Characterization of soluble iron in urban aerosols using near-real time data

We present the first near‐real time (12 min) measurements of fine particle (PM2.5) water soluble ferrous iron (WS_Fe(II)) measured in two urban settings: Dearborn Michigan, and Atlanta, Georgia. A new approach was used to measure WS_Fe(II) involving a Particle‐into‐Liquid Sampler (PILS) coupled to a liquid waveguide capillary cell (LWCC) and UV/VIS spectrometer. We found no clear diurnal trends in WS_Fe(II) at any urban site studied. High temporal variability, however, was observed at all urban sites, where concentrations often changed from the method limit of detection (4.6 ng m−3) to approximately 300 to 400 ng m−3, lasting only a few hours. These transient events predominately occurred during times of low wind speeds and appeared to be from local sources or processes. In Atlanta, several WS_Fe(II) events were associated with sulfate plumes, and highest WS_Fe(II) concentrations were found in plumes of highest apparent aerosol acidity. At all locations studied, WS_Fe(II) was poorly correlated (R2 < 0.34) with light‐absorbing aerosol, indicating no direct linkage between mobile source emissions and enhanced WS_Fe(II) concentrations. WS_Fe(II) measured within a prescribed forest‐burn was strongly correlated with water soluble potassium (R2 = 0.88; WS_Fe(II)/WS_K = 15 mg/g), pointing to biomass burning as a source of WS_Fe(II); however, peak concentrations within the fire were low compared to transient events observed at the urban sites. Overall, WS_Fe(II) temporal trends for these urban sites consisted of low background concentrations with periodic short duration transient events that appear to be linked to unique industrial emissions or atmospheric processing of industrial emissions that form WS_Fe(II).