Many organizations interested in renewable, domestic energy have switched from petroleum diesel to biodiesel blends for use in transportation and heavy-duty equipment. Although considerable evidence exists on the negative health effects of petroleum diesel exhaust exposures in occupational settings, there has been little research examining biodiesel exposures. Working collaboratively with a local municipality, concentrations of particulate matter (PM) and other air toxics were measured at a recycling facility in southwestern New Hampshire while heavy equipment operated first on petroleum diesel and then on a B20 blend (20% soy-based biodiesel/80% petroleum diesel). This pilot study used a combination of established industrial hygiene and environmental air monitoring methods to estimate occupational exposure profiles to PM and air toxics from combustion of petroleum diesel and biodiesel. Results indicate that B20 use dramatically reduces work area respirable particle, PM2.5 (PM 2.5 m in aerodynamic diameter), and formaldehyde levels compared with petroleum diesel. Some volatile organic compound concentrations were higher for petroleum diesel and others were higher for the B20 blend. Overall, this study suggests that biodiesel blends reduce worker exposure to and health risk from petroleum diesel exhaust, but additional exposure research is recommended.