Empirical mathematical models have been frequently used to estimate emissions and to act in the prevention of possible impacts from odorous compounds. Based on the regulatory WATER9 model, the present study had the aim to evaluate the deviations originating from the simplification of using the effective diameter (in contrast to the conceptually appropriate use of the linear physical fetch) as fetch parameter in the calculation of the global mass transfer coefficient at passive liquid surfaces at wastewater treatment plants (WWTPs). The present analysis incorporated the influence of different values of wind velocity, molecular diffusivity and Henry's Law constant. The analyses for the calculation of the mass transfer coefficients were developed for 1,000 wind speeds, chosen using the Monte Carlo method, three WWTPs and three compounds of environmental relevance, spanning different behaviour regarding their volatilisation. The wind speed had a direct influence on the deviations for all types of compounds analysed. However, this parameter was found to be more representative for the compounds whose volatilisation is limited by conditions in the liquid phase. Furthermore, the deviations for the calculation of the mass transfer coefficient arising from the use of the effective diameter as fetch parameter were significantly larger for liquid phase-dominated compounds, compared to gas phase-dominated compounds. Comparison against available experimental data confirm that the use of the effective diameter as the fetch parameter makes the model predictions further depart from the experimental values. The present analysis shows that, for a varied range of wind speed and WWTP configurations, the use of the actual physical fetch shall be preferred over the use of the effective diameter in emission models for WWTPs, so as to avoid the introduction of potentially large systematic deviations.