Slow desorption behavior of one highly resistant aromatic amine in Lake Macatawa, Michigan, USA, sediment

The desorption behavior of benzidine from Lake Macatawa (Holland, MI, USA) sediment was investigated in this study using batch solvent extraction method. Seven solvents were tested as the extracting reagents: Deionized water (DI), calcium chloride in DI (CaCl2), sodium hydroxide in DI (NaOH), acetonitrile (ACN), a mixture of acetonitrile and ammonium acetate in DI (ACN-NH4OAc), methanol (MeOH), and hydrochloric acid in DI (HCl). These solvents are proposed to react with sediment-associated benzidine by different mechanisms (e.g., cation exchange, hydrophobic partitioning, and covalent binding). Three sets of sorption isotherm experiments were conducted separately in these seven solvents with a 7-d, three-week, and two-month contact time. The results demonstrated nonlinear isotherms with Freundlich 1/n values varying from 0.25 to 0.52. The desorption behavior of benzidine in the solvents was evaluated after the sorption of benzidine onto the sediment with same contact times of 7 d, three weeks, and two months. A two-stage model subsequently was applied to simulate the experimental data. The rapidly desorbing rate constants were on the order of one to two per day for ACN, ACN-NH4OAc, and NaOH solvents, and the slowly desorbing rate constants were on the order of 10(-5) to 10(-4)/d. Sequential desorption experiment demonstrated low total extraction efficiency of less than 40%. Both the observed sorption and desorption phenomena suggested that hysteresis and/or mass-transfer limited diffusion may result in the slow desorption behavior observed in this study.