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PubMed2002

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows.

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 microg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4-10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3,500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.

Alkanes↗

PubMed1997

Inhalation toxicokinetics of 1,2,4-trimethylbenzene in volunteers: comparison between exposure to white spirit and 1,2,4-trimethylbenzene alone.

The objective of this study was to compare the toxicokinetics of inhaled 1,2,4-trimethylbenzene (1,2,4-TMB) in man after exposure to white spirit with that observed after exposure to 1,2,4-TMB alone. TMBs occur mainly in petroleum products and the TMBs or their metabolites have been suggested as suitable biomarkers of exposure to white spirit and other distillation products. The toxicokinetics were studied in 9 male, healthy volunteers exposed to solvent vapours in an exposure chamber for 2 h during a work load of 50 W. The subjects were exposed to 11 mg/m3 of 1,2,4-TMB on two occasions; during exposure to 1,2,4-TMB vapour alone and during exposure to 300 mg/m3 of white spirit. The 1,2,4-TMB isomer was analyzed in blood and exhaled air by gas chromatography. In addition, a major urinary metabolite of 1,2,4-TMB, 3,4-dimethylhippuric acid (3,4-DMHA), was analyzed by high performance liquid chromatography. Further the occurrence of acute effects was studied by means of a questionnaire. Irritation and central nervous system symptoms were recorded by ratings on a 100-mm visual analogue scale. Blood levels of 1,2,4-TMB and excretion rates of 3,4-DMHA in urine were markedly elevated both during and after exposure to white spirit as compared to exposure to TMB alone. Thus, it appears that components in white spirit inhibit the metabolic elimination of 1,2,4-TMB. This should be considered in biological exposure monitoring as well as in risk assessment. No irritation or central nervous system effects were reported at these conditions.

Administration, Inhalation↗

PubMed2000

The history of mercury emissions from fuel combustion in Maritime Canada.

In this study, we present an inventory of historical emissions of mercury resulting from combustion of wood, coal and refined petroleum products in Maritime Canada. The pattern of emissions illustrates the strong influences of population growth, industrial development and prevailing fuel preferences in the region. According to our calculations, anthropogenic mercury releases from fuel combustion in Maritime Canada have cumulatively totaled more than 50 tonnes since 1800. We have compiled both high and low estimates of annual mercury releases in this region. Mercury emissions from fuel combustion in Maritime Canada reached a maximum level in the 1940s. At this time, emissions were between 778 (low) and 1494 (high) kg per year, coinciding with the period of most intensive coal use in Maritime Canada. In 1995, emissions were approximately 54% of the level reached in 1940, at 427 (low)-800 (high) kg per year. In presenting this emissions inventory, we hope to refine past estimates with current information on the mercury content of different fuel types, and create a comprehensive database on how mercury emissions from various sources have changed over time.

Journal Article↗

PubMedDate not supplied

Comparative analysis of traumatic deaths in Nigeria.

INTRODUCTION: The number of deaths due to trauma from road traffic accidents (RTAs), and from the use of firearms either for homicide or armed robbery, ethnic conflicts, and other events, such as flooding, explosions from petroleum products, and religious violence, is on the rise in Nigeria. This preliminary study is a comparative analysis of the frequency of deaths caused by RTAs and the deaths caused by the use of firearms during armed robbery. The study sought to identify the number of traumatic deaths caused by RTAs or armed robbery as well as the number of victims who sustained injuries in the process of RTA or armed robberies. METHODS: An indigenous, non-governmental organization (NGO) network was used to abstract data for the frequency of RTAs associated with death or injuries and for deaths caused by armed robberies and was supplemented with data obtained from the Nigerian police. RESULTS: For RTAs, the victims included drivers, passengers, and pedestrians. In 3,032 cases of RTAs, the total number of deaths was 1,239 (29.1%): one Nigerian dies for every three to four crashes. The total number of deaths due to RTAs was significantly higher than was the number of deaths due to the use of firearms in commission of robbery. Police reports relative to the use of firearms during armed robberies indicate that of a total of the 652 victims who were killed, 348 (68.1%) were the armed robbers, 134 (26.2%) were bystanders, and 29 (5.7%) were policemen. CONCLUSIONS: The enormity of the problems of traumatic deaths from RTAs and armed robberies in a developing country has been highlighted.

Accidents, Traffic↗

PubMed2001

Anodized aluminum wire as a solid-phase microextraction fiber.

The efficiency of anodized aluminum wire was investigated as a new fiber for solid-phase microextraction (SPME). Aluminum wires were anodized by direct current in a solution of sulfuric acid at room temperature and were conditioned at 300 degrees C for 30 min. These fibers were used for the extraction of some aliphatic alcohols, BTEX, and petroleum products from gaseous samples. The extracted analytes were transferred to a GC injector using an (inhouse-designed) SPME syringe that also allowed for an easy change of SPME fibers. The results obtained prove the ability of anodized aluminum wire as a new fiber for sampling of organic compounds from gaseous samples. This behavior is due most probably to the porous layer of aluminum oxide, which is formed on the metal surfaces. In this work, the optimum conditions for the preparation and conditioning of fibers and the extraction of analytes from gaseous samples were obtained. In the optimum conditions, one fiber was used in several equal analyses and the relative standard deviations were below 5% (n = 5). However, fiber-to-fiber reproducibility was 8% (n = 5). This fiber is firm, inexpensive, and durable and can be prepared simply.

Journal Article↗

PubMed2005

Using passive air samplers to assess urban-rural trends for persistent organic pollutants and polycyclic aromatic hydrocarbons. 2. Seasonal trends for PAHs, PCBs, and organochlorine pesticides.

This is the second of two papers demonstrating the feasibility of using passive air samplers to investigate persistent organic pollutants along an urban-rural transect in Toronto. The first paper investigated spatial trends for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). This second paper investigates the seasonality of air concentrations for polycyclic aromatic hydrocarbons (PAHs), PCBs, and OCPs along this transect. Air samplers, consisting of polyurethane foam (PUF) disks housed in stainless steel domed chambers, were deployed for three 4-month integration periods from June 2000 to July 2001. The seasonal variations of derived air concentrations for PAHs, PCBs, and OCPs reflected the different source characteristics for these compounds. PAHs showed a strong urban-rural gradient with maximum concentrations at urban sites during the summer period (July-October). These high summer values in Toronto were attributed to increases in evaporative emissions from petroleum products such as asphalt. PCBs also exhibited a strong urban-rural gradient with maximum air concentrations (approximately 2-3 times higher) during the spring period (April-June). This was attributed to increased surface-air exchange of PCBs that had accumulated in the surface layer over the winter. alpha-HCH was fairly uniformly distributed, spatially and temporally, as expected. This pattern and the derived air concentration of approximately 35 to approximately 100 pg m(-3) agreed well with high volume air data from this region, adding confidence to the operation of the passive samplers and showing that site-to-site differences in sampling rates was not an issue. For other OCPs, highest concentrations were observed during the spring period. This was associated with either (i) their local and/or regional application (gamma-HCH, endosulfan) and (ii) their revolatilization (chlordanes, DDT isomers, dieldrin, and toxaphene). Principal component analysis resulted in clusters for the different target chemicals according to their chemical class/source type. The results of this study demonstrate how such a simple sampling technique can provide both spatial and seasonal information. These data, integrated over seasons, can be used to evaluate contaminant trends and the potential role of large urban centers as sources of some semivolatile compounds to the regional environment, including the Great Lakes ecosystem.

Air↗

PubMed2001

Observation of shear-induced nematic-isotropic transition in side-chain liquid crystal polymers.

Flow-induced phase transitions are a fundamental (but poorly understood) property of non-equilibrium systems, and are also of practical importance for tuning the processing conditions for plastics, petroleum products, and other related materials. Recognition that polymers may exhibit liquid crystal properties has led to the discovery of the first tailored side-chain liquid crystal polymers (SCLCPs), which are formed by inserting a spacer between the main polymer chain and the lateral mesogen liquid-crystalline graftings. Subsequent research has sought to understand the nature of the coupling between the main polymer chain and the mesogens, with a view to obtaining better control of the properties of these tailored structures. We show here that the parallel or perpendicular orientation of the mesogens with respect to the main chain can be reversed by the application of an external field produced by a shear flow, demonstrating the existence of an isotropic nematic phase transition in SCLCPs. Such a transition, which was theoretically predicted for low-molecular-weight liquid crystals but never observed, is shown to be a general property of SCLCPs too. We expect that these SCLCPs will prove to be good candidate systems for the experimental study of these non-equilibrium phenomena.

Journal Article↗

PubMed2000

Mutagen exposures and chromosome 3 aberrations in acute myelocytic leukemia.

Thirteen patients with acute myelocytic leukemia (AML) and with clonal aberrations involving chromosome 3 were studied. Three patients had monosomy 3, four had trisomy 3, and six had structural aberrations of chromosome 3. In the majority of cases chromosome 3 aberrations were parts of complex karyotypes, but in two patients, the abnormalities appeared as single aberrations, one as an interstitial deletion del(3)(p13p21) and the other as monosomy 3. All breakpoints of chromosome 3 were found in the fragile site regions 3p14.2, 3q21 and 3q26-27. All patients with monosomy 3 or structural aberrations of chromosome 3 and one of the four patients with trisomy 3 had been exposed to mutagens, such as occupational exposures to organic solvents and/or petroleum products or treatments with irradiation or antineoplastic agents. The association among mutagen exposure, structural chromosome 3 aberrations and fragile sites in AML may indicate that targeting of the mutagens to these sites is of importance for the etiology of the disease. Leukemia (2000) 14, 112-118.

Adolescent↗

PubMed2000

Surveillance of occupational skin disease: EPIDERM and OPRA.

Consultant dermatologists in the U.K. have been reporting to EPIDERM, a voluntary surveillance scheme for occupational skin disease, since February 1993; reporting by occupational physicians to the scheme began in May 1994 and was superseded in January 1996 by OPRA (Occupational Physicians Reporting Activity). Currently 244 dermatologists and 790 occupational physicians report incident cases to these schemes. During the 6 years to January 1999 a total of 12, 574 new cases of occupational skin disease was estimated from reports by consultant dermatologists and 10,136 cases estimated from occupational physicians (since May 1994). The annual incidence of occupational contact dermatitis using data from both schemes was 12. 9 per 100,000 workers. The incidence of contact dermatitis per 100, 000 workers increased with age in men from 4.9 (age 16-29 years) to 6.6 (age 45-60 years); in women a higher rate (9.5) was apparent in the younger age group, with lower rates in older female workers. High rates in young workers were associated with wet work and in older workers with exposure to oils. For men, high rates of contact dermatitis were seen in reports from both schemes for chemical operatives, machine tool setters and operatives, coach and spray painters and metal workers. For women, high rates were found for hairdressers, biological scientists and laboratory workers, nurses and those working in catering. The most frequent agents for contact dermatitis were rubber chemicals and materials (14.1% of cases reported by dermatologists), soaps and cleaners (12.7%), nickel (11. 9%), wet work (11.1%), personal protective equipment (6.2%), petroleum products (6.3%), cutting oils and coolants (5.6%), and epoxy and other resins (6.1%). In the 1608 estimated cases of skin cancer all but 4% were attributed to ultraviolet radiation. Cases of contact urticaria attributed to latex peaked in 1996, with a decline in cases since that time.

Adolescent↗

PubMed2001

Washing of marine coastal sand in a batch reactor: sorption and desorption of BTEX.

This study addresses the issues related to decontamination of marine beach sand accidentally contaminated by petroleum products. Sorption and desorption of BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) onto the sand from Uran Beach, located near the city of Mumbai, India, were studied, and isotherms were determined using the bottle point method to estimate sorption coefficients. Alternatively, QSARs (i.e., quantitative structure activity relationships) were developed and used to estimate the sorption coefficients. Experiments for kinetics of volatilization as well as for kinetics of sorption and desorption in the presence of volatilization were conducted in a fabricated laboratory batch reactor. A mathematical model describing the fate of volatile hydrophobic organic pollutants like BTEX (via sorption and desorption in presence of volatilization) in a batch sediment-washing reactor was proposed. The experimental kinetic data were compared with the values predicted using the proposed models for sorption and desorption, and the optimum values of overall mass transfer coefficients for sorption (K(s)a(s)) and desorption (K(d)a(d)) were estimated. This was achieved by minimization of errors while using the sorption coefficients (Kp) obtained from either laboratory isotherm studies or the QSARs developed in the present study. Independent experimental data were also collected and used for calibration of the model for volatilization, and the values of the overall mass transfer coefficient for volatilization (K(g)a(g)) were estimated for BTEX. In these exercises of minimization of errors, comparable cumulative errors were obtained from the use of Kp values derived from experimental isotherms and QSARs.

Adsorption↗

PubMed1998

Risk Assessment in the Working Environment in Estonia.

The first step to chart hazards in the working environment in Estonia (labour force: 0.65 million) was taken by the National Board of Health Protection in the beginning of 1996. The existing chemical, physical, and biological agents in the working environment were investigated with the help of local health inspectors in all counties. An identification of hazards and workers at risk was carried out. The results of the analysis showed that 16% of Estonian industrial workers are exposed to different hazards: 20,000 persons are exposed to noise, 11,000 are working in the conditions of vibration, 10,000 are affected by unsatisfactory microclimate, 6,000 complain about long-lasting work in a compulsory posture, the overexertion of eyes is suffered by 5,500 persons, and physical overload by 3,500 workers. In the group of chemical hazards the greatest numbers of workers are exposed to organic dust (6,500) and welding aerosols (5,400), followed by petroleum products (2,700), and oil-shale dust (4,300). The measurements of working conditions showed that an average of 30.3% of the results are above the standards. Proposals for the improvement of the situation in occupational safety and health are presented.

chemicals↗

PubMed1987

Development of luminescence procedures to evaluate permeation of multi-ring polyaromatic compounds through protective materials.

This study describes two practical and simple luminescence techniques developed to evaluate the efficacy of protective clothing materials against permeation of multi-ring polyaromatic compounds contained in heavy oil and petroleum products. The procedures use a rapid and simple technique based on room temperature phosphorimetry and fluorescence detection in which a portable fiberoptics luminoscope was used.

Environmental Monitoring↗

PubMed2004

A simultaneous job- and task-based exposure evaluation of petroleum tanker drivers to benzene and total hydrocarbons.

A simultaneous job- and task-based exposure study was conducted for tanker drivers delivering petroleum products from several bulk terminals and an agency to retail outlets. Full-shift (job-based) samples and job component tasks samples were collected simultaneously. The tasks sampled included loading, unloading, and travel. Three hundred sixty-six personal charcoal tube samples were collected. Full-shift visual observations of work practices and real-time monitoring using a data logging hydrocarbon analyzer were also conducted. Multiple measurements per worker were made, which permitted an assessment of sampling variability within and between workers. The highest exposures for drivers occurred during unloading at the agency. The mean benzene exposure for agency drivers was 0.88 ppm for full-shift time-weighted average, 2.86 ppm for unloading, and 0.54 ppm for loading. For bulk terminal drivers, the mean benzene level without vapor control was 0.12 ppm for time weighted average, 0.24 ppm for unloading, and 0.33 ppm for loading. The time-weighted average exposure of the agency and bulk terminal drivers based on the data collected and the lognormal model can be expected to exceed threshold limit value-time weighted average of 0.5 ppm for benzene about 70 and 2% of the time, respectively. Agency drivers' unloading and loading tasks accounted for approximately 30% and 7% of the total time, and 95% and 4% of total exposure, respectively. For the bulk terminal drivers, mean unloading and loading tasks constituted 24% and 12% of the total time, and 68% and 19% of the total exposure, respectively. Travel activity accounted for an average of 63% of the total time for agency and 64% for bulk terminal drivers, but only contributed < 1 and 13% of the total exposure, respectively. The actual job-based time-weighted average concentration and the calculated time-weighted average derived from the time-weighted summation of the components tasks are in very good agreement. Within-worker variability was generally higher than between-worker variability. Exposure control strategies are required primarily for unloading at the agencies. Vapor control technology at the terminal effectively reduces exposure (by almost 50%) and fugitive emissions.

Automobile Driving↗

PubMed2000

Quantitation of a metal deactivator additive by derivatization and gas chromatography--mass spectrometry

The quantitative analysis of phenolic and amine-containing petroleum additives can be challenging. One such compound-N,N'-disalicylidene-1,2-propanediamine, a common metal deactivator additive (MDA)--is thought to inhibit fuel oxidation catalyzed by metals both in the fuel and on surfaces. The ability to measure the concentration of MDA in storage stability tests, thermal-stressing studies, and field samples is important. Quantitating low concentrations of MDA can be difficult because of surface adsorptivity due to the phenol and amine functional groups. This paper describes the shortcomings of direct-injection gas chromatography-mass spectrometry to quantitate MDA as well as a solution to the analytical problem using the common silylation agent BSA to derivatize the MDA. Results demonstrate that the silylation technique is suitable for the determination of MDA concentrations in aviation fuel samples and suggests that the MDA may be readily determined in other petroleum products with a lower detection limit for MDA of 0.5 mg/L. Measurements conducted in heated batch reactors indicate that MDA concentration is reduced as hydrocarbon fuels are stressed. In addition, only free or available MDA is measured by this technique, not MDA that is complexed with metals.

Journal Article↗

PubMed2000

Occupational contact dermatitis in the UK: a surveillance report from EPIDERM and OPRA.

Since February 1993 the EPIDERM surveillance scheme has collected data on occupational skin disease from consultant dermatologists in the UK. Reporting by occupational physicians to the scheme began in May 1994 and was superseded in January 1996 by the Occupational Physicians Reporting Activity (OPRA). The schemes currently receive reports on incident cases from 244 dermatologists and 790 occupational physicians. An estimated total of 9937 cases of contact dermatitis reported by dermatologists was calculated from surveillance data; 8129 contact dermatitis cases were estimated from reports by occupational physicians. The annual incidence of occupational contact dermatitis from dermatologist reports was 6.4 cases per 100,000 workers and 6.5 per 100,000 from reports by occupational physicians, an overall rate of 12.9 cases per 100,000 workers. Manufacturing industries account for the greatest number of cases seen by both sets of reporting physicians, with health care employment second. Reports from dermatologists also indicate high rates of dermatitis in the personal service industries (mainly hairdressers and barbers) and in agriculture. With the exception of an increase in cases seen in nurses in both schemes, the numbers and proportions of cases of contact dermatitis within occupations have remained fairly constant over the 6-year reporting period. Agents accounting for the highest number of allergic contact dermatitis cases were rubber (23.4% of allergic cases reported by dermatologists), nickel (18.2), epoxies and other resins (15.6), aromatic amines (8.6), chromium and chromates (8.1), fragrances and cosmetics (8.0), and preservatives (7.3). Soaps (22.0% of cases), wet work (19.8), petroleum products (8.7), solvents (8.0), and cutting oils and coolants (7.8) were the most frequently cited agents in cases of irritant dermatitis. The national scope of the data, together with the parallel structure by which both dermatologists and occupational physicians report incident cases, is useful in determining the extent of skin hazards in UK industry and may help in better targeting efforts to reduce the burden of skin disease at work.

Dermatitis, Occupational↗

PubMed1985

Childhood leukemia and parental occupation. A register-based case-control study.

To explore possible etiologic factors of childhood leukemia, a case-control study was performed in the Netherlands. Cases were selected from a complete nationwide register of cases of childhood leukemia which were diagnosed between 1973 and 1980. Controls were matched with cases for year of birth, sex, and place of residence at the time of diagnosis. Information about possible exposures was collected by a postal questionnaire addressed to the parents. This report concerns the results of the analysis of parental occupations and occupational exposures for 519 children with acute lymphocytic leukemia and 507 controls. During pregnancy, more mothers of patients were working in "hydrocarbon-related" occupations; relative risk (RR) = 2.5 (95% confidence interval (CI) = 0.7-9.4). Likewise, greater occupational exposure to chemicals (paint, petroleum products, and unspecified chemicals) during pregnancy was found for mothers of patients (RR = 2.4, 95% CI = 1.2-4.6). The kind of work being performed by the mothers one year before diagnosis did not differ between cases and controls. For the fathers, no relationship was found between a hydro-carbon-related occupation or occupational exposure to chemicals and leukemia in the offspring. Adjustment for birth order, social class, and degree of urbanization did not materially change the relative risks.

Adolescent↗

PubMed1989

Occupational risk of colon cancer. An analysis by anatomic subsite.

A case-control study was conducted to investigate occupational risks for colon cancer. The Missouri Cancer Registry was used to identify a total of 1,993 white male cases and 9,965 age-matched cancer controls diagnosed between 1984 and 1987. Effect estimates were calculated for specific occupations and industries and for three levels of occupational physical activity. Odds ratios (ORs) and 95% confidence intervals (Cls) were also calculated according to anatomic subsite of colon cancer. Elevated risks were identified for workers in several occupations and industries including printing machine operators (OR = 1.9, 95% Cl 1.0-3.3), workers in food manufacturing (OR = 1.6, 95% Cl 1.2-2.2), communications workers (OR = 1.8, 95% Cl 1.0-3.3), and workers employed in the petroleum product trade (OR = 2.7, 95% Cl 1.0-7.2). Previous findings of excess risk among selected occupations of higher socioeconomic status were confirmed. Analyses by anatomic subsite showed that excess risk for an occupational group was usually confined to a single subsite, which suggests some specificity of effect. For example, elevated risk among males employed in manufacturing-related industries was shown primarily for cancer of the cecum. The findings by level of occupational physical activity corroborated recent reports of increased colon cancer risk associated with employment in sedentary occupations. Excess risk (OR = 1.4, 95% Cl 1.0-1.9) was shown among males employed in sedentary jobs and an inverse linear trend in risk was shown according to level of occupational physical activity. Risk associated with sedentary occupations was highest for cancer of the cecum (OR = 2.1, 95% Cl 1.1-4.0). Despite the limitations of the cancer registry-collected data, some associations were observed that deserve further study.

Adult↗

PubMed1996

Exposure in a household using gasoline-contaminated water.

Contamination of drinking water with petroleum products is an increasingly common problem. Physicians are often asked to advise patients about such exposures. This study assessed household exposure from gasoline-contaminated drinking water in a New England household. A sampling strategy was designed to estimate inhalation and ingestion exposure to benzene and three other aromatic hydrocarbons typically found in gasoline-contaminated water. The estimated inhaled doses of all agents were similar to the estimated ingested dose. Over half the inhaled dose of all four agents was associated with shower activities as was over half the estimated total dose by all routes of exposure. Under these conditions, discontinuing ingestion of water contaminated with these agents may decrease the dose of benzene by less than one third, whereas discontinuing both ingestion and showering may decrease the dose of benzene by over three quarters. This limited study suggests that routes of exposure other than ingestion are important and should receive attention in the regulatory and risk-assessment process.

Air Pollution, Indoor↗