. Current evidence indicates that PAHs are activated enzymatically to mutagenic metabolites that interact with DNA. There is evidence for three pathways of activation: the diol epoxide path, the radical-cation path, and the quinone path. The relative importance of these paths for human lung cancer has not been established. We now report syntheses of the principal phenol and quinone isomers of the prototype PAH carcinogen benzo[a]pyrene (BP) that are known or are suspected to be formed as metabolites of BP in human bronchoalveolar cells. The methods of synthesis were designed to be adaptable to the preparation of the (13)C-labeled analogues of the BP metabolites. These compounds are needed as standards for sensitive LC-MS/MS methods for analysis of BP metabolites formed in lung cells. Efficient novel syntheses of the 1-, 3-, 6-, 9-, and 12-BP phenols and the BP 1,6-, 3,6-, 6,12-, and 9,10-quinones are now reported. The syntheses of the BP phenols (except 6-HO-BP) involve the key steps of Pd-catalyzed Suzuki-Miyaura cross-coupling of a naphthalene boronate ester with a substituted aryl bromide or triflate ester. The BP quinones were synthesized from the corresponding BP phenols by direct oxidation with the hypervalent iodine reagents IBX or TBI. These reagents exhibited different regiospecificities. IBX oxidation of the 7- and 9-BP phenols provided the ortho-quinone isomers (BP 7,8- and 9,10-diones, respectively), whereas TBI oxidation of the 1-, 3-, and 12-BP phenols furnished BP quinone isomers with carbonyl functions in separate rings (BP 1,6-, 3,6-, and 6,12-diones, respectively).

Abstract  Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants formed from combustion products of fossil fuels, cigarette smoking and in grilled/smoked foods. They are reported to alter trophoblast proliferation in placenta, in addition to disturbing its endocrine functions, which may be able to increase the risk of preterm delivery in pregnant women. The present study was planned to assess possible involvement of PAHs exposure of pregnant women (measured as placental PAHs concentrations) with preterm delivery cases among women of Lucknow city (India). We performed a case-control study and a total of 60 mothers (n=31 full term and n=29 preterm deliveries) were recruited at a local nursing home of Lucknow, for the period of August 2005-February 2006. Subsequent to parturition, placental tissues from each participant were immediately collected and kept at -20 degrees C until PAHs analyses. Placental tissue PAHs concentrations were determined by HPLC, using a fluorescence detector. Mean+/-SD placental level (61.91+/-12.43ppb) of benzo(b)fluoranthene, a carcinogenic PAH, was found significantly elevated (p<0.05) among women with preterm delivery when compared with the level (23.84+/-7.01) in women having full-term deliveries. In the same way, non-carcinogenic fluoranthene level (325.91+/-45.14ppb) was also detected to be higher in the preterm delivery group compared to 208.6+/-21.93ppb level from the full-term delivery group of women. Additionally naphthalene, acenaphthylene, phenanthrene, anthracene, benzo(a)pyrene and dibenzo(a,h)anthracene levels in placental tissue were also found to be higher in the preterm delivery group of women but the difference did not reach statistically significant levels. This foremost study from India with modest samples size and limited statistical power does not show a substantial involvement of PAHs with preterm delivery, but higher concentrations of placental PAHs detected among preterm delivery group of women could show some possible association with these environmental toxicants. Further study with large sample size, controlled for confounders and great statistical power, is reasonable to elucidate the association of PAHs exposure with preterm delivery of women in India.

Abstract  To explore the relationship between the susceptibility to arsenic trioxide (As(2)O(3))-induced apoptosis of leukemia cells and the level of reactive oxygen species (ROS) of cells, flow cytometry and electron microscopy were applied to identify apoptosis, and dihydrorhodamine123 was used to display the ROS level of cells. As(2)O(3) alone or in combination with 2,3-dimethoxy-1,4-naphthoquinone (DMNQ, 2.5 &mgr;mol/L for NB4 cells, 10 &mgr;mol/L for U937 cells) were used to induce cell apoptosis. The results showed that NB4 cells possessed higher level of ROS than U937 cells. DMNQ raised ROS levels of NB4 and U937 cells, sensitized U937 cells to As(2)O(3)-induced apoptosis, and enhanced the efficacy of As(2)O(3)-induced apoptosis of NB4 cells. Catalase reversed the effect of DMNQ on NB4 and U937 cells. It was concluded that the susceptibility of leukemia cells to arsenic trioxide-induced apoptosis is determined by ROS level in the cells.

Abstract  A wide range of epidemiological studies was reported, each of which dealt with a sample of a working population and examined the effects on these workers of the chemicals and other hazardous materials to which they were exposed. Specific materials or exposures noted in these studies included acrylamide (79061), acrylonitrile (107131), aldrin (309002), arsenic (7440382), asbestos (1332214), benzene (71432), benzidine (92875), beryllium (7440417), budgerigars, carbon-disulfide (75150), carbon-monoxide (630080), chromium-oxide (1308389), Portland cement, chlorinated naphthalenes, chloromethyl-methyl-ether (107302), bischloromethyl-ether (542881), chromic-acid (1333820), coal, coke manufacture, cotton (along with flax, hemp, jute, and sisal), DDT (50293), dichlorvos (62737), diphenyl (92524), ferrosilicon, fibrous glass, fluorides, grain, granite, graphite (7782425), gum acacia, hair spray lacquer, iron-oxide (1309371), lead (7439921), lindane (58899), manganese (7439965), mercury (7439976), methyl-n-butylketone (591786), methylene-chloride (75092), nitrogen-oxides, oil mists, parathion (56382), paraquat (1910425), pesticides, polyvinyl-chloride (9002862), potash, proteolytic enzymes, silica (7631869), styrene (100425), solvents, sulfuric-acid (7664939), talc (14807966), trichloroethylene (79016), trichlorotrifluoroethane (76131), 2,4,5-trichlorophenoxyacetic-acid (93765), wood, and xylene (1330207).

Abstract  HEEP COPYRIGHT: BIOL ABS. GAS CHROMATOGRAPHY

Abstract  Two experimental approaches were used to examine transport in saturated porous media. One design, the box experiment, allowed two-dimensional sampling of the solute plume. The more traditional column design was one-dimensional with sample collection only at the effluent end. A total of three box and two column experiments were conducted. The method of moments was used to analyze plume behavior in both experiments. Comparison between the experiments were made using the moments. For similar porous materials the same retardation was observed despite an order of magnitude different in velocities. Data from the one-dimensional column experiments were used to estimate dispersivities that were used to predict the behavior in the multidimensional box experiment. Results indicated that velocity information from the box experiment was needed in order to attain an adequate prediction of its response. 8 refs., 9 figs., 12 tabs.

Abstract  HEEP COPYRIGHT: BIOL ABS. AIRBORNE PARTICULATES

Abstract  HEEP COPYRIGHT: BIOL ABS. Mud crabs were exposed continuously for 6 mo. after hatching to water-soluble fractions (WSF) of no. 2 fuel oil. Survival, growth and development rate were monitored during this time. The zoeal stages were the most sensitive to fuel oil. A 20% WSF (0.36 ppm total naphthalenes, 1.26 ppm total hydrocarbons) was acutely toxic to these stages. Of the zoeal stages, the 1st stage appeared to be the most sensitive. The combined duration of the 4 zoeal stages was significantly increased by increasing WSF exposure concentrations. The megalopa and crab stages were not particularly sensitive to continued petroleum hydrocarbon exposure, particularly when compared to zoeal stages. However, mean duration of the megalopa and 1st crab stages was significantly affected by oil exposure. Individuals which survived the highest exposure concentrations as larvae appeared to grow larger during the crab stages, so that at the end of 6 mo. comparably staged crabs were equal to or larger than both control crabs and those exposed to low WSF concentrations. Stage distributions at the end of 6 mo. showed no differences due to WSF exposure. Sex ratios, which could be determined at the end of 6 mo., were approximately 1, indicating no sex-related differential sensitivity to WSF exposure, at least as larvae or juveniles. These crabs possess considerable ability to recover from the effects of chronic sublethal exposure to petroleum hydrocarbons. The most deleterious effects of oil pollution on this species may be due to its impact on larval recruitment into the adult population.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. RRM FUNGAL LIGNINOLYSIS ORGANOPOLLUTANT BIODEGRADATION POLYCYCLIC AROMATIC HYDROCARBONS CHLOROPHENOLS BISPHENYLALKANE PESTICIDES

Abstract  The repair of human DNA after damage by known and potential metabolites of benzo(a)pyrene was examined utilizing the bromodeoxyuridine photolysis assay. Repair was characterized as either UV (long) or ionizing radiation type (short) repair utilizing normal cells and cells deficient in UV-type repair endonuclease from a patient with xeroderma pigmentosum (XP). Only (|)-7beta,8alpha-dihydroxy-9beta,10beta-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene (BP diol epoxide 1) and its disastereomer, (|)-7beta,8alpha-dihydroxy-9alpha,10alpha-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene (BP diol epoxide 2) elicit damage to DNA which is recognizable by the UV excision repair system in normal human cells. Benzo(a)pyrene 4,5-, 9,10-, 11,12-oxides do not elicit damage which is repairable by this repair system. The 1,2-diol-3,4-epoxides from naphthalene have no measurable activity in the assay. Both the benzo(a)pyrene ring structure and the diol epoxide groups evidently are important in causing the damage to DNA which is repairable by the UV excision repair system. These results parallel the reported high mutagenic activity of these compounds and support the concept that benzo(a)pyrene 7,8-diol-9,10-epoxides may be the ultimate, metabolically activated forms of benzo(a)pyrene.

Abstract  A laboratory investigation was conducted on the ozonation of a liquid waste sample from an experimental coal gasification plant. A 30-in. high, 2.75-in. i.d. (internal diameter) packed glass column is used to countercurrently scrub the wastewater with a gas stream of 74 mg/l O3. Specific component analyses are presented of the wastewater and its ozonated end products. These were done via wet analyses and gas chromatography. Data examination indicates that higher O3 levels yield substantial reduction of cyanogen compounds and polyduric phenols, with a simultaneous increase in the concentration of low boiling compounds measured as acetone, benzene and methanol.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. The sensitivity of a biomarker for environmental contamination with persistent organochlorines and PAHs (cytochrome P450-1A1 induction in feral fish) was evaluated at six sites along 314 km of the Willamette River, Oregon. Whole-body contamination of Northern squawfish with approximately 2 pg/g of TCDD and 20 pg/g of TCDF in Portland Harbor was significantly higher than upstream sites. Carp muscle TCDF and hepatic biomarker response were also elevated at this site, as were sediment TCDD, TCDF, and PAHs concentrations. In July, cutthroat trout TCDD concentrations above and below a bleached kraft pulp mill were similar. In October cutthroat trout below the mill contained about 2-fold more TCDD than fish upstream. Similar hepatic biomarker profiles occurred in cutthroat trout above and below the mill at both times. Histopathological examination suggested existing organochlorine burdens in adult Willamette River fish were not overtly toxic at any site.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. To concentrate natural and refinery-derived inducers of mixed function oxygenase (MFO), semipermeable membrane devices (SPMDs) were deployed for 11-12 days in Norman Wells refinery effluent and upstream and downstream on the Mackenzie River, Northwest Territories, Canada. SPMDs, which are layflat polyethylene membrane tubes containing a thin film of purified triolein, absorb freely dissolved neutral organic chemicals that diffuse through the polyethylene membrane. Fish liver cells (Poeciliopsiscts of SPMDs from downstream of the refinery outfall were over20 times as potent as those from upstream SPMDs. Polyaromatic hydrocarbons (PAHs) and C1- to C3-substituted PAHs were abundant in extracts of SPMDs from the effluent and, to a lesser degree, in extracts of SPMDs from 0.5 km downstream. In effluent-exposed and downstream SPMDs, concentrations of parent PAHs were lower than those of C1-substituted PAHs. The highest concentrations were those of C2- and rivers) and the utili