Uptake and release kinetics of 22 polar organic chemicals in the Chemcatcher passive sampler

The Chemcatcher passive sampler, which uses Empore (TM) disks as sampling phase, is frequently used to monitor polar organic chemicals in river water and effluents. Uptake kinetics need to be quantified to calculate time-weighted average concentrations from Chemcatcher field deployments. Information on release kinetics is needed if performance reference compounds (PRCs) are used to quantify the influence of environmental conditions on the uptake. In a series of uptake and elimination experiments, we used Empore (TM) SDB disks (poly(styrenedivinylbenzene) copolymer modified with sulfonic acid groups) as a sampling phase and 22 compounds with a logK (ow) (octanol-water partitioning coefficient) range from -2.6 to 3.8. Uptake experiments were conducted in river water or tap water and lasted up to 25 days. Only 1 of 22 compounds (sulfamethoxazole) approached equilibrium in the uptake trials. Other compounds showed continuing non-linear uptake, even after 25 days. All compounds could be released from SDB disks, and desorption was proportionally higher in disks loaded for shorter periods. Desorption showed two-phase characteristics, and desorption was proportionally higher for passively sorbed compounds compared to actively loaded compounds (active loading was performed by pulling spiked river water over SDB disks using vacuum). We hypothesise that the two-phase kinetics and better retention of actively loaded compounds-and compounds loaded for a longer period-may be caused by slow diffusion of chemicals within the polymer. As sorption and desorption did not show isotropic kinetics, it is not possible to develop robust PRCs for adsorbent material like SDB disks

Transfer kinetics of polar organic compounds over polyethersulfone membranes in the passive samplers Pocis and Chemcatcher

Passive samplers for polar organic compounds often use a polyethersulfone (PES) membrane to retain the particulate sorbent material (e.g., in a POCIS; polar organic chemical integrative sampler) or to reduce the sampling rate and thus extend the kinetic regime (e.g., in a Chemcatcher). The transport kinetics over the PES membrane are evaluated here in a short-term (6 days) and a long-term (32 days) experiment with POCIS and Chemcatchers. Passive samplers were placed in a channel with flowing river water that was spiked with 22 organic chemicals including pharmaceuticals, pesticides and biocides; with logK(ow) (logarithmic octanol-water partitioning coefficient) values between -2.6 and 3.8. Samplers were removed at intervals and membranes and sorbent material were extracted and analyzed with LC-MS/MS. Uptake kinetics of the compounds fell between two extremes: (1) charged chemicals and chemicals of low hydrophobicity did not accumulate in PES and rapidly transferred to the sorbent (e.g., diclofenac) and (2) more hydrophobic chemicals accumulated strongly in the PES and appeared in the sorbent after a lag-phase (e.g., diazinon and diuron). Sorption kinetics were modeled with a three-compartment first-order kinetic model to determine uptake and elimination rate constants and partitioning coefficients. Water PES partitioning coefficients fitted with the model correlated well with experimentally determined values and logK(ow). Sampling rates of Chemcatcher (0.02-0.10 L/d) and POCIS (0.02-0.30 L/d) showed similar patterns and correlated well. Thus the samplers are interchangeable in practical applications. Longer lag-phases may pose problems when calculating time-weighted average aqueous concentrations for short passive sampling windows and for a correct integrative sampling of fluctuating concentrations