Development and field testing of an online instrument for measuring the real-time oxidative potential of ambient particulate matter based on dithiothreitol assay

Abstract

<p><strong>Abstract.</strong> We developed an online instrument for measuring the oxidative potential (OP) of ambient particulate matter (PM) using the dithiothreitol (DTT) assay. The instrument uses a mist chamber (MC) to continuously collect the ambient PM<span class="inline-formula">_2.5</span> in water, and then determines its DTT activity using an automated syringe pump system. The instrument was deployed at an urban site in the University of Illinois campus, and its field performance was evaluated by comparing the results with the offline DTT activity measurements of simultaneously collected PM-laden filters. The online DTT activity measurements correlated well with the offline measurements but were higher than both methanol (slope<span class="thinspace"></span><span class="inline-formula">=1.0</span>8, <span class="inline-formula"><i>R</i>²=0.93</span>) and Milli-Q water (slope<span class="thinspace"></span><span class="inline-formula">=1.86</span>, <span class="inline-formula"><i>R</i>²=0.86</span>) extracts of the PM filters, indicating a better efficiency of the MC for collecting the water-insoluble fraction of PM. The hourly measurements of ambient PM<span class="inline-formula">_2.5</span> OP were obtained by running the online instrument intermittently for 50 days with minimal manual assistance. The daytime DTT activity levels were generally higher than at night. However, a 4-fold increase in the hourly averaged activity was observed on the night of 4 July (Independence Day fireworks display). The diurnal profile of the hourly averaged OP during weekdays showed a bimodal trend, with a sharp peak in the morning (around 07:00<span class="thinspace"></span>LT), followed by a broader afternoon peak which plateaus around 14:00<span class="thinspace"></span>LT and starts subsiding at night (around 19:00<span class="thinspace"></span>LT).</p> <p>To investigate the association of the diurnal profile of DTT activity with the emission sources at the site, we collected time-segregated composite PM filter samples in four different time periods of the day (morning, 07:00–10:00<span class="thinspace"></span>LT; afternoon, 10:00–15:00<span class="thinspace"></span>LT; evening, 15:00–19:00<span class="thinspace"></span>LT; and night, 19:00–07:00<span class="thinspace"></span>LT) and determined the diurnal variations in the redox active components (i.e., water-soluble Cu, Fe, Mn, organic carbon, elemental carbon, and water-soluble organic carbon). Based on this comparison, we attributed the daytime OP of ambient PM<span class="inline-formula">_2.5</span> to the vehicular (both exhaust and non-exhaust) emissions and resuspended dust, whereas secondary photochemical transformation of primary emissions appear to enhance the OP of PM during the afternoon and evening period.</p>