Phosphine is a dangerous gas commonly used in fumigations of stored grains throughout the world. Grain that has not fully released the phosphine it absorbed during fumigation may continue to desorb phosphine into the headspace of a shipping container or storage. USOSHA standards for handling phosphine state the acceptable Threshold Limit Value (TLV) of 0.3 ppm. In many cases, during grain transport and handling, the level of phosphine in work environments can exceed the 0.3 ppm TLV which resulted from desorption of phosphine from fumigated grains. It is also important to note that desorbing grain, with low concentrations of phosphine, can facilitate insect resistance. Therefore, it is important to understand the process of phosphine venting and desorption in order to ensure safe handling of fumigated grain. In order to achieve this, the venting and release of phosphine was studied on location in a well-sealed grain silo in Lake Grace, Western Australia. The data set served for verification of a 3D finite element ecosystem model and were compared to the predicted results. Results were calculated using two different fumigant desorption models based on previous literature, i.e., a reversed sorption model and an air-grain equilibrium model. Simulations reproduced accurate trends of desorption but did not accurately reproduce the quantity of fumigant, with 55.5% error for the model based on reversed sorption equations, and 86.3% error for the air-grain equilibrium based model. For both models, additional simulations were conducted to compare the effectiveness of existing grain venting regulations at producing grain that is within post-fumigation safe handling limits. Results revealed that current U.S. standards may be insufficient to guarantee safety based on minimum venting times needed. These results highlight the necessity for continued research into phosphine desorption and the importance for establishing realistic post-fumigation venting guidelines.