Critical review of technologies for the on-site treatment of hospital wastewater: From conventional to combined advanced processes.

This review aims to assess different technologies for the on-site treatment of hospital wastewater (HWW) to remove pharmaceutical compounds (PhCs) as sustances of emerging concern at a bench, pilot, and full scales from 2014 to 2020. Moreover, a rough characterisation of hospital effluents is presented. The main detected PhCs are antibiotics and psychiatric drugs, with concentrations up to 1.1 mg/L. On the one hand, regarding the presented technologies, membrane bioreactors (MBRs) are a good alternative for treating HWW with PhCs removal values higher than 80% in removing analgesics, anti-inflammatories, cardiovascular drugs, and some antibiotics. Moreover, this system has been scaled up to the pilot plant scale. However, some target compounds are still present in the treated effluent, such as psychiatric and contrast media drugs and recalcitrant antibiotics (erythromycin and sulfamethoxazole). On the other hand, ozonation effectively removes antibiotics found in the HWW (>93%), and some studies are carried out at the pilot plant scale. Even though, some families, such as the X-ray contrast media, are recalcitrant to ozone. Other advanced oxidation processes (AOPs), such as Fenton-like or UV treatments, seem very effective for removing pharmaceuticals, Antibiotic Resistance Bacteria (ARBs) and Antibiotic Resistance Genes (ARGs). However, they are not implanted at pilot plant or full scale as they usually consider extra reactants such as ozone, iron, or UV-light, making the scale-up of the processes a challenging task to treat high-loading wastewater. Thus, several examples of biological wastewater treatment methods combined with AOPs have been proposed as the better strategy to treat HWW with high removal of PhCs (generally over 98%) and ARGs/ARBs (below the detection limit) and lower spending on reactants. However, it still requires further development and optimisation of the integrated processes.

New insights on the removal of diclofenac and ibuprofen by CWPO using a magnetite-based catalyst in an up-flow fixed-bed reactor.

This research has been focused on the removal of two anti-inflammatory drugs, diclofenac (DCF) and ibuprofen (IBU), by a continuous catalytic wet peroxide oxidation (CWPO) process using a lab-synthesized nanomagnetic catalyst (Fe3O4/MWCNTs). The central composite rotatable design (CCRD) method was used to study the effect of DCF and IBU concentration (expressed as theoretical oxygen demand (ThOD) between 0 and 52.5 mg L-1) and of the feed stream pH (from 3 to 7) on the removal of total organic carbon (TOC) and the concentration of aromatic compounds (Arm) and total phenolic compounds (TP) by CWPO. It could be observed that DCF was preferably removed from the DCF-IBU aqueous mixture at pH values ranging from 3 to 5. In addition, feed stream pH had a significant effect on the pollutants removal, as well as on TOC, TP and aromatic compounds removal, observing an increasing in the pollutants degradation when feed stream pH decreased from 7 to 3. Quadratic models predicted for response variable, such as TOC, TP and aromatic compounds removal, and their maximum model-predicted removal values were of 90.0, 80.2 and 90.0%, respectively. Finally, as a proof of concept, three environmentally-relevant aqueous matrices, spiked with DCF-IBU mixture, were treated. In this case, relatively high TOC degradation values were found after 20 h reaction time (ca. 57.7, 73.9 and 54.5% in surface water, WWTP effluent and hospital wastewater, respectively). This work deals the first study about DCF-IBU removal in aqueous solution by CWPO, as well as a continuous study using real wastewater that allow to extend the experimental results to a real scenario.

Enhanced removal of the endocrine disruptor compound Bisphenol A by adsorption onto green-carbon materials. Effect of real effluents on the adsorption process.

The high exposure to the endocrine disrupting compounds (EDC) in water represents a relevant issue for the health of living beings. The xenoestrogen Bisphenol A (BPA), a suspected EDC, is an industrial additive broadly used for manufacturing polycarbonate and epoxy resins. Due to its harmful effect in humans and the aquatic environment, an efficient method to remove BPA from wastewater is urgently required. The present work aims to study the adsorption of BPA from aqueous solutions onto carbonaceous materials, e.g., a synthesized carbon xerogel (RFX), a chemical-activated carbon from Kraft lignin (KLP) and a commercial activated carbon (F400) for comparative purposes. Batch kinetic and adsorption tests of BPA in ultrapure water were accomplished, finding higher adsorption capacities of BPA onto both F400 activated carbon (qsat = 407 mg g-1) and the biochar KLP (qsat = 220 mg g-1), versus to that obtained for the xerogel (qsat = 78 mg g-1). Furthermore, kinetic experiments revealed faster kinetic adsorption for RFX and KLP materials, achieving the equilibrium time within 24 h, attributed to their more-opened porous structure. Pseudo-first order, pseudo-second order, Elovich, intra-particle diffusion and film diffusion models were used to fit the experimental data. Thus, the BPA adsorption isotherms were analysed by Langmuir, Freundlich, Sips, Redlich-Peterson and Dual-site Langmuir (DLS) isotherm models.In addition, the influence of different aqueous matrices, such as a hospital wastewater, a wastewater treatment plant (WWTP) effluent and a river water, on BPA removal efficiency has been explored. These adsorption tests revealed a clear competitive effect between the target compound (BPA) and the natural organic matter content (NOM) present in the matrices for the active sites, resulting in a high decreasing of BPA adsorption removal.

New insights from modelling and estimation of mass transfer parameters in fixed-bed adsorption of Bisphenol A onto carbon materials.

The removal of Bisphenol A, 2,2-bis (4-hydroxyphenyl) propane (BPA) in fixed-bed columns was investigated by breakthrough adsorption tests at different operation conditions and further prediction by a mathematical model to describe the adsorption-diffusion process onto two synthesized carbon porous materials. In this study, a xerogel (RFX) prepared by an optimized conventional sol-gel method and a lignin-based activated carbon (KLP) obtained via chemical activation were used in batch and fixed-bed adsorption experiments. The materials were fully characterized and their adsorptive properties were compared to those obtained with a commercial activated carbon (F400). RFX and KLP materials reached the equilibrium adsorption in only 24 h, whereas F400 activated carbon required 48 h. In addition, F400 and KLP adsorbents showed higher equilibrium adsorption capacity values (qe = 0.40 and 0.22 kg/kg, for F400 and KLP, respectively) than that obtained for the xerogel (qe = 0.08 kg/kg). Both synthesized carbon-adsorbents were studied in fixed-bed adsorption tests, exploring the effect of the operation conditions, e.g., initial BPA concentration (0.005-0.04 kg/m3), weight of adsorbent (0.01-0.05 g) and volumetric flow rate (0.2 to 1.0 mL/min), on the adsorption performance of the column. All the tested adsorption columns reached the equilibrium in a very short time, due to the efficient dimensionless of the bed. Additionally, the regeneration of the exhausted adsorbent was studied, achieving the total reuse of the solids after three consecutive cycles using methanol as regeneration agent. Finally, a mathematical model based on mass conservation equations was proposed, allowing to efficiently fit the experimental BPA breakthrough curves and estimate the external and adsorbed-phase mass transfer coefficients with a high accuracy.

Synthesis of high surface area carbon adsorbents prepared from pine sawdust-Onopordum acanthium L. for nonsteroidal anti-inflammatory drugs adsorption.

Chemically activated carbon materials prepared from pine sawdust-Onopordum acanthium L. were studied for the removal of diclofenac and naproxen from aqueous solution. Several carbons, using different proportions of precursors were obtained (carbon C1 to carbon C5) and the chemical modification by liquid acid and basic treatments of C1 were carried out. The textural properties of the carbons, evaluated by N2 adsorption-desorption isotherms, revealed that the treatments with nitric acid and potassium hydroxide dramatically reduced the specific surface area and the pore volume of the carbon samples. The surface chemistry characterization, made by thermal programmed decomposition studies, determination of isoelectric point and Boehm's titration, showed the major presence of lactone and phenol groups on the activated carbons surface, being higher the content when the acidic strength of the carbon increased. Diclofenac and naproxen kinetic data onto C1 carbon followed pseudo-second order model. The adsorption equilibrium isotherms of C1 and the modified carbons were well described by both Sips and GAB isotherm equations. The highest adsorption capacity was found for naproxen onto C1 activated carbon, 325 mg g(-1), since the liquid acid and basic functionalization of the carbon led to a severe decreasing in the adsorption removal of the target compounds.