Assessing the effects of sunlight and water on asphalt binder and pavement leachability related to the environment.

Extensive global research conducted over 30 years explores asphalt leachability and stormwater runoff. Asphalt's widespread usage in construction materials underscores the importance of understanding its environmental consequences. This study aims to assess the influence of sunlight exposure on water quality, particularly regarding the release of hazardous organic compounds such as polycyclic aromatic compounds. We investigated the effect of concurrent versus sequential exposure to water and sunlight, and dark versus light trials utilizing thin films of asphalt binder as well as old and freshly prepared pavement cores for analysis. Initial laboratory experiments reveal significant water-soluble species when thin asphalt films are exposed to solar simulation while underwater. However, simulating environmental conditions found in roadways by exposing the asphalt binder to solar simulation followed by water immersion leads to a substantial decrease in compound formation. Leachate water from 17-year-old asphalt and 15-year-old concrete pavements exhibits complex compound compositions associated with atmospheric and/or vehicular deposition, posing challenges in deconvoluting their origins. Light and dark trials conducted on freshly prepared asphalt pavement under environmental conditions of sunlight and rain demonstrate minimal runoff variation, with semi-volatile organic compound levels resembling the background. Future investigations will focus on applying insights gained from this study to analyze larger sample sets, with an emphasis on inherent hazardous compound variations.

Assessing cancer hazards of bitumen emissions - a case study for complex petroleum substances.

When assessing cancer hazard and risk associated with a complex petroleum substance, like bitumen emissions, there are often conflicting results related to human, animal and mechanistic studies. Validation of the complex composition to assure that it matches real-world exposures and control of confounders are pivotal factors in study design to allow the necessary read-across during assessments. Several key studies on bitumen emissions in two-year dermal cancer assays reported variable outcomes ranging from high cancer incidence to no cancer incidence. Here, we synthesize findings from published studies to explain the differences and discuss critical factors in cancer hazard evaluation for complex petroleum substances. Using these critical factors, we reviewed relevant human genetic toxicity, mammalian toxicity and mechanistic studies with bitumen to understand the divergence in results. We assess the most reliable and scientifically supported information on the potential carcinogenic hazards of bitumen emissions and comment on quality and completeness of data. Human hazard data are typically considered highest priority because they eliminate the need for interspecies extrapolation and reduce the range of high -to low-dose extrapolation during the risk assessment process. Finally, two well-conducted comprehensive animal studies are discussed that have well-defined test material, exposure concentration and composition representative of worker exposure, evidence of systemic uptake, no confounding exposures and provide consistency across all elements within both studies. Studies that allow effective read-across from human, animal and mechanistic components, control for confounders and are well-validated analytically against workplace exposures, provide the strongest evidence base for evaluating cancer hazard.

Airborne Exposures to Polycyclic Aromatic Compounds Among Workers in Asphalt Roofing Manufacturing Facilities.

We studied exposure of 151 workers to polycyclic aromatic compounds and asphalt emissions during the manufacturing of asphalt roofing products-including 64 workers from 10 asphalt plants producing oxidized, straight-run, cutback, and wax- or polymer-modified asphalts, and 87 workers from 11 roofing plants producing asphalt shingles and granulated roll roofing. The facilities were located throughout the United States and used asphalt from many refiners and crude oils. This article helps fill a gap in exposure data for asphalt roofing manufacturing workers by using a fluorescence technique that targets biologically active 4-6 ring polycyclic aromatic compounds and is strongly correlated with carcinogenic activity in animal studies. Worker exposures to polycyclic aromatic compounds were compared between manufacturing plants, at different temperatures and using different raw materials, and to important external benchmarks. High levels of fine limestone particulate in the plant air during roofing manufacturing increased polycyclic aromatic compound exposure, resulting in the hypothesis that the particulate brought adsorbed polycyclic aromatic compounds to the worker breathing zone. Elevated asphalt temperatures increased exposures during the pouring of asphalt. Co-exposures in these workplaces which act as confounders for both the measurement of total organic matter and fluorescence were detected and their influence discussed. Exposures to polycyclic aromatic compounds in asphalt roofing manufacturing facilities were lower than or similar to those reported in hot-mix paving application studies, and much below those reported in studies of hot application of built-up roofing asphalt. These relatively low exposures in manufacturing are primarily attributed to air emission controls in the facilities, and the relatively moderate temperatures, compared to built-up roofing, used in these facilities for oxidized asphalt. The exposure to polycyclic aromatic compounds was a very small part of the overall worker exposure to asphalt fume, on average less than 0.07% of the benzene-soluble fraction. Measurements of benzene-soluble fraction were uniformly below the American Conference of Governmental Industrial Hygienists' Threshold Limit Value for asphalt fume.

Effect of Temperature and Process on Quantity and Composition of Laboratory-generated Bitumen Emissions.

In this study we investigated the impact of temperature on emissions as related to various bitumen applications and processes used in commercial products. Bitumen emissions are very complex and can be influenced in quantity and composition by differences in crude source, refining processes, application temperature, and work practices. This study provided a controlled laboratory environment to study five bitumen test materials from three European refineries; three paving grade, one used for primarily roofing and some paving applications, and one oxidized industrial specialty bitumen. Emissions were generated at temperatures between 140°C and 230°C based on typical application temperatures of each product. Emissions were characterized by aerodynamic particle size, total organic matter (TOM), simulated distillation, 40 individual PACs, and fluorescence (FL-PACs) spectroscopy. Results showed that composition of bitumen emissions is influenced by temperature under studied experimental conditions. A distinction between the oxidized bitumen with flux oil (industrial specialty bitumen) and the remaining bitumens was observed. Under typical temperatures used for paving (150°C-170°C), the TOM and PAC concentrations in the emissions were low. However, bitumen with flux oil produced significantly higher emissions at 230°C, laden with high levels of PACs. Flux oil in this bitumen mixture enhanced release of higher boiling-ranged compounds during application conditions. At 200°C and below, concentrations of 4-6 ring PACs were ≤6.51 µg/m(3) for all test materials, even when flux oil was used. Trends learned about emission temperature-process relationships from this study can be used to guide industry decisions to reduce worker exposure during processing and application of hot bitumen.

Personal breathing zone exposures among hot-mix asphalt paving workers; preliminary analysis for trends and analysis of work practices that resulted in the highest exposure concentrations.

An exposure assessment of hot-mix asphalt (HMA) paving workers was conducted to determine which of four exposure scenarios impacted worker exposure and dose. Goals of this report are to present the personal-breathing zone (PBZ) data, discuss the impact of substituting the releasing/cleaning agent, and discuss work practices that resulted in the highest exposure concentration for each analyte. One-hundred-seven PBZ samples were collected from HMA paving workers on days when diesel oil was used as a releasing/cleaning agent. An additional 36 PBZ samples were collected on days when B-100 (100% biodiesel, containing no petroleum-derived products) was used as a substitute releasing/cleaning agent. Twenty-four PBZ samples were collected from a reference group of concrete workers, who also worked in outdoor construction but had no exposure to asphalt emissions. Background and field blank samples were also collected daily. Total particulates and the benzene soluble fraction were determined gravimetrically. Total organic matter was determined using gas chromatography (GC) with flame ionization detection and provided qualitative information about other exposure sources contributing to worker exposure besides asphalt emissions. Thirty-three individual polycyclic aromatic compounds (PACs) were determined using GC with time-of-flight mass spectrometry; results were presented as either the concentration of an individual PAC or a summation of the individual PACs containing either 2- to 3-rings or 4- to 6-rings. Samples were also screened for PACs containing 4- to 6-rings using fluorescence spectroscopy. Arithmetic means, medians, and box plots of the PBZ data were used to evaluate trends in the data. Box plots illustrating the diesel oil results were more variable than the B-100. Also, the highest diesel oil results were much higher in concentration than the highest B-100 results. An analysis of the highest exposure results and field notes revealed a probable association between these exposures and the use of diesel oil, use of a diesel-powered screed, elevated HMA paving application temperatures, lubricating and working on broken-down equipment, and operation of a broom machine.

Predictors of airborne exposures to polycyclic aromatic compounds and total organic matter among hot-mix asphalt paving workers and influence of work conditions and practices.

OBJECTIVES: We evaluated personal airborne exposures to polycyclic aromatic compounds (PACs) and total organic matter (TOM) among hot-mix asphalt (HMA) paving workers. The primary objectives of this study were to identify predictors of airborne PAC exposures, identify PAC exposure sources, and characterize how work practices may affect personal airborne exposure to PACs. METHODS: Four workers were recruited from each of three asphalt paving crews (12 workers) and were monitored for three consecutive days over 4 weeks for a total of 12 sampling days per worker (144 worker-days). Three sampling weeks were conducted while maintaining standard working conditions with regard to airborne exposures. The fourth week included the substitution of biodiesel for diesel oil used to clean tools and equipment. Linear mixed-effects models were used to evaluate predictors of airborne exposures including weather parameters (air temperature, wind speed, and relative humidity), worksite conditions (HMA application temperature, work rate, asphalt grade, and biodiesel use), and personal factors (minutes sampled, minutes of downtime, and smoking status). RESULTS: Concentrations of the 33 individual PACs measured in personal air samples were generally below detection limits under all conditions with the exception of fluorene [geometric mean (GM) = 65 ng m(-3)], naphthalene (GM = 833 ng m(-3)), phenanthrene (GM = 385 ng m(-3)), and pyrene (GM = 57 ng m(-3)). The summary measures of TOM (GM = 864 µg m(-3)) and four- to six-ring PAC (GM = 0.13 µg m(-3)) were detected in the majority of air samples. Although task was not a predictor of airborne exposures, job site characteristics such as HMA application temperature were found to significantly (P ≤ 0.001) affect summary and individual PAC exposures. Based on the results of multivariate linear mixed-effects models, substituting biodiesel for diesel oil as a cleaning agent was associated with significant (P ≤ 0.01) reductions in TOM, four- to six-ring PACs, and naphthalene and pyrene concentrations that ranged from 31 to 56%. Using multivariate linear mixed-effects models under standard conditions, reducing the application temperature of HMA from 149°C (300°F) to 127°C (260°F) could be expected to reduce airborne exposures by 42-82%, varying by analyte. CONCLUSIONS: Promising strategies for reducing airborne exposures to PACs among HMA paving workers include substituting biodiesel for diesel oil as a cleaning agent and decreasing the HMA application temperature.

Predictors of dermal exposures to polycyclic aromatic compounds among hot-mix asphalt paving workers.

OBJECTIVES: The primary objective of this study was to identify the source and work practices that affect dermal exposure to polycyclic aromatic compounds (PACs) among hot-mix asphalt (HMA) paving workers. METHODS: Four workers were recruited from each of three asphalt paving crews (12 workers) and were monitored for three consecutive days over 4 weeks for a total of 12 sampling days per worker (144 worker days). Two sampling weeks were conducted under standard conditions for dermal exposures. The third week included the substitution of biodiesel for diesel oil used to clean tools and equipment and the fourth week included dermal protection through the use of gloves, hat and neck cloth, clean pants, and long-sleeved shirts. Dermal exposure to PACs was quantified using two methods: a passive organic dermal (POD) sampler specifically developed for this study and a sunflower oil hand wash technique. Linear mixed-effects models were used to evaluate predictors of PAC exposures. RESULTS: Dermal exposures measured under all conditions via POD and hand wash were low with most samples for each analyte being below the limit of the detection with the exception of phenanthrene and pyrene. The geometric mean (GM) concentrations of phenanthrene were 0.69 ng cm(-2) on the polypropylene layer of the POD sampler and 1.37 ng cm(-2) in the hand wash sample. The GM concentrations of pyrene were 0.30 ng cm(-2) on the polypropylene layer of the POD sampler and 0.29 ng cm(-2) in the hand wash sample. Both the biodiesel substitution and dermal protection scenarios were effective in reducing dermal exposures. Based on the results of multivariate linear mixed-effects models, increasing frequency of glove use was associated with significant (P < 0.0001) reductions for hand wash and POD phenanthrene and pyrene concentrations; percent reductions ranged from 40 to 90%. Similar reductions in hand wash concentrations of phenanthrene (P = 0.01) and pyrene (P = 0.003) were observed when biodiesel was substituted for diesel oil as a cleaning agent, although reductions were not significant for the POD sampler data. Although task was not a predictor of dermal exposure, job site characteristics such as HMA application temperature, asphalt grade, and asphalt application rate (tons per hour) were found to significantly affect exposure. Predictive models suggest that the combined effect of substituting biodiesel for diesel oil as a cleaning agent, frequent glove use, and reducing the HMA application temperature from 149°C (300°F) to 127°C (260°F) may reduce dermal exposures by 76-86%, varying by analyte and assessment method. CONCLUSIONS: Promising strategies for reducing dermal exposure to PACs among asphalt paving workers include requiring the use of dermal coverage (e.g. wearing gloves and/or long sleeves), substituting biodiesel for diesel oil as a cleaning agent, and decreasing the HMA application temperature.

Using urinary biomarkers of polycyclic aromatic compound exposure to guide exposure-reduction strategies among asphalt paving workers.

INTRODUCTION: Paving workers are exposed to polycyclic aromatic compounds (PACs) while working with hot-mix asphalt (HMA). Further characterization of the source and route of these exposures is necessary to guide exposure-reduction strategies. METHODS: Personal air (n=144), hand-wash (n=144), and urine (n=480) samples were collected from 12 paving workers over 3 workdays during 4 workweeks. Urine samples were collected at preshift, postshift, and bedtime and analyzed for 10 hydroxylated PACs (1-OH-pyrene; 1-, 2-, 3-, 4-OH-phenanthrene; 1-, 2-OH-naphthalene; 2-, 3-, 9-OH-fluorene) by an immunochemical quantification of PACs (I-PACs). The air and hand-wash samples were analyzed for the parent compounds corresponding to the urinary analytes. Using a crossover study design, each of the 4 weeks represented a different exposure scenario: a baseline week (normal conditions), a dermal protection week (protective clothing), a powered air-purifying respirator (PAPR) week, and a biodiesel substitution week (100% biodiesel provided to replace the diesel oil normally used by workers to clean tools and equipment). The urinary analytes were analyzed using linear mixed-effects models. RESULTS: Postshift and bedtime concentrations were significantly higher than preshift concentrations for most urinary biomarkers. Compared with baseline, urinary analytes were reduced during the dermal protection (29% for 1-OH-pyrene, 15% for I-PACs), the PAPR (24% for 1-OH-pyrene, 15% for I-PACs), and the biodiesel substitution (15% for 1-OH-pyrene) weeks. The effect of PACs in air was different by exposure scenario (biodiesel substitution>dermal protection>PAPR and baseline) and was still a significant predictor of most urinary analytes during the week of PAPR use, suggesting that PACs in air were dermally absorbed. The application temperature of HMA was positively associated with urinary measures, such that an increase from the lowest application temperature (121°C) to the highest (154°C) was associated with a 72% increase in ΣOH-fluorene and 1-OH-pyrene and an 82% increase in ΣOH-phenanthrene. Though PACs in hand-wash samples were not predictors of urinary analytes, the effects observed during the PAPR scenario and the week of increased dermal protection provide evidence of dermal absorption. CONCLUSIONS: Our results provide evidence that PACs in air are dermally absorbed. Reducing the application temperature of asphalt mix appears to be a promising strategy for reducing PAC exposure among paving workers. Additional reductions may be achieved by requiring increased dermal coverage of workers and by substituting biodiesel for diesel oil as a cleaning agent.

Asphalt fume dermal carcinogenicity potential: I. dermal carcinogenicity evaluation of asphalt (bitumen) fume condensates.

Asphalt (bitumen) fume condensates collected from the headspace above paving and Type III built up roofing asphalt (BURA) tanks were evaluated in two-year dermal carcinogenicity assays in male C3H/HeNCrl mice. A third sample was generated from the BURA using a NIOSH laboratory generation method. Similar to earlier NIOSH studies, the BURA fume condensates were applied dermally in mineral oil twice per week; the paving sample was applied 7 days/week for a total weekly dose of 50 mg/wk in both studies. A single benign papilloma was observed in a group of 80 mice exposed to paving fume condensate at the end of the two-year study and only mild skin irritation was observed. The lab generated BURA fume condensate resulted in statistically significant (P<0.0001) increases in squamous cell carcinomas (35 animals or 55% of animals at risk). The field-matched BURA condensate showed a weaker but significant (P=0.0063) increase (8 carcinomas or 13% of animals) and a longer average latency (90 weeks vs. 76 for the lab fume). Significant irritation was observed in both BURA condensates. It is concluded that the paving fume condensate was not carcinogenic under the test conditions and that the field-matched BURA fume condensate produced a weak tumor response compared to the lab generated sample.

Side-by-side comparison of field monitoring methods for hot bitumen emission exposures: the German IFA Method 6305, U.S. NIOSH Method 5042, and the Total Organic Matter Method.

Field studies were conducted at paving and roofing sites to compare the German Institute for Occupational Safety and Health of the German Social Accident Insurance (IFA) Fourier transform infrared spectroscopy method 6305 with the National Institute for Occupational Science and Health (NIOSH) benzene soluble fraction method 5042 plus total organic matter. Sampling using both methods was performed in multiple bitumen-related workplace environments. To provide comparable data all samplings were performed in parallel, and the analytical data were related to the same representative bitumen condensate standard. An outline of the differences between the sampling and analytical methods is provided along with comparative data obtained from these site investigations. A total of 55 bitumen paving sampler pairs were reported and statistical comparisons made using the 35 pairs of detectable data. First, the German inhalable aerosol data and the NIOSH benzene soluble fraction (BSF) method showed a correlation coefficient of R²= 0.88 (y((BSF))= 0.60 x((aerosol))). Second, the aerosol data compared with total particulate matter (TPM) show a R² of 0.83 (y((TPM))= 1.01 x((aerosol))). Finally, total organic matter (TOM) and "aerosol + vapor" data yielded a R² of 0.78 (y((TOM))= 0.44 x((aerosol+vapor))). Twenty-nine pairs of roofing data were also collected; 37% were below the limit of detection. When comparing the TOM data with the aerosol + vapor data, using the 13 of 29 pairs where both samplers showed detectable results, the relationship was y((TOM))= 0.74 x((aerosol+vapor)) (R²= 0.91). The slopes within these equations provide predictive factors between these sampling and analysis methods; intended for use with large sets of data, they are not applicable to single point measurements.

Status of worker exposure to asphalt paving fumes with the use of engineering controls.

Since 1996, industry, labor, and government have partnered to minimize workers' exposure to asphalt fumes using engineering controls. The objective of this study was to determine the use after some years of experience and to benchmark the effectiveness of the engineering controls as compared to the current exposure limits. To accomplish this objective, the current highway class pavers equipped with controls to reduce asphalt fumes, occupational exposure levels, and ventilation flow rates were monitored, and a user acceptance survey was conducted. Personal breathing-zone sampling was administered to determine concentrations of total particulate matter (TPM) and benzene soluble matter (BSM). Personal monitoring of workers yielded a BSM arithmetic mean of 0.13 mg/m3 (95% confidence limits (0.07, 0.43) mg/m3). All site average worker BSM values are below the American Conference of Governmental Industrial Hygienists (ACGIH) adopted threshold limit value (TLV) time weighted average (TWA) of 0.5 mg/m3 as benzene soluble inhalable particulate, although five sites contained 95% confidence limits slightly above the ACGIH TLV. The TPM arithmetic mean was 0.35 mg/m3 (95% confidence limits (0.27, 0.69) mg/m3). All sites showed average worker and area TPM values below NIOSH's recommended exposure limit for asphalt fumes (5 mg/m3, 15 min). One screed area sample and one operator area sample were also taken each day. Area samples followed a similar pattern to the worker breathing zone samples, but were generally slightly higher in TPM and BSM concentration. The effect of work practices and application temperatures appears to have an impact on the ability of the engineering controls to keep exposure below the TLV for BSM. To gain a better understanding of the aerodynamic properties of asphalt fumes, particle size and airborne concentrations were also monitored using a TSI model 3320 aerodynamic particle sizer spectrometer. The geometric mean particle size was between 0.64 and 0.98 micrometers for the worker breathing zone samples, with a geometric mean of 0.73 micrometers for all sites. Total airborne concentrations were typically higher for the asphalt fume exposed groups than for the background samples. During high fume events, four 15-minute samples were taken each day. Only one 15-minute sample was above the limit of quantification. Stack flow rates were measured, and results are discussed and compared to the manufacturers' nominal values. Survey results were generally positive, with recommendations discussed for continuous improvement.

Evaluation of worker exposure to asphalt roofing fumes: influence of work practices and materials.

A field study was conducted on 42 asphalt-roofing workers at 7 built-up roofing sites across the United States. Sixteen out of 42 samples show levels of exposure to asphalt fumes that exceed the current American Conference of Governmental Industrial Hygienists' (ACGIH)-recommended threshold limit value of 0.5 mg/m(3) as benzene extractable inhalable particulate. Statistically, the geometric mean of all 42 worker samples was 0.27 mg/m(3) (geometric standard deviation = 3.40), the average was 0.70 mg/m(3) (standard deviation = 1.69) and the median value was 0.24 mg/m(3). The impact of work practices is discussed including the use of a novel product that uses a polymer skin to reduce fumes from built up roofing asphalt. Its use resulted in a reduction of benzene soluble matter (BSM) of >70%. Other testing measures utilized included total particulate matter, total organic matter, simulated distillation, and fluorescence analysis. Additionally, a controlled pilot study using 16 kettle-area and 16 worker samples clearly showed that when the temperature of the kettle was reduced by 28 degrees C, there was a 38-59% reduction in fume exposure and a 54% reduction in fluorescence with standard asphalts. Reduction of BSM exposures using fuming-suppressed asphalt was also confirmed during this pilot plant study (81-92%), with fluorescence lowered by 88%. Confounding agents such as roof tear-off materials were also analyzed and their contribution to worker exposure is discussed.

Evaluation of worker exposure to asphalt paving fumes using traditional and nontraditional techniques.

Forty-five workers at 11 paving sites across the United States were evaluated for exposure to paving asphalt (bitumen) fumes. Traditional measures of exposure such as total particulate matter (TPM) and benzene soluble matter (BSM) were monitored. In addition, total organic matter (TOM), which includes both the BSM residue and the more volatile components that pass through the filter and are collected on sorption material, was quantified and further characterized using a gas chromatography technique and a recently developed fluorescence test. The latter method, which indirectly estimates the content of four- to six-ring polycyclic aromatic compounds, is used as a predictor of carcinogenicity. The correlation between fluorescence emission intensity and carcinogenicity for 36 laboratory generated fume fractions, as measured in a mouse skin-painting bioassay, was then used to estimate the carcinogenic potential of worker monitoring samples. Emission levels, and therefore predicted carcinogenicity, for these samples were at least 17-fold below the value corresponding to a minimal carcinogenic effect. This result was consistent with more extensive chemical analysis (using gas chromatography/mass spectrometry) of two of the samples, which showed the predominant constituents to be alkanes, monocycloparaffins, alkyl-benzenes, alkyl-naphthalenes, and alkyl-benzothiophenes. The geometric mean exposures for all worker studies were 0.21 mg/m3 (TPM), 0.06 mg/m3 (BSM), and 1.23 mg/m3 (TOM).

Total versus inhalable sampler comparison study for the determination of asphalt fume exposures within the road paving industry.

Exposure to asphalt fumes has a threshold limit value (TLV of 0.5 mg m(-3) (benzene extractable inhalable particulate) as recommended by the American Conference of Governmental Industrial Hygienists (ACGIH). This reflects a recent change (2000) whereby two variables are different from the previous recommendation. First is a 10-fold reduction in quantity from 5 mg m(-3) to 0.5 mg m(-3). Secondly, the new TLV specifies the "inhalable" fraction as compared to what is presumed to be total particulate. To assess the impact of these changes, this study compares the differences between measurements of paving asphalt fume exposure in the field using an "inhalable" instrument versus the historically used 'total' sampler. Particle size is also examined to assist in the understanding of the aerodynamic collection differences as related to asphalt fumes and confounders. Results show that when exposures are limited to asphalt fumes, a 1:1 relationship exists between samplers, showing no statistically significant differences in benzene soluble matter (BSM). This means that for the asphalt fume ACGIH TLV, the 'total' 37-mm sampler is an equivalent method to the "inhalable" method, referred to as IOM (Institute of Occupational Medicine), and should be acceptable for use against the TLV. However, the study found that when confounders (dust or old asphalt millings) are present in the workplace, there can be significant differences between the two samplers' reported exposure. The ratio of IOM/Total was 1.37 for milling asphalt sites, 1.41 for asphalt paving over granular base, and 1.02 for asphalt over asphalt pavements.