Vegetal Waste as a Sustainable Option to Boost Sorption for the Efficient Removal of Steroid Hormones in Constructed Wetlands

Steroid hormones (SHs) have a high estrogenic potential, and urban wastewater is one of their main ways into the aquatic environment. Constructed wetlands (CWs) are considered one of the most sustainable alternatives for the treatment of wastewater from small communities. However, the use of gravel and sand implies a significant environmental impact associated with their extraction and transport. A more sustainable alternative is the use of plant residues, as they are abundant, inexpensive, and readily available, and they can improve the efficiency of hormone removal through sorption. Thus, the sorption of 15 SHs was studied on conventional, mineral substrates (gravel, sand, and volcanic ash) and alternative vegetal wastes, i.e., mulches from giant reed, palm tree, balsa wood, and pine needles. These materials were characterized by determining their Point of Zero Charge (pHPZC), ash content, content of leachable polycyclic aromatic hydrocarbons (PAH) and heavy metals, total surface area (BET), and pore characteristics. Results indicated that SH sorption on the mineral substrates was quite low, in most cases less than 10–15%. However, in the mulches it reached between 50 and 95%, except for corticosteroids (11–43%). The pseudo-second-order kinetics provided the best fit in all cases, with R2 values between 0.97 and 0.9999. Experiments with a contact time of 7 days showed that the palm tree was the only substrate that completely removed the three corticosteroids studied (cortisone, prednisone, and prednisolone). Additionally, a significant correlation was observed between removal due to sorption (%) and log octanol–water partition coefficient (log Kow). Freundlich isotherm provided a higher number of best fits than Langmuir. Lastly, to compare sand with palm mulch under more realistic experimental conditions, four lab-scale CWs (two with palm mulch and two with sand, with/without plants) were studied. The sand-based CWs achieved faster SH percentage removals, while after 24 h, SH mass removals were significantly higher in the palm mulch-based CWs.