Influence of mussel shell, oak ash and pine bark on the adsorption and desorption of sulfonamides in agricultural soils.

Taking into account the high mobility and environmental risks due to sulfonamide antibiotics as emerging pollutants, batch-type experiments were performed to study adsorption/desorption of three sulfonamides (sulfadiazine -SDZ-, sulfamethazine -SMT- and sulfachloropyridazine -SCP-) in three agricultural soils. The study was carried out both for un-amended and amended soil samples, using different doses (0, 12, 24 and 48 Mg ha) of three different by-products (mussel shell, oak ash and pine bark). Adsorption on un-amended soils was rather low, with percentages between 11 and 45% for SDZ, 20-64% for SMT, and 19-65% for SCP. Both the Linear and Freundlich models fitted well to adsorption curves. In the case of un-amended soils, and regarding the Linear model, the values of the coefficient of distribution (K, expressed in L kg) were between 0.6 and 1.3 for SDZ, between 0.7 and 1.1 for SMT, and between 0.6 and 2.6 for SCP. As regards the Freundlich model, the values of the adsorption constant (K, expressed in L μmol kg), were in the range 0.4-1.9 for SDZ, 0.9-2.9 for SMT, and 1.2-3.8 for SCP. Simultaneously, desorption percentages were high, reaching 13.7-47.7% for SDZ, 12.6-35.1% for SMT, and 13.7-34.3% for SCP, when the highest initial antibiotic concentration (50 μmol L) was added, thus indicating low retention and high mobility for these compounds in soils. Mussel shell and oak ash amendments did not increase retention of any of the three sulfonamides. However, the incorporation of pine bark resulted in an increase in the adsorption and decrease in desorption for all three antibiotics. Specifically, for soils amended with pine bark at 48 Mg ha, K values (expressed in L kg) were between 2.1 and 2.9 for SDZ, between 3.4 and 3.6 for SMT, and between 2.5 and 8.2 for SCP. Regarding K (expressed in L μmol kg), its values ranged from 5.6 to 6.3 for SDZ, 6.2-8.8 for SMT, and 5.3-7.1 for SCP. These scores were clearly higher than those of un-amended soils, and pine bark amendment also resulted in lower desorption percentages, ranging 8.7-11.4% for SDZ, 4.0-10.7% for SMT, and 6.5-16.9% for SCP. This positive effect on the retention of sulfonamides due to pine bark can be attributed to its high organic carbon content (48.6%), as well as to its acidic pH (4.0). Therefore, pine bark amendment can be considered an effective alternative to increase the retention of sulfonamides in soils, thus reducing their bioavailability and transport to other environmental compartments, and subsequent risks of negative impacts on human and environmental health.