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.

Toxicity and inhibition assessment of ionic liquids by activated sludge.

Toxicity of 13 ionic liquids (ILs) corresponding to different families were studied by inhibition respiration assays (15 min) using activated sludge. Toxicity increased as increasing the number of carbons in the alkyl-chain of imidazolium-based ILs, with EC50 values from 4.19 to 0.17 for 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]) and 1-octyl-3-methylimidazolium chloride ([Omim][Cl]), respectively. An increase in toxicity was observed for aromatic-based ILs (pyridinium- and imidazolium-based ILs) due to the hydrophobic character of the head groups in comparison with linear structures as phosphonium and ammonium cations. Among to the anions studied fixing [Emim]+ as cation, [HSO4]- and [NTf2]- presented low EC50 values (0.34 mM and 1.69 mM, respectively) while [Cl]- and [EtSO4]- were considered harmless anions due to the hydrophilic character of chloride and the organic nature of [EtSO4]-. ILs toxicity/inhibition was determined by adding a biodegradable compound and measuring the sludge response after being in contact with the ILs for at least 15 h. The exposure of sewage sludge to ILs for more than 15 min used in short inhibition assays caused more toxic effect on microorganisms, even for [Choline][NTf2], previously defined as practically harmless (EC50 = 2.79 mM). Biodegradability assays confirmed the biodegradable nature of choline cation, related with TOC conversion of 40%, only due to cation consumption. No oxygen consumption or even lysis of microbial cells was observed for Tetrabutylammonium bis(trifluoromethylsulfonyl)imide and for 1-Ethyl-3-methylimidazolium hydrogensulphate due to the presence of anions previously defined as hazardous ([NTf2]- and [HSO4]-), maintaining their recalcitrant character to sewage systems.

Biowaste management by hydrothermal carbonization and anaerobic co-digestion: Synergistic effects and comparative metagenomic analysis.

The feasibility of anaerobic co-digestion in semicontinuous mode of two major urban biowaste, food waste (FW) and garden and park waste (GPW) (75 % FW and 25 % GPW) as well as the co-digestion of FW with the process water originated from the hydrothermal carbonization of GPW (95 % FW and 5 % process water), both on a COD basis, has been assessed. The effect of varying organic loading rate (OLR) from 1.5 to 3.5 g COD/L·d on methane yield, gross energy recovery, and microbiome population was evaluated. For comparison, anaerobic digestion of FW was also conducted to determine the best strategy for sustainable biowaste management. This study showed an optimal OLR of 2.5 g COD/L·d. Acetic and propionic acid content increased as OLR raised for each condition studied, while methane yield decreased at the highest OLR tested indicating overloading of the system. The anaerobic co-digestion of FW and process water showed a 10 % increase on methane production compared to anaerobic digestion of FW (324 vs. 294 mL CH4 STP/L·d). Moreover, it enhances the process due to a greater abundance and diversity of hydrolytic and acidogenic bacteria belonging to Bacterioidota, Firmicutes, and Chloroflexi phyla, as well as promotes the hydrogenotrophic pathway under higher propionic concentrations which is not usually favoured for methane production. The integration of hydrothermal carbonization of GPW with the anaerobic co-digestion of 95 % FW and 5 % of process water results in the highest potential energy recovery and could be a good strategy for sustainable management of urban biowaste.

Comparison of experimental methods for determination of toxicity and biodegradability of xenobiotic compounds.

Different methods for determining the toxicity and biodegradability of hazardous compounds evaluating their susceptibility to biological treatment were studied. Several compounds including chlorophenols and herbicides have been evaluated. Toxicity was analyzed in terms of EC50 and by a simple respirometric procedure based on the OECD Method 209 and by the Microtox® bioassay. The values of EC50 obtained from respirometry were in all the cases higher than those from the Microtox® test. The respirometric inhibition values of chlorophenols were related well with the number of chlorine atoms and their position in the aromatic ring. In general, herbicides showed lower inhibition, being alachlor the less toxic from this criterion. For determination of biodegradability an easier and faster alternative to the OECD Method 301, with a higher biomass to substrate ratio is proposed. When this test was negative, the Zahn-Wellens one was performed in order to evaluate the inherent biodegradability. In the fast test of biodegradability, 4-chlorocatechol and 4-chlorophenol showed a complete biodegradation by an unacclimated sludge upon 48 h. These results together with their low respirometric inhibition, allow concluding that these compounds could be conveniently removed in a WWTP. Alachlor, 2,4-dichlorophenol, 2,4,6-trichlorophenol and MCPA showed a partial biodegradation upon 28 days by the Zahn-Wellens inherent biodegradability test.

Coupling Fenton and biological oxidation for the removal of nitrochlorinated herbicides from water.

The combination of Fenton and biological oxidation for the removal of the nitrochlorinated herbicides alachlor, atrazine and diuron in aqueous solution has been studied. The H2O2 dose was varied from 20 to 100% of the stoichiometric amount related to the initial chemical oxygen demand (COD). The effluents from Fenton oxidation were analyzed for ecotoxicity, biodegradability, total organic carbon (TOC), COD and intermediate byproducts. The chemical step resulted in a significant improvement of the biodegradability in spite of its negligible or even slightly negative effect on the ecotoxicity. Working at 60% of the stoichiometric H2O2 dose allowed obtaining highly biodegradable effluents in the cases of alachlor and atrazine. That dose was even lower (40% of the stoichiometric) for diuron. The subsequent biological treatment was carried out in a sequencing batch reactor (SBR) and the combined Fenton-biological treatment allowed up to around 80% of COD reduction.

Strategies to evaluate biodegradability: application to chlorinated herbicides.

The biodegradability of nitrochlorinated (diuron and atrazine) and chlorophenoxy herbicides (2,4-D and MCPA) has been studied through several bioassays using different testing times and biomass/substrate ratios. A fast biodegradability test using unacclimated activated sludge yielded no biodegradation of the herbicides in 24 h. The inherent biodegradability test gave degradation percentages of around 20-30% for the nitrochlorinated herbicides and almost complete removal of the chlorophenoxy compounds. Long-term biodegradability assays were performed using sequencing batch reactor (SBR) and sequencing batch membrane bioreactor (SB-MBR). Fixed concentrations of each herbicide below the corresponding EC50 value for activated sludge were used (30 mg L(-1) for diuron and atrazine and 50 mg L(-1) for 2,4-D and MCPA). No signs of herbicide degradation appeared before 35 days in the case of diuron and atrazine and 21 days for 2,4-D, whereas MCPA was partially degraded since the early stages. Around 25-36% degradation of the nitrochlorinated herbicides and 53-77% of the chlorophenoxy ones was achieved after 180 and 135 days, respectively, in SBR, whereas complete disappearance of 2,4-D was reached after 80 days in SB-MBR.