The introduction of three-way catalytic converter (TWC) to meet stringent vehicular NOx emission standards worldwide has led to an unintended consequence of vehicle-derived ammonia (NH3) emission, which might degrade air quality and affect human health, especially in urban areas. The nitrogen stable isotope composition of NH3 (δ15N-NH3) may be a useful tool to trace NH3 sources, but the isotopic signature of vehicle-emitted NH3 is lacking. Here we report the δ15N-NH3 measured from tailpipe exhausts collected directly from 19 different vehicles equipped with TWC using "grab" sample technique optimized to avoid isotopic fractionation. We found a large of range of NH3 concentration (from 1 to 37 ppm, x̄ ± 1σ = 10 ± 8 ppm) and δ15N value (from -38.1 ‰ to 49.0 ‰, x̄ ± 1σ = 1.2 ± 20.9 ‰) for our samples (n = 57). Our results indicate a correlation between δ15N-NH3 and NH3 concentrations (i.e. δ15N-NH3 (‰) = 16.9(± 2.2)In(NH3 concentration; ppm) - 31.7(± 4.7) (R2 = 0.53, P < 0.01) that is associated with the catalyst temperature, which is generally agree with the results of theoretical calculation. After consideration of the vehicle emission evolution, dominant driving condition and tunnel δ15N-NH3 variation, a representative δ15N-NH3 value (meanminmax) of vehicle source is identified as 0.8000-2.20005.2000, which is distinct from (larger than) other NH3 volatilization-related emission sources. Using our newly measured δ15N values and Bayesian mixing model, we approximate the overall contribution of vehicles to ambient NH3 before, during, and after an international event in Beijing was 14.1 %, 7.9 %, and 21.5 %, respectively, which agree well with the course of traffic restriction. Collectively, our findings demonstrate the importance of using vehicle-emitted δ15N-NH3 to quantify vehicular NH3 contribution in urban atmospheres.
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