The health risk assessment paradigm is progressively being included in the French regulatory process. In this context, the French Ministry of Environment asked INERIS to assess the health risks incurred by populations living in the vicinity of industrial sites. This study gives the results of the risk assessment carried out on populations living nearby synthetic rubber's manufacturers which have among the most polluting activities concerning 1,3-butadiene and concomitant pollutants. To achieve this target, a bibliographical synthesis was first done to identify the different types of industrial sites releasing 1,3-butadiene. As a result, a national inventory was set up. The pollutants toxicity was also studied as well as the dose-response relationships for the most relevant effects (i.e. for butadiene: carcinogenic, reproduction and developmental effects) and the main way of exposure (inhalation). Preliminary exposure results focused on butadiene and gave an estimate of its concentrations in the air around synthetic rubber's manufacturers using factories production capacities as a proxy according to the European calculation methodology. Site specific studies, in partnership with industrial sites, were undergone to illustrate the predictive approach described before and demonstrate its (in)adequacy in exposure and risk assessment for populations living nearby local sources. Ambient air levels of butadiene gathered in these studies have generated original data in France, compatible with toxicity levels. In the theoretical approach, 1,3-butadiene exposure concentration and the risk calculation are computed using the probabilistic approach. Monte Carlo simulations show risks which were not negligible for population living in the vicinity of synthetic rubber's manufacturers. For carcinogenic effects, the order of magnitude of individual life-long cancer risk is 10–3 (P90 = 2,7.10–3) which leads to an health impact ranging from 2 (P10) to 114 (P90) cases of Feukemia in the target population (estimated to be 42 128 persons nationwide). These results are based on the unit risk derived recently by EPA (3.10–5 (μg/m3)−1) but they do not take into account several factors i.e. the fact that butadiene is not persistent in the atmosphere: as a result, contact with population is very limited in time and space. Measurements at 3 industrial sites borders show concentrations in ambient air ranging from 0.2 to 1 μg/m3 on average for butadiene (10 hours measurements using Restek SilicoCan canisters and US-EPA-TO 14 methodology) by comparison with estimations ranging from 100 to 200 μg/m3 for the same sites using the European methodology. Individual life-long cancer risk for 3 sites representative of the various types of industrial sites releasing 1,3-butadiene in France are 100 to 1000 less significant (ranging from 10–6 to 10–5) compared with the predictive EU approach. These results tend to show the inadequacy of the European local scenario methodology in 1,3-butadiene exposure and risk assessment. However, results are in adequacy with the regional scenario of the European evaluation and with results obtained in an urban context during this study. Comparable conclusions are reached for acrylonitrile. For styrene, site specific results are between the local and regional European scenarios.