Pesticide concentrations in agricultural streams are often characterised by a low level of baseline exposure and episodic peak concentrations associated with heavy rainfall events. Traditional sampling methods such as grab sampling, which are still largely used in governmental monitoring, typically miss peak concentrations. Passive sampling represents a cost-efficient alternative but requires the additional determination of sampling rates to calculate time-weighted average (TWA) water concentrations from the accumulated pesticide mass in the sampler. To date, sampling rates have largely been determined in experiments with constant exposure, which does not necessarily reflect field situations. Using Empore styrene-divinylbenzene (SDB) passive sampler disks mounted in metal holders, we determined sampling rates for 42 organic pesticides, of which 27 sampling rates were lacking before. The SDB disks were in an artificial channel system exposed to a field-relevant pesticide peak. We used an open-source algorithm to estimate coefficients of equations for the accumulated pesticide mass in disks and to determine exposure time-dependent sampling rates. These sampling rates ranged from 0.02 to 0.98 L d⁻¹ and corresponded to those from previous studies determined with constant exposure. The prediction of sampling rates using compound properties was unreliable. Hence, experiments are required to determine reliable sampling rates. We discuss the use of passive sampling to estimate peak concentrations. Overall, our study provides sampling rates and computer code to determine these under peak exposure designs and suggests that passive sampling is suitable to estimate peak pesticide concentrations in field studies.