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The objective of this paper is to use remote sensing to measure on-road emissions and to examine the impact and usefulness of additional measurement devices at three sites. Supplementing remote sensing device (RSD) equipment with additional equipment increased the capture rate by almost 10%. Post-processing of raw data is essential to obtain useful and accurate information. A method is presented to identify vehicles with excessive emission levels (high emitters). First, an anomaly detection method is applied, followed by identification of cold start operating conditions using infrared vehicle profiles. Using this method, 0.6% of the vehicles in the full (enhanced) RSD data were identified as high emitters, of which 35% are likely in cold start mode where emissions typically stabilize to low hot running emission levels within a few minutes. Analysis of NOx RSD data confirms that poor real-world NOx performance of Euro 4/5 light-duty diesel vehicles observed around the world is also evident in Australian measurements. This research suggests that the continued dieselisation in Australia, in particular under the current Euro 5 emission standards and the more stringent NO2 air quality criteria expected in 2020 and 2025, could potentially result in local air quality issues near busy roads. [ABSTRACT FROM AUTHOR]