Project description:After a biological terrorist attack, understanding the migration of agents such as Bacillus anthracis is critical due to their deadly nature. This is important in urban settings with higher likelihood of human exposure and a large fraction of impervious materials contributing to pollutant washoff. The study goals were to understand the removal of spores from urban surfaces under different rainfall conditions, to compare washoff of two B. anthracis surrogate spores, and to compare two empirical fits for the first flush of spores from small areas. Concrete and asphalt were inoculated with either Bacillus atrophaeus or Bacillus thuringiensis kurstaki spores and exposed to simulated rainfall. The study assessed goodness-of-fit for the Storm Water Management Model (SWMM)'s exponential washoff function compared to an alternative two-stage exponential function. The highest average washoff of spores was 15% for an hour-long experiment. Spore washoff was not significantly different for the two spore types, but there were significant differences in washoff from asphalt versus concrete with more occurring from asphalt. Average kinetic energy of the storm event impacted washoff from asphalt, but not concrete. The two-stage function had a better goodness-of-fit than the SWMM exponential function. As such, emergency responders should be aware that the spread of contamination is impacted by the droplet characteristics of the storm event and the surface material type in the contaminated area; modelers should be aware that different data-fitting approaches may be more appropriate for first-flush calculations of small washoff areas than those used for continuous long-term simulation of large subcatchments.
Project description:The rubber antioxidant 6PPD has gained significant attention due to its highly toxic transformation product, 6PPD-quinone (6PPDQ). Despite their detection in urines of pregnant women, the placental transfer and developmental toxicity of 6PPD and 6PPDQ are unknown. Here, we treated C57Bl/6 mice with 4 mg/kg 6PPD or 6PPDQ to investigate their urine excretion and placental transfer. Female and male mice exhibited sex difference in excretion profiles of 6PPD and 6PPDQ. Urine concentrations of 6PPDQ were one order of magnitude lower than those of 6PPD, suggesting lower excretion and higher bioaccumulation of 6PPDQ. In pregnant mice treated with 6PPD or 6PPDQ from embryonic day 11.5 to 15.5, 6PPDQ showed ∼1.5-8 times higher concentrations than 6PPD in placenta, embryo body, and embryo brain, suggesting higher placental transfer of 6PPDQ. Using in vitro dual-luciferase reporter assays, we revealed that 6PPDQ activated the human retinoic acid receptor α (RARα) and retinoid X receptor α (RXRα) at concentrations as low as 0.3 μM, which was ∼10-fold higher than the concentrations detected in human urines. 6PPD activated the RXRα at concentrations as low as 1.2 μM. These results demonstrate the exposure risks of 6PPD and 6PPDQ during pregnancy and emphasize the need for further toxicological and epidemiological investigations.
Project description:Prompted by a recent report that 6PPD-quinone (6PPD-q), a by-product of a common tire manufacturing additive that is present in road runoff, is toxic to coho salmon (Oncorhynchus kisutch), extracts of water samples collected from an urban river were re-analyzed to determine if this compound was present in stormwater-influenced flows. In addition, extracts were analyzed for 1,3-diphenylguanidine (DPG), which is also used in tire manufacturing. Samples were originally collected in the fall of 2019 and winter of 2020 in the Greater Toronto Area of Canada from the Don River, a highly urbanized watershed in close proximity to several major multi-lane highways. These target compounds were analyzed using ultra-high pressure liquid chromatography with high resolution mass spectrometric detection with parallel reaction monitoring. Both 6PPD-q and DPG were detected above limits of quantification (i.e., 0.0098 µg/L) in all extracts. Maximum concentrations for 6PPD-quinone of 2.30 ± 0.05 µg/L observed in the river during storm events exceeded the LC50 for this compound for coho salmon (i.e., > 0.8 µg/L). In composite samples collected at intervals throughout one rain event, both compounds reached peak concentrations a few hours after initiation of the event (i.e., 0.52 µg/L for DPG and 2.85 µg/L for 6PPD-q), but the concentrations of 6PPD-q remained elevated above 2 µg/L for over 10-h in the middle of the event. Estimates of cumulative loads of these compounds in composite samples indicated that kg amounts of these compounds entered the Don River during each hydrological event, and the loads were proportional to the amounts of precipitation. This study contributes to the growing literature indicating that potentially toxic tire-wear compounds are present at elevated levels and are transported via road runoff into urban surface waters during rain events.
Project description:6PPDQ is a tire-derived contaminant toxic to coho salmon (LC50 = 41-95 ng/L) found widely distributed in urban environments. Most monitoring efforts have relied on relatively few discrete samples collected at select locations across rain events. Early work has revealed that 6PPDQ concentrations vary widely over time and space, raising questions about when and where to collect samples. Here, we employ condensed phase membrane introduction mass spectrometry, a high-throughput analysis approach to characterize spatiotemporal variability of 6PPDQ in urban streams. Analytical method detection limits of 0.3-8 ng/L and a duty cycle of 2.5 min/sample enabled high-throughput adaptive sampling. Temporal sampling revealed dynamic 6PPDQ concentrations, with significant changes occurring over minutes during peak rainfall. Spatial variability was characterized at multiple sites along three watercourses during the first significant precipitation of autumn 2023 on central Vancouver Island, B.C., Canada. Site-specific concentrations suggest attenuation of 6PPDQ after point source inputs by some combination of physical (dilution, sorption) or chemical (degradation) processes. This is the first report of an intensive sampling campaign describing the spatiotemporal distribution of 6PPDQ, highlighting the need for careful consideration of sampling strategies to evaluate the risk and impact of 6PPDQ in urban waterways.
Project description:As an antioxidant and antiozonant, N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) is predominantly used in the rubber industry to prevent degradation. However, 6PPD can be ozonated to generate a highly toxic transformation product called N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine quinone (6PPD-quinone), which is toxic to aquatic and terrestrial organisms. Thus, 6PPD and 6PPD-quinone, two emerging contaminants, have attracted extensive attention recently. This review discussed the levels and distribution of 6PPD and 6PPD-quinone in the environment and investigated their toxic effects on a series of organisms. 6PPD and 6PPD-quinone have been widely found in air, water, and dust, while data on soil, sediment, and biota are scarce. 6PPD-quinone can cause teratogenic, developmental, reproductive, neuronal, and genetic toxicity for organisms, at environmentally relevant concentrations. Future research should pay more attention to the bioaccumulation, biomagnification, transformation, and toxic mechanisms of 6PPD and 6PPD-quinone.
Project description:Rutting has always been considered the main disease in asphalt pavement. Dealing with rutting disease would be benefitted by understanding the formation of rutting and testing the rutting performance of mixtures more reasonably. The objective of this paper is to systematically investigate the rutting mechanism by employing a self-designed rutting tester along with the corresponding numerical simulations. The deformation of different positions of the existing tracking tester was found to be inconsistent, and the loading was not in line with reality. Accordingly, a more practical tester was proposed: the reduced scale circular tracking (RSCT) tester integrates the functions of asphalt mixture fabrication and rutting monitoring. The results demonstrated that the loading of the new tester is closer to the actual situation. In addition, determining the stress and displacement characteristics of particles in the asphalt mixture was found to be difficult due to the limitations of the testing methods. Therefore, a two-dimensional virtual rutting test based on the RSCT was built using PFC2D (Particle Flow Code 2 Dimension) to investigate the mechanism of formation in rutting and to obtain the corresponding guidance. The numerical simulation showed that all particles of the specimen tended to move away from the load location. The main cause of rutting formation was the eddy current flow of asphalt mastic driven by coarse aggregates. The aggregates with diameters ranging from 9.5 to 4.75 mm were observed to have the greatest contribution to rutting deformation. Therefore, the aggregate amount of these spans should be focused on in the design of mixture grading.
Project description:The use of recycled materials in pavement construction has seen, over the years, a significant increase closely associated with substantial economic and environmental benefits. During the past decades, many transportation agencies have evaluated the effect of adding Reclaimed Asphalt Pavement (RAP), and, more recently, Recycled Asphalt Shingles (RAS) on the performance of asphalt pavement, while limits were proposed on the amount of recycled materials which can be used. In this paper, the effect of adding RAP and RAS on the microstructural and low temperature properties of asphalt mixtures is investigated using digital image processing (DIP) and modeling of rheological data obtained with the Bending Beam Rheometer (BBR). Detailed information on the internal microstructure of asphalt mixtures is acquired based on digital images of small beam specimens and numerical estimations of spatial correlation functions. It is found that RAP increases the autocorrelation length (ACL) of the spatial distribution of aggregates, asphalt mastic and air voids phases, while an opposite trend is observed when RAS is included. Analogical and semi empirical models are used to back-calculate binder creep stiffness from mixture experimental data. Differences between back-calculated results and experimental data suggest limited or partial blending between new and aged binder.
Project description:Despite widespread agreement on the beneficial nature of hydrated lime (HL) addition to asphalt concrete mixes, understanding of the effect of HL particle size is still limited. Previous investigations have focused mainly on two different size comparisons, and so certain guidance for a practical application cannot yet be produced. This study investigates three distinct sizes of HL, in the range of regular, nano, and sub-nano scales, for their effects on the properties of modified asphalt concretes. Five different percentages of HL as a partial replacement of ordinary limestone filler in asphalt concrete mixes were studied for wearing course application purposes. Experimental tests were conducted to evaluate the mechanical properties, including resistance to plastic flow, volumetric properties, moisture susceptibility, resilient modulus, and permanent deformation. The results revealed that a positive correlation exists between the mechanical properties and the fineness of HL particle sizes.