Seasonal and Spatial Relationship of Chemistry and Toxicity in Atmospheric Particulate Matter Using Aquatic Bioassays

In light of current interest in better understanding the environmental impact of atmospheric particulate matter (PM), a new strategy has been employed to screen the relative toxicities of ambient and source aerosols. Short-term and acute aquatic bioassays using Ceriodaphnia dubia and a green alga (Selenastrum capricornutum) as test organisms have been in use for many years in the regulation of wastewater effluents. These tests have been employed in the present study to compare the toxicity of water extracts of atmospheric particulate matter and dichloromethane (DCM) extracts that have been transferred to dimethyl sulfoxide and diluted in water. Atmospheric PM was collected at four sites located near the south shore of Lake Michigan and one site in Michigan's Upper Peninsula at discrete events during three seasons. Parallel chemical analyses of the two extracts directly assessed the relation between the chemical composition and the toxicity of the extract. Inductively coupled plasma analysis of the metals in the water extract and gas chromatography−mass spectroscopy of the organics in the DCM extract showed a relationship between high toxicity and high water-soluble copper concentration and high secondary organic aerosol tracers in the extracted aerosol. Although previous fractionation studies have not looked at water-soluble copper, significant toxicity has been measured in the semipolar and polar organic fractions of ambient aerosols and diesel exhaust particles, which are the fractions in which secondary organic aerosol components would be expected. For the water extracts, the summer samples were consistently more toxic than the autumn or spring samples. There was not a seasonal pattern for the toxicity of the DCM extracts; however, spatial differences were apparent. The toxicity end points of select samples from one site qualitatively correlate with the high polycyclic aromatic hydrocarbon concentrations. Additionally, high toxicity in the July DCM extracts from another site may be tied to the presence of the insecticide carbaril. The seasonal and spatial variations captured in the toxicity results in this study tend to qualitatively correlate with trace organic components and metals and not bulk particulate matter composition.