Tetracyclines are one of the most widely used class of veterinary and human antibiotics. The conventional treatment of wastewater based on activated sludge is not effective to remove antibiotics and their residues are still biologically active, which represents a problem in terms of bacterial resistance. The main objective of this work is to assess ability of stevensite and two biochars to adsorb three tetracycline antibiotics from water. Batch adsorption experiments were carried out to test the ability of these materials to adsorb tetracyclines. Then desorption experiments were performed to determine the adsorption strength on stevensite. In order to elucidate the adsorption mechanism of tetracyclines on stevensite, cation exchange analysis and spectroscopic analyses by IR and XRD were performed. The adsorption of tetracyclines on stevensite was tested on continuous system with water artificially contaminated. Finally, the designed filter was validated with tetracyclines spiked wastewater. The two biochars and stevensite were able to adsorb between 60 and 100% of the tetracyclines present in the batch system. Stevensite was the material with the highest tetracyclines removal capacity (around 100% at low concentrations of tetracyclines). Biochars showed less affinity for tetracyclines adsorption (70%). Tetracyclines desorption from stevensite reached values lower than 10% for low tetracyclines concentrations. The IR spectroscopy suggested that cation exchange is the main mechanism of tetracyclines adsorption on clay and also proved the role of amide and amine groups in this adsorption. The cation exchange mechanism was confirmed by displacement of Ca and Mg from stevensite. A continuous wastewater flow through a system composed by stevensite leaved this system with no tetracyclines, indicating water purification by tetracyclines adsorption in clay.

The presence of antibiotics in crops is mainly caused by their irrigation with reclaimed wastewater and by the use of organic amendments of animal origin. During this work, the fate of sulfonamide antibiotics in tomato crop has been assessed in two commercial greenhouses located in Almería (Spain) irrigated with reclaimed wastewater. Samplings were made annually for two years. Sulfonamides in several parts of the plant (roots, leaves and fruits) as well as reclaimed wastewater, amendments and soils were analyzed by UHPLC-MS/MS. The results showed that sulfonamides accumulated in soils (sulfamethoxazole between 2 and 14 µg Kg−1; sulfadiazine, sulfathiazole, sulfapyridine, sulfamerazine and sulfadimethoxine in concentrations below 1 µg Kg−1) were in the reclaimed wastewater at concentrations in the ng L−1 range. Their distribution in plants depended on the sulfonamide. The sulfonamides detected in tomato were sulfadiazine, sulfapyridine, sulfamethazole, sulfamethoxazole and sulfadimethoxine. Sulfamethoxazole was the antibiotic with highest concentration in tomato fruit, exceeding 30 µg Kg−1. All sulfonamides were below the Acceptable Daily Intake, however, further studies and legislation are needed to assure food safety.

A double strategy based on the removal of sulfonamide antibiotics by Pleurotus ostreatus and adsorption on spent mushroom substrate was assessed to reclaim contaminated wastewater. P. ostreatus was firstly tested a in liquid medium fortified with five sulfonamides: sulfamethoxazole, sulfadiazine, sulfathiazole, sulfapyridine and sulfamethazine, to evaluate its capacity to remove them, to test for any adverse effects on fungal growth and for any reduction in residual antibiotic activity. P. ostreatus was effective in removing sulfonamides up to 83 to 91 % of the applied doses over 14 days. The antibiotic activity of the sulfonamide residues was reduced by 50 %. Sulfamethoxazole transformation products by laccase were identified and the degradation pathway was proposed. In addition, P. ostreatus growth on a semi-solid medium of spent mushroom substrate and malt extract agar was used to develop a biofilter for the removal of sulfonamides from real wastewater. The biofilter was able to remove more than 90% of the sulfonamide concentrations over 24 hours by combining adsorption and biodegradation mechanisms.

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Bioremediation techniques are being developed as substitutes for physical–chemical methodologies that are expensive and not sustainable. For example, using the agricultural waste spent mushroom substrate (SMS) which contains valuable microbiota for soil bioremediation. In this work, SMSs of four cultivated fungal species, Pleurotus eryngii, Lentinula edodes, Pleurotus ostreatus, and Agaricus bisporus were evaluated for the bioremediation of soils contaminated by petroleum hydrocarbons (TPHs). The bioremediation test was carried out by mixing the four different SMSs with the TPH-contaminated soil in comparison with an unamended soil control to assess its natural attenuation. To determine the most efficient bioremediation strategy, hydrolase, dehydrogenase, and ligninolytic activities, ergosterol content, and percentage of TPHs degradation (total and by chains) were determined at the end of the assay at 40 days. The application of SMS significantly improved the degradation of TPHs with respect to the control. The most effective spent mushroom substrate to degrade TPHs was A. bisporus, followed by L. edodes and P. ostreatus. Similar results were obtained for the removal of aliphatic and aromatic hydrocarbons. The results showed the effectiveness of SMS to remove aliphatic and aromatic hydrocarbons from C10 to C35. This work demonstrates an alternative to valorizing an abundant agricultural waste as SMS to bioremediate contaminated soils.