Factors affecting diffusion of polar organic compounds in agarose hydrogel applied to control mass transfer in...

Diffusive hydrogel-based passive sampler (HPS) based on diffusive gradients in thin films (DGT) is designed for monitoring polar organic contaminants in the aquatic environment. DGT technique controls the compound's overall uptake rate by adding a hydrogel layer of known thickness, which minimizes the importance of the resistive water boundary layer in the compound uptake process. In this work, we investigated several factors which may influence the diffusion of a range of aquatic contaminants in 1.5% agarose hydrogel. Diffusion in hydrogel was tested using the sheet stacking method. We demonstrated that a thin nylon netting incorporated into the diffusive hydrogel for mechanical strengthening does not significantly affect the diffusion of 11 perfluoroalkyl compounds. Further, we investigated the effect of pH in the range from 3 to 11 on the diffusion of a range of 39 aromatic amines (AAs) -36 aromatic, 2 aliphatic, and azobenzene in hydrogel. AAs were chosen as representatives of compounds with pH-dependent dissociation in water. Analysis of variance showed no significant difference in mean diffusion coefficient log D value at five pH values. The demonstration that the diffusion coefficient D and thus the sampling rate R_s are independent on pH simplifies the interpretation of data from field studies because we can neglect the influence of pH on the R_s. log D values (m² s^-1) of tested AAs ranged from to - 9.77 for 3,3'-dimethylbenzidine to - 9.19 for azobenzene. A negative correlation of log D with molar mass (log M) and molecular volume (log V_m) was observed (R =  - 0.57 and - 0.56, respectively). The diffusion coefficient presents a critical parameter for the sampling rate estimation of HPS. Theoretical sampling rates R_s of AAs were calculated for a HPS using the average D values. Theoretical R_s values calculated for AAs at 22°C ranged from 29 mL day^-1 for 3,3'-dimethylbenzidine to 106 mL day^-1 for 2-aminopyridine. Our calculated values of R_s are in the same range as those already published for a range of low-molecular polar organic contaminants, which supports the possibility of deriving sampler performance parameters in the field from laboratory-derived diffusivity of analytes in hydrogel.