Biomedical subjects

D L Ashley

Publications and source records attributed to D L Ashley.

At least 19 recordsLinked to original sources

PubMed1999

Supercritical fluid extraction and gas chromatography/mass spectrometry for the analysis of tobacco-specific nitrosamines in cigarettes.

A method for measuring four tobacco-specific nitrosamines (TSNAs), an important group of compounds in tobacco products, was developed. These compounds were extracted using supercritical fluid extraction (SFE) and purified by a sodium hydroxide wash of the ethyl acetate eluting solvent and solid-phase extraction. Quantitation was performed using gas chromatography/mass spectrometry (GC/MS). Spiking experiments were carried out to determine the recovery, precision, and limits of detection of this method. The detection limits were 0.04 microgram per sample for N'-nitrosonornicotine and N'-nitrosoanatabine and 0.02 microgram for 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone and N'-nitrosoanabasine. This method was used to measure TSNAs in various brands of cigarette tobacco with excellent reproducibility. The variation of TSNA levels among the cigarettes of different packs and types was significantly smaller than that among different brands. Comparable TSNA levels were obtained with SFE and liquid extraction methods. Signal-to-noise levels were similar for GC/MS and GC/thermal energy analysis when low-level tobacco samples were analyzed.

Gas Chromatography-Mass Spectrometry↗

PubMed1998

Sample purification for the analysis of caffeine in tobacco by gas chromatography-mass spectrometry.

A commonly used additive to tobacco products is cocoa. A sensitive an selective method was developed to measure caffeine, a marker for cocoa, in tobacco by using gas chromatography-mass spectrometry (GC-MS). Tobacco components usually produce high background signals in GC-MS analysis. Therefore, a series of extraction steps were designed to effectively purify the tobacco extracts. The analytical recovery of caffeine was 100 when [trimethyl-13C3] caffeine was used as an isotope-dilution reference. A linear calibration curve was generated with caffeine concentration ranging from 0.01 to 20 micrograms/ml. The detection limit of caffeine was 0.02 microgram/ml in the final solution. This method was applied to several commercial tobacco products, of which the corresponding caffeine levels varied from below the detection limit to 125 micrograms/g.

Caffeine↗

PubMed1997

Blood benzene concentrations in workers exposed to oxygenated fuel in Fairbanks, Alaska.

OBJECTIVE: In November 1992 residents of Fairbanks, Alaska became concerned about the potential health effects of an oxygenated fuel program during which 15% (by volume) methyl tertiary butyl ether (MTBE) was added to gasoline. To address those concerns, we earlier completed a survey of occupational exposure to MTBE. We conducted a follow-up survey of workers' exposure to benzene from gasoline in Fairbanks. DESIGN: Cross-sectional exposure survey. METHODS: We examined blood concentrations of benzene from a convenience sample of workers taken in December 1992 during the oxygenated fuel program and from another convenience sample of workers taken in February 1993 after the program was suspended. RESULTS: In December, the median blood benzene concentration of samples taken from four mechanics after their workshift (postshift) was 1.32 micrograms/l (range, 0.84-2.61 micrograms/l), and seven nonmechanics (drivers and other garage workers) had a median postshift blood benzene concentration of 0.27 microgram/l (range, 0.09-0.45 microgram/l). In February, nine mechanics had a median postshift blood benzene concentration of 1.99 micrograms/l (range, 0.92-3.23 micrograms/l), and nine nonmechanics had a median postshift blood benzene concentration of 0.26 microgram/l (range, 0.2-0.46 microgram/l). CONCLUSION: Mechanics had higher blood benzene concentrations than did nonmechanics, but further study is needed to determine the impact of the oxygenated fuel program on exposure to benzene.

Benzene↗

PubMed1997

Correlation of environmental carbaryl measurements with serum and urinary 1-naphthol measurements in a farmer applicator and his family.

In exposure or risk assessments, both environmental and biological measurements are often used. Environmental measurements are an excellent means for evaluating regulatory compliance, but the models used to estimate body burden from these measurements are complex. Unless all possible routes of exposure (i.e., inhalation, dermal absorption, ingestion) are evaluated, exposure to a toxicant can be underestimated. To circumvent this problem, measurements of the internal dose of a toxicant in blood, serum, urine, or tissues can be used singularly or in combination with environmental data for exposure assessment. In three separate laboratories, carbaryl or its primary metabolite, 1-naphthol, was measured in personal air, dermal samples, blood serum, and urine from farmer applicators and their families. The usefulness of both environmental and biological data has been demonstrated. For the farmer applicator, the environmental levels of carbaryl would have been sufficient to determine that an exposure had occurred. However, biological measurements were necessary to determine the absorbed dose of each member of the applicator's family. In addition, a correlation between serum and urinary 1-naphthol measurements has been shown; therefore, either matrix can be used to accurately evaluate occupational carbaryl exposure.

Agriculture↗

PubMed1997

Exposure to regular gasoline and ethanol oxyfuel during refueling in Alaska.

Although most people are thought to receive their highest acute exposures to gasoline while refueling, relatively little is actually known about personal, nonoccupational exposures to gasoline during refueling activities. This study was designed to measure exposures associated with the use of an oxygenated fuel under cold conditions in Fairbanks, Alaska. We compared concentrations of gasoline components in the blood and in the personal breathing zone (PBZ) of people who pumped regular unleaded gasoline (referred to as regular gasoline) with concentrations in the blood of those who pumped an oxygenated fuel that was 10% ethanol (E-10). A subset of participants in a wintertime engine performance study provided blood samples before and after pumping gasoline (30 using regular gasoline and 30 using E-10). The biological and environmental samples were analyzed for selected aromatic volatile organic compounds (VOCs) found in gasoline (benzene, ethylbenzene, toluene, m-/p-xylene, and o-xylene); the biological samples were also analyzed for three chemicals not found in gasoline (1,4-dichlorobenzene, chloroform, and styrene). People in our study had significantly higher levels of gasoline components in their blood after pumping gasoline than they had before pumping gasoline. The changes in VOC levels in blood were similar whether the individuals pumped regular gasoline or the E-10 blend. The analysis of PBZ samples indicated that there were also measurable levels of gasoline components in the air during refueling. The VOC levels in PBZ air were similar for the two groups. In this study, we demonstrate that people are briefly exposed to low (ppm and sub-ppm) levels of known carcinogens and other potentially toxic compounds while pumping gasoline, regardless of the type of gasoline used.

Adult↗

PubMed1996

Using the blood concentration of 2,5-dimethylfuran as a marker for smoking.

Correct analysis of whole blood volatile organic compounds (VOCs) in evaluating possible exposure situations requires differentiation of smokers from nonsmokers. Whole blood concentrations of 2,5-dimethylfuran are determined using an internal standard method, and the concentrations of this compound are evaluated as a marker for smoking in exposure-study subjects. Results indicate that the concentration of 2,5-dimethylfuran can be adequately determined in whole blood by a method already in use for determining VOCs in blood. The whole blood concentration of 2,5-dimethylfuran was an excellent predictor of smoking when compared with positive responses about smoking on questionnaires. Using a detection limit of 0.024 ppb, 2,5-dimethylfuran concentrations in blood correctly identified the smoking status of 96.4% of the subjects in this study. The blood 2,5-dimethylfuran concentration was linearly related to the number of cigarettes smoked per day. This method is advantageous since blood 2,5-dimethylfuran concentrations can be determined using the same method used to determine concentrations of other VOCs, thus obviating the need for additional analytical procedures.

Biomarkers↗

PubMed1996

Measurement of volatile organic compounds in human blood.

Volatile organic compounds (VOCs) are an important public health problem throughout the developed world. Many important questions remain to be addressed in assessing exposure to these compounds. Because they are ubiquitous and highly volatile, special techniques must be applied in the analytical determination of VOCs. The analytical methodology chosen to measure toxicants in biological materials must be well validated and carefully carried out; poor quality assurance can lead to invalid results that can have a direct bearing on treating exposed persons. The pharmacokinetics of VOCs show that most of the internal dose of these compounds is quickly eliminated, but there is a fraction that is only slowly removed, and these compounds may bioaccumulate. VOCs are found in the general population at the high parts-per-trillion range, but some people with much higher levels have apparently been exposed to VOC sources away from the workplace. Smoking is the most significant confounder to internal dose levels of VOCs and must be considered when evaluating suspected cases of exposure.

Benzene↗

PubMed1995

Removing the smoking confounder from blood volatile organic compounds measurements.

Because smoking is a major contributor to the internal dose levels of many volatile organic compounds (VOCs), it is difficult to assess other VOC exposures among smokers. Purge and trap/gas chromatography/isotope-dilution mass spectrometry was used to determine the internal dose of VOCs of smokers and nonsmokers. Median whole blood concentrations of benzene, styrene, and toluene were shown to be approximately two times higher among smokers than among nonsmokers. In addition, smoking elevated the blood levels of ethylbenzene, m-/p-xylene, and o-xylene when the log-transformed data were compared. Smoking also led to greatly increased levels of 2,5-dimethylfuran. These results indicate that blood levels of many VOCs are highly correlated with blood levels of 2,5-dimethylfuran and that this effect is primarily a result of smoking. The smoking confounder to blood levels of VOCs can be removed by including the concentration of blood 2,5-dimethylfuran concentration when evaluating results from a health and exposure evaluation. Determining the blood 2,5-dimethylfuran concentration appears to be an effective means of correcting the confounding influence of smoking and supplies a way of determining lower-level exposures that previously could not have been distinguished from the effects of smoking.

Air Pollutants↗

PubMed1995

Case studies of the use of biomarkers to assess exposures.

Because many environmental toxicants are ubiquitous, humans are continuously exposed to them. At other times, certain populations may be more highly exposed to these toxicants from point sources. The evaluation of the degree of the exposure to either a population or an individual is frequently based on indirect surrogates of exposure, such as questionnaire data on time-activities and/or concentrations measured in environmental media. We prefer to assess the degree of the exposure to a given toxicant by measuring the concentration of the toxicant, its metabolite(s), or reaction product(s) in human specimens. Then by applying pharmacokinetic information for that toxicant, we can best reconstruct the exposure scenario. These data are then compared to reference range levels of these toxicants in the preferred biologic specimen. The development and uses of the reference range data are exemplified by case studies including potential exposure to dioxin and solvents.

Animals↗

PubMed1995

Treatment of vacutainers for use in the analysis of volatile organic compounds in human blood at the low parts-per-trillion level.

Vacutainers that are routinely used for blood collection contain significant amounts of volatile organic compounds (VOCs). These VOCs interfere with the low parts-per-trillion analysis of VOCs in whole blood either by causing false positives or by masking the presence of VOCs because of high background levels. Benzene, bromoform, ethylbenzene, m/p-xylene, o-xylene, styrene, and various hydrocarbons are the most significant sources of VOC contamination present in the vacutainers. A method of removing VOCs from 10-mL gray-top vacutainers is presented. This method uses a combination of heat and vacuum to reduce the VOCs to levels compatible with low parts-per-trillion analysis of VOCs in whole blood.

Blood Specimen Collection↗

PubMed1995

Using biological monitoring to assess human exposure to priority toxicants.

Scientifically valid exposure assessment is crucial to risk assessment, risk management, and prevention of environmental disease. Scientists have used three tools to assess exposure: exposure history/questionnaire, environmental monitoring (including personal monitoring), and biological monitoring. Combinations of these tools usually provide the exposure information needed to meet objectives of human studies evaluating the exposure-health effect relationship. Biological monitoring is a capable exposure assessment tool that has provided important information used in public health decisions. We briefly describe how risk assessment and risk management decisions for lead, dioxin, and volatile organic compounds have substantially benefited from exposure information obtained from biological monitoring.

Dioxins↗

PubMed1995

The priority toxicant reference range study: interim report.

The relationship between human exposure to environmental toxicants and health effects is of utmost interest to public health scientists. To define this relationship, these scientists need accurate and precise methods for assessing human exposure and effects. One of the most accurate and precise means of assessing exposure is to measure the level of the toxicant or its primary metabolite in a biologic specimen; this has been defined as measuring the internal dose. This measurement must be quantitative to best study the dose-response relationship. Pertinent questions asked during an exposure assessment include "How do the levels of a given toxicant in a particular population compare with the levels of that toxicant in other populations?" and "What is the prevalence of exposure to that toxicant in other populations?" To answer these questions for two chemical classes of environmental toxicants, we developed state-of-the-art analytic methods and then applied them to measure the levels of 44 environmental toxicants in biologic specimens from 1000 United States residents who participated in the Third National Health and Nutrition Examination Survey (NHANES III). These 1000 people are a cross-sectional subset of the NHANES III population and were selected from urban and rural communities in four regions of the United States; all were between 20 and 59 years of age. This subset is not a probability-based sample.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗

PubMed1994

Volatile organic compounds in the blood of persons in Kuwait during the oil fires.

Between March and November of 1991, approximately 9000 workers from 43 different countries battled the burning oil wells in Kuwait. To document the exposure of persons in Kuwait during the oil well fires to volatile organic compounds (VOCs), we obtained samples of blood from 14 U.S. personnel in Kuwait City in May of 1991 (group I) and 40 American firefighters working in the oil fields in October of 1991 (group II). Concentrations of VOCs in group I and group II were compared with those of a random sample of 114 persons in the United States (reference group). The median concentrations of VOCs in group I were equal to or lower than those in the reference group. We found significant differences between the median concentrations of several VOCs in group II and the reference group. Median levels of ethylbenzene were about 10 times higher among group II than among the reference group (0.53 microgram/l vs 0.052 microgram/l). Median levels of benzene, m-/p-xylene, o-xylene, styrene, and toluene among group II were more than double those of the reference group. Although firefighters had higher median concentrations of VOCs than the reference group, those American personnel in Kuwait not involved in fighting the oil fires had concentrations of VOCs comparable to those in the reference group. Blood VOC measurements indicate a significant increase in exposure to VOCs in firefighters, but do not demonstrate this in personnel in Kuwait City.

Adult↗

PubMed1994

Production of blank water for the analysis of volatile organic compounds in human blood at the low parts-per-trillion level.

Blank water with low levels of volatile organic compounds (VOCs) is of critical importance in many analytical procedures. Because of the increased use of more sophisticated instrumentation, the detection limits for these compounds have dropped dramatically. Consequently, techniques in use in the analytical laboratory to generate blank water may now prove inadequate. The need for blank water with low levels of VOCs was recently underscored by the development of an analytical procedure to analyze 32 VOCs in whole blood; this procedure has detection limits in the tens of parts-per-trillion level for most VOCs. Common sources of blank water in the laboratory such as deionized, cartridge-filtered, and HPLC-grade bottled water are analyzed. These sources contained high concentrations of some VOCs that would interfere with low parts-per-trillion analyses. Well water and bottled water used for human consumption are analyzed, but both prove inadequate for the analysis of VOCs at parts-per-trillion levels. A combination of distillation and purging with helium produced blank water with VOC levels of less than 10 parts-per-trillion for most of the 16 VOCs studied.

Blood Chemical Analysis↗

PubMed1994

Technical and scientific developments in exposure marker methodology.

Recent advances in techniques to measure markers of exposure to environmental toxicants in humans are changing the ways in which environmental scientists, epidemiologists, and policymakers characterize and interpret such exposure. In this article we review some major technical and scientific developments in exposure marker methodology for estimating internal dose, with special reference to studies conducted at the US Centers for Disease Control and Prevention. We consider important characteristics of laboratory methods, advances in laboratory technology, analytical standards, and quality assurance of laboratory measurements; comparisons with indirect methods for estimating exposures, such as exposure indices and questionnaires; human pharmacokinetic data; sampling problems; surveillance of human exposures to toxicants; and interpretation of measurements. With a view to increasing the reliability of exposure assessment, we make recommendations for obtaining more data on human exposure to toxicants.

Biomarkers↗

PubMed1994

Blood concentrations of volatile organic compounds in a nonoccupationally exposed US population and in groups with suspected exposure.

Exposure to certain volatile organic compounds (VOCs) commonly occurs in industrialized countries. We developed a method for measuring 32 VOCs in 10 mL of whole blood at low concentration. We used this method to determine the internal dose of these compounds in 600 or more people in the US who participated in the Third National Health and Nutrition Examination Survey. From our study results, we established a reference range for these VOCs in the general population of the US. We found detectable concentrations of 1,1,1-trichloroethane, 1,4-dichlorobenzene, 2-butanone, acetone, benzene, chloroform, ethylbenzene, m,p-xylene, styrene, tetrachloroethane, and toluene in most of the blood samples of nonoccupationally exposed persons. The accuracy of VOC evaluations depends on the ability of investigators to make sensitive and reproducible measurements of low concentrations of VOCs and to eliminate all sources of interference and contamination.

Environmental Exposure↗

PubMed1992

Performance characteristics of a composite multivariate quality control system.

We present the results of an evaluation of the performance characteristics of a composite multivariate quality control (CMQC) system that incorporates quality control rules for univariate, multivariate, and correlation conditions. The CMQC system evaluated is designed to help analysts detect unacceptable trends and systematic error in one or more variables, unacceptable random error in one or more variables, and unacceptable changes in the correlation structure of any pair of variables. It is also designed to be tolerant of missing data, to allow analysts to reject as few as one or as many as all variables in a run, and to provide analysts with control statistics and graphics that logically relate to sources of analytical error. We show that the various components of the CMQC system have adequate statistical power to detect systematic errors, random errors, and correlation changes under the conditions likely to be encountered with multivariate analytical measurement systems: (1) a single variable with increased systematic or random error; (2) all variables or a subgroup of variables affected by a common problem that increases systematic or random error; and (3) missing data for one or more variables in a run. We also show that the power of the multivariate component of the CMQC system to detect systematic and random errors is higher than the power of an alternative multivariate test criterion.

Chemistry Techniques, Analytical↗

PubMed1992

Determining volatile organic compounds in human blood from a large sample population by using purge and trap gas chromatography/mass spectrometry.

Volatile organic compounds (VOCs) are a major public health concern, because of their ubiquitous nature and the possible health effects associated with exposure to them. An analytical method has been developed that enabled the determination of parts per trillion levels of 32 VOCs in 10 mL of blood. Special efforts toward reducing blank levels and improving measurement sensitivity have resulted in an analytical method that shows excellent reproducibility and recovery even at these ultratrace levels. Results on normal human blood indicate that quantifiable levels of eleven VOCs can be found in virtually all whole blood samples. In a fraction of the samples, six other VOCs can also be determined at levels above detection limits. This method shows promise as a technique for estimating the normal baseline level of VOCs in human blood and may have future applications in cases of exposure.

Blood Chemical Analysis↗