Acute toxicity of petroleum asphalt seal coat leachates to Ceriodaphnia dubia is linked to polymer preservatives.

Low-VOC waterborne asphalt-emulsion (AE) seal coat is considered more sustainable than solvent-based coal-tar emulsion seal coat because asphalt emulsions contain negligible amounts of carcinogenic PAHs and release fewer harmful volatile organic compounds. Yet, many low-VOC coatings leach water-soluble substances under outdoor conditions. To investigate the chemical composition of seal coat leachates, three AE formulations were cured under natural weathering conditions and exposed to simulated runoff over a 10-day field trial. Runoff was collected and concentrated using ion-exchange solid-phase extraction (SPE) and analyzed using gas chromatography/mass spectrometry (GC-MS). Leached compounds included hydrocarbons, esters, amines, siloxanes, plasticizers, biocides, polyethylene glycol (PEG) ethers, urethanes, and toluene diisocyanate (TDI). Glycol ethers comprised 29-97 % of the measured leachate mass. Two seal coat formulations contained isothiazolinone biocides, methylchloro- and methylisothiazolinone (CMIT/MIT; 0.5 mg/L in runoff), while a third seal coat formulation continuously leached TDI, a reactive polyurethane (PU) precursor (0.7 mg/L in runoff). Biocide-containing leachates showed acute toxicity to the freshwater water flea, Ceriodaphnia dubia after 48 h, while TDI-containing leachate showed no acute toxicity, suggesting that leachate toxicity was due to in-can polymer preservatives. As biocides are implicated in impaired reproductive signaling, these results support the use of alkaline pH to avoid biofouling and reinforce the goal of reducing and/or avoiding the use of biocides altogether, especially for environmentally friendly products.

Quantification of azaarenes, hydroxylated azaarene derivatives, and other polar compounds released in urban runoff from two commercial sealcoat products.

Sealcoat is an emulsified coating product applied to asphalt to protect against surface weathering. Sealcoat products contain coal-tar (CT) or petroleum-derived residues and are a recognized source of polycyclic aromatic hydrocarbons (PAHs) in urban areas. Although the toxicity of urban runoff from CT-sealed asphalt is established, chemical characterization has focused more on PAHs and alkylated derivatives and less on polar transformation products. In this study, solid-phase extraction (SPE) was used to concentrate dissolved (<0.2 µm) species in runoff collected from asphalt surfaces sealed with CT pitch or steam-cracked petroleum (SCP) residues. CT-sealed surfaces released a 20-fold greater concentration of SPE-extractable compounds in runoff compared to SCP-sealed surfaces. Representative compounds were sorted into four groups: nitrogen heterocycles (azaarenes) and other oxygen- and sulfur-containing species (N HET); hydroxylated N heterocycles (hydroxylated N HET); the nonionic surfactant 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD); and styrene-acrylonitrile polymer byproducts (SAN Trimer). Species concentrations and weathering-related disappearance behavior differed among the four subgroups. While hydroxylated N HET concentrations decreased by 94% in runoff from CT-sealed surfaces 60 h after sealcoat application, SAN Trimer concentrations in CT and SCP runoff increased over time as polymerization progressed, illustrating the complex changes the chemicals in sealcoat undergo as it cures under environmentally-relevant conditions. Overall, this study shows that urban runoff collected from CT-sealed and SCP-sealed asphalt surfaces is a potential source of water-soluble contaminants with unknown long-term ecotoxicological effects to aquatic systems.

Determination of oxygen, nitrogen, and sulfur-containing polycyclic aromatic hydrocarbons (PAHs) in urban stream sediments.

Recent studies indicate that PAH transformation products such as ketone or quinone-substituted PAHs (OPAHs) are potent aryl hydrocarbon receptor (AhR) activators that elicit toxicological effects independent of those observed for PAHs. Here, we measured eight OPAHs, two sulfur-containing (SPAH), one oxygen-containing (DBF), and one nitrogen-containing (CARB) heterocyclic PAHs (i.e. ΣONS-PAHs = OPAH8 + SPAH + DBF + CARB) in 35 stream sediments collected from a small (∼1303 km(2)) urban watershed located in south-central Pennsylvania, USA. Combined ΣONS-PAH concentrations ranged from 59 to 1897 µg kg(-1) (mean = 568 µg kg(-1); median = 425 µg kg(-1)) and were 2.4 times higher in urban versus rural areas, suggesting that activities taking place on urban land serve as a source of ΣONS-PAHs to sediments. To evaluate urban land use metrics that might explain these data, Spearman rank correlation analyses was used to evaluate the degree of association between ΣONS-PAH concentrations and urban land-use/land-cover metrics along an urban-rural transect at two spatial scales (500-m and 1000-m upstream). Combined ΣONS-PAH concentrations showed highly significant (p < 0.0001) correlations with ΣPAH19, residential and commercial/industrial land use (RESCI), and combined state and local road miles (MILES), suggesting that ΣONS-PAHs originate from similar sources as PAHs. To evaluate OPAH sources, a subset of ΣONS-PAHs for which reference assemblages exist, an average OPAH fractional assemblage for urban sediments was derived using agglomerative hierarchal cluster (AHC) analysis, and compared to published OPAH source profiles. Urban sediments from the Condoguinet Creek (n = 21) showed highly significant correlations with urban particulate matter (X(2) = 0.05, r = 0.91, p = 0.0047), suggesting that urban particulate matter is an important OPAH source to sediments in this watershed. Results suggest the inclusion of ΣONS-PAH measurements adds value to traditional PAH analyses, and may help elucidate and refine pollutant source identification in urban watersheds.

Coal-tar-based sealcoated pavement: a major PAH source to urban stream sediments.

We used land-use analysis, PAH concentrations and assemblages, and multivariate statistics to identify sediment PAH sources in a small (~1303 km(2)) urbanizing watershed located in South-Central, Pennsylvania, USA. A geographic information system (GIS) was employed to quantify land-use features that may serve as PAH sources. Urban PAH concentrations were three times higher than rural levels, and were significantly and highly correlated with combined residential/commercial/industrial land use. Principal components analysis (PCA) was used to group sediments with similar PAH assemblages, and correlation analysis compared PAH sediment assemblages to common PAH sources. The strongest correlations were observed between rural sediments (n = 7) and coke-oven emissions sources (r = 0.69-0.78, n = 5), and between urban sediments (n = 22) and coal-tar-based sealcoat dust (r = 0.94, n = 47) suggesting that coal-tar-based sealcoat is an important urban PAH source in this watershed linked to residential and commercial/industrial land use.