Considerable uncertainties are associated with the experimental estimates of emission rates of different volatile organic compound (VOC) species from the biosphere to the atmosphere. Some of this uncertainty derives from the sampling and analytical procedures used in emission rate measurements. A calibration system was developed in order to evaluate possible errors in the measurements of biogenic emission rates using a branch enclosure system. Two types of calibration procedures were tested, a standard additions technique and an internal standard procedure. Both techniques were used to evaluate possible losses while sampling isoprene and monoterpenes, which are the most abundant VOCs of biogenic origin. The losses to Teflon lines and the empty sampling system were tested and losses to the branch enclosure system installed on two VOC emitting plant species were evaluated. A considerable loss of isoprene (∼18% of inflow concentration 65 ng l⁻¹) to the empty enclosure system and to the system installed on the plant was measured, but no losses of monoterpenes were observed.