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The influence of ambient temperature on exhaust emissions for an instrumented Euro 1 SI car was determined for urban congested traffic conditions. In UK cities cold-starting vehicles directly into congested traffic conditions is a common occurrence that is not currently taken into account when modeling urban traffic pollution. In-vehicle emission samples were taken directly from the exhaust, upstream and downstream of the catalyst, using the bag sampling technique. The first bag was for the cold start emissions and approximately the first 1.1 km of travel. The following three bags were with a hotter catalyst. The cold start tests were conducted over a year, with ambient temperatures ranging from 2°C to 30°C. The results showed that CO emissions for the cold start were reduced by 70% downstream of the catalyst when the ambient temperature rose from 2°C to 30°C. The corresponding hydrocarbon emissions were reduced by 41% and NOx emissions were increased by 90%.