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PubMed2002

On-Line HPLC-UV-mass spectrometry and tandem mass spectrometry for the rapid delineation and characterization of differences in complex mixtures: a case study using toxic oil variants.

An integrated differential approach to the characterization of complex mixtures is presented which includes the targeting of liquid chromatography (LC) peaks for identification using characteristic UV adsorption of the LC peak, subsequent molecular weight and formula determination using accurate mass LC mass spectrometry (MS), and structure characterization using accurate mass LC-tandem mass spectrometry. The use of differential UV adsorption aids in narrowing the scope of the study to only specific peaks of interest. Accurate mass measurement of the molecular ion species provides molecular weight information as well as atomic composition information. The tandem MS (MS/MS) spectra provide fragmentation information which allows for structural characterization of each component. Accurate mass assignment of each of the fragment ions in the MS/MS spectrum provides atomic composition for each of the fragment ions and thus further aids in the structural characterization. These experiments are facilitated through the use of on-line LC-MS and LC-MS/MS with in-line UV detection. A synthetic toxic oil (STO) related to Toxic Oil Syndrome is studied with a focus on possible contaminants resulting from the interaction of aniline, used as a denaturant, with the normal components of the oil. A differential analysis between the STO and a control oil is performed. LC peaks were targeted using UV absorbance to indicate the possible presence of the aniline moiety. Further differential analysis was performed through the determination of the MS signals associated with each component separated on the LC. Finally, the MS/MS data was also used to determine if the fragmentation of the targeted components indicated the presence of aniline. The MS/MS and accurate mass data were used to assign the structures for the targeted components.

Chromatography, High Pressure Liquid↗
PubMedDate not supplied

Toxicological evaluation of mixtures of ten widely used pesticides.

Toxicities of pesticidal mixtures in biological systems have not been explored adequately. Therefore, mixtures of ten widely used pesticides were evaluated for their toxicity in ICR male mice (21-24 g). Mice were given four mixtures of alachlor, aldrin, atrazine, 2,4-dichlorophenoxyacetic acid, DDT, dieldrin, endosulfan, lindane, parathion and toxaphene, at 0.01, 0.1, 1.0 and 10 ppm of each of these pesticides, in drinking water for 90 days ad libitum. Also, two mixtures at 2.5 and 5 mg kg-1 of each pesticide in 7.5% Tween-80 in water were administered to additional groups of mice by oral intubation daily for up to 14 days. In relation to the control, the 90-day exposure caused a dose-dependent increase in the liver/body weight ratio (3-44%), a decrease in the pentobarbital (60 mg kg-1, i.p.)-induced sleep time (11-79%) and an increase in the metabolism of aniline (233-399%), amidopyrine (79-231%), phenacetin (127-318%) and benzo[a]pyrene (286-1633%) in the 9000 g hepatic supernatants from the mixture-treated mice. Proliferation, dilatation and fragmentation of the endoplasmic reticulum and scattering of ribosomes were noticed with mixture livers. In the 5 mg kg-1 group, 90% of the animals died by Day 8; incidence of death was considerably less in the 2.5 mg kg-1 group. The serum cholinesterase activity was inhibited by ca. 50% in the 2.5 and 5 mg kg-1 groups on either one or both of Days 8 and 15; the liver/body weight ratio increased by 24-79% and the pentobarbital-induced sleep time decreased by 80-96%.(ABSTRACT TRUNCATED AT 250 WORDS)

Administration, Oral↗
PubMed2002

Baseline toxicity (narcosis) of organic chemicals determined by in vitro membrane potential measurements in energy-transducing membranes.

Baseline toxicity of a selection of industrial chemicals and pharmaceuticals is determined experimentally with a new in vitro test system (Kinspec) using membrane vesicles isolated from a photosynthetic bacterium, Rhodobacter sphaeroides. This test system is selective and more sensitive than other mechanistic test systems for baseline toxicity. The only concomitantly determined mechanism is uncoupling, which can be distinguished from baseline toxicity by pH-dependent measurements. Because the tests system contains only the target site for baseline toxicants, the biological membrane, effective target site concentrations can be directly related to observed effects by combining the in vitro test with membrane-water partition experiments. No differences were found between the effective membrane concentrations of nonpolar and polar compounds, confirming the earlier hypothesis that differences in lethal body burdens are primarily caused by unequal distribution of the compounds between target and nontarget lipids and not by different mechanisms. A selection of pharmaceuticals with various specific modes of toxic action exhibited the same constant effective membrane concentrations as found for pure baseline toxicants. In mixtures of four to six components, the pharmaceuticals were concentration-additive with each other and with the pure baseline toxicants. A potential application of the proposed test system lies, therefore, in assessing the cumulative baseline toxicity in complex environmental mixtures.

Drug-Related Side Effects and Adverse Reactions↗
PubMed2002

Developmental toxicity of a commercial herbicide mixture in mice: I. Effects on embryo implantation and litter size.

We investigated the developmental toxicity in mice of a common commercial formulation of herbicide containing a mixture of 2,4-dichlorophenoxyacetic acid (2,4-D), mecoprop, dicamba, and inactive ingredients. Pregnant mice were exposed to one of four different doses of the herbicide mixture diluted in their drinking water, either during preimplantation and organogenesis or only during organogenesis. Litter size, birth weight, and crown-rump length were determined at birth, and pups were allowed to lactate and grow without additional herbicide exposure so that they could be subjected to additional immune, endocrine, and behavioral studies, the results of which will be reported in a separate article. At weaning, dams were sacrificed, and the number of implantation sites was determined. The data, although apparently influenced by season, showed an inverted or U-shaped dose-response pattern for reduced litter size, with the low end of the dose range producing the greatest decrease in the number of live pups born. The decrease in litter size was associated with a decrease in the number of implantation sites, but only at very low and low environmentally relevant doses. Fetotoxicity, as evidenced by a decrease in weight and crown-rump length of the newborn pups or embryo resorption, was not significantly different in the herbicide-treated litters.

2,4-Dichlorophenoxyacetic Acid↗
PubMedDate not supplied

Implications of chemical mixtures in public health practice.

The Agency for Toxic Substances and Disease Registry (ATSDR) is a federal public health agency that investigates and strives to prevent human health problems produced by exposure to toxic chemicals and their mixtures in the environment. Most human exposures involving toxic chemicals or mixtures are thought to originate from environmental and occupational sources; however, concurrent exposures are also likely from other sources, such as prescription and nonprescription drugs, indoor air pollutants, alcohol, and tobacco smoke. Thus, in evaluating the potential hazard following exposure to environmental mixtures, ATSDR not only considers the inherent joint toxicity of the mixture but also the influence of environmental, demographic, occupational, and lifestyle factors. To foster these goals, ATSDR has pursued a Mixtures Research and Assessment Program that consists of three component efforts: trend analysis, joint toxicity assessment, and experimental testing. Through trend analysis, ATSDR sets priorities for environmental mixtures of concern for which joint toxicity assessments are conducted as needed. If data are not available to conduct appropriate assessments, a research agenda is pursued through established extramural mechanisms. Ultimately, the data generated are used to support ATSDR's work at sites involving exposure to chemical mixtures. This pragmatic approach allows testable hypotheses or research needs to be identified and resolved and enhances our understanding of the mechanisms of joint toxicity. Several collaborative and cooperative efforts with national and international organizations such as the Toxicology and Nutrition Office, the Netherlands, and the Department of Energy are being pursued as part of these activities. ATSDR also develops guidance manuals to consistently and accurately apply current methodologies for the joint toxicity assessment of chemicals. Further, expert panels often are assembled to resolve outstanding scientific issues or obtain expert advice on pertinent issues. Recently, the need for studies on chemical mixtures has been proposed as one of the six priority areas the agency identified in its agenda for public health environmental research. This has been reinforced through the agency's close work with communities whose leaders have spoken passionately about their concern for information on exposures to chemical mixtures. The five other priority research areas the agency identified are exposure, susceptible populations, communities and tribal involvement, evaluation/surveillance of health effects, and health promotion/prevention.

Algorithms↗
PubMed2004

Adsorption, transformation, and bioavailability of the fungicides carbendazim and iprodione in soil, alone and in combination.

When studying the effect of mixtures of toxic substances on soil organisms, attention must be paid to peculiarities in exposure to mixtures as opposed to that of single toxicants. The fungicides carbendazim and iprodione compete in the adsorption to soil. The presence of iprodione reduced the adsorption of carbendazim by 30%, while carbendazim reduced the adsorption of iprodione by 70%. Iprodione had little effect on the transformation rate of carbendazim in soil. However, carbendazim retarded the transformation of iprodione in soil by 26%. The concentration of the fungicides in pore water was found to be substantially higher for mixtures than when a fungicide alone was present in the soil. The effect of the additional fungicide on the concentration is especially apparent in the period following the first 1 to 2 weeks of the incubation. The inclusion of copper in the mixture has little additional effect on the concentration of the fungicides in pore water.

Adsorption↗
PubMed1992

Comparative study of the acute lung toxicity of pure cobalt powder and cobalt-tungsten carbide mixture in rat.

Alveolitis progressing to lung fibrosis has been reported in workers exposed to cobalt containing dust (e.g., tungsten carbide-cobalt mixture as produced by the hard metal industry) but rarely following exposure to pure cobalt dust (e.g., in cobalt-producing factories). We have previously demonstrated that tungsten carbide-cobalt mixture is more toxic toward rat alveolar macrophages in vitro than pure cobalt metal powder. The present study was undertaken to compare in female rats the acute pulmonary response (lung weight, lung histology, cellular and biochemical analyses of bronchoalveolar lavage fluid, and mortality) following the intratracheal instillation of pure cobalt (Co) particles (median particle size, d50:4 microns), pure tungsten carbide (WC) particles (d50:2 microns), tungsten carbide-cobalt (WC-Co) powder (d50:2 microns; cobalt 6.3%, tungsten 84%, carbon 5.4%) and crystalline silica (d50 less than 5 micron) used as pneumotoxic reference material. WC alone (15.67 mg/100 g body wt) behaves as an inert dust producing only a mild accumulation of macrophages in the alveolar duct walls. Co alone (1.0 mg/100 g) only causes a moderate inflammatory response. An identical amount of Co given as WC-Co mixture (16.67 mg/100 g; corresponding to 1.0 mg Co/100 g) produces a severe alveolitis and fatal pulmonary edema. Cellular and biochemical characteristics of bronchoalveolar lavage fluid collected 24 hr after the intratracheal instillation of WC (1.0 mg/100 g) or Co (0.06 mg/100 g) are not significantly different from those of control animals instilled with sterile saline. On the contrary, bronchoalveolar lavage fluid changes following administration of the WC-Co mixture (1.0 mg/100 g; corresponding to 0.06 mg Co/100 g) are very similar to those induced by crystalline silica (1.0 mg/100 g). The amount of cobalt excreted in urine is significantly higher when the animals are exposed to WC-Co powder as compared to an equivalent amount of pure cobalt particles, suggesting an increased bioavailability of cobalt metal when combined with tungsten carbide. This study demonstrates that the acute lung toxicity of tungsten carbide-cobalt mixture is much higher than that of each individual component and may explain why lung fibrosis is rarely if ever induced by exposure to pure cobalt dust.

Animals↗
PubMed2004

Hazardous chemicals in complex mixtures--a role for direct toxicity assessment.

Whole sample toxicity assessment can help identify, diagnose and control impacts in the environment arising from the release of hazardous chemicals in complex mixtures. This role for direct toxicity assessment is considered against a background of increased international activity in the regulation of chemicals and reported improvements in the quality of surface waters in England and Wales. International legislation is largely focussed on the regulatory control of chemicals as individual substances although the majority of substances released to the environment enter in complex mixtures either as point source discharges or diffuse inputs. Whole sample measures of biological effect support the traditional substance by substance approach and provide a diagnostic capability to direct investigation into the likely chemicals or groups of chemicals of concern. Reported improvements in surface water quality in England and Wales are considered in the context of current impacts associated with hazardous substances.

Animals↗
PubMed2002

Toxicity of brake oil.

Brake oil is an automobile transmission fluid composed of a mixture of toxic glycols and glycol ethers. Three cases of poisoning with toxic glycol based brake fluid are reported who presented with mild metabolic acidosis and acute renal failure. As all the cases had presented late, treatment with ethanol was not started. All of them were treated successfully with haemodialysis.

Acidosis↗
PubMed1988

Enhancement of Butanol Formation by Clostridium acetobutylicum in the Presence of Decanol-Oleyl Alcohol Mixed Extractants.

Extractive fermentation has been proposed to enhance the productivity of fermentations that are end product inhibited. Unfortunately, good extractants for butanol, such as decanol, are toxic to Clostridium acetobutylicum. The use of mixed extractants, namely, mixtures of toxic and nontoxic coextractants, was proposed to circumvent this toxicity. Decanol appeared to inhibit butanol formation by C. acetobutylicum when present in a mixed extractant that also contained oleyl alcohol. However, maintenance of the pH at 4.5 alleviated the inhibition of butanol production and the consumption of butyrate during solventogenesis. A mixed extractant that contained 20% decanol in oleyl alcohol enhanced butanol formation by 72% under pH-controlled conditions. The production of acetone and acetoin was also increased, even though these two products were not extractable. The enhancement of butanol formation was not limited by the toxicity of decanol. Supplementation of glucose and butyrate in the extractive fermentation yielded a 47% increase in butanol. The enhancement of butanol formation appeared to be dependent on the presence of dissolved decanol in the broth but was not observed unless an organic phase was present to extract butanol. A mechanism for the effects of decanol on product formation is proposed.

Journal Article↗
PubMed2002

International issues on human health effects of exposure to chemical mixtures.

In this article, we highlight new developments and recent studies concerning adverse human health effects related to chemical mixtures. One group of activities comprises the development of a new computer program for analyzing mixture studies and a mathematical model as a basis for combination rules that predict the toxicity of mixtures. Other new activities in the area of experimental studies are the application of gene expression technologies in mixture research, and pattern recognition as a tool in safety evaluation of complex mixtures. A "bottom-up" approach for chemosensory detection of mixtures has recently been presented. Other topics include a method for the safety evaluation of natural flavoring complexes, and an evaluation of the possible health effects of the simultaneous intake of food additives. Examples of issues related to mixtures of airborne chemicals are potential interaction of fine particles and gaseous pollutants in ambient air, nasal cancer associated with inhaled chemical mixtures, and the recommendation of a limit value for volatile organic compounds. Topics of a more strategic nature include studies concerning the public health effects of large airports, and the development of criteria for a harmonized classification of chemical mixtures. This overview illustrates that strategies to tackle the safety evaluation of combined exposures and complex mixtures as well as models facilitating the interpretation of findings in the context of risk assessment of mixtures have become increasingly important. It is true that exposure of humans to chemical mixtures is the rule rather than the exception, and therefore health risk assessments should focus on mixtures and not on single chemicals. It is also true, however, that humans have learned to cope with exposure to huge numbers of chemicals simultaneously (food, water, air, soil, and consumer products). Therefore, in view of limited resources for toxicological research, the focus in toxicology should be on priority mixtures--priority being determined by (estimated) health risk (= toxicity and exposure).

Air Pollutants↗
PubMed1983

Detection of industrial pollutants and toxic chemical wastes in sewage treatment plant influents by use of a biological monitor.

Heterogeneous mixtures of toxic chemical wastes affecting the normal operations of a sewage treatment facility employing anaerobic digestion were detected by dark-field observation of uncoordinate flagellar orientation patterns displayed by cells of Spirillum volutans. These results were compared with plant parameters determined by gas production, volatile fatty acids, and alkalinity measurements.

Journal Article↗