Monica Escola Casas

Can those organic micro-pollutants that are recalcitrant in activated sludge treatment be removed from wastewater by biofilm reactors (slow sand filters)?

The degradation of seven compounds which are usually recalcitrant in classical activated sludge treatment (e.g., diclofenac, propranolol, iopromide, iohexol, iomeprol tebuconazole and propiconazole) was studied in a biofilm reactor (slow sand filtration). This reactor was used to treat real effluent-wastewater at different flow rates (hydraulic loadings) under aerobic conditions so removal and degradation kinetics of these recalcitrant compounds were calculated. With the hydraulic loading rate of 0.012 m(3)m(2)h(-1) the reactor removed 41, 94, 58, 57 and 85% of diclofenac, propranolol, iopromide, iohexol and iomeprol respectively. For these compounds the removal efficiency was dependent on hydraulic residence-times. Only 59 and 21% of the incoming tebuconazole and propiconazole respectively were removed but their removal did not depend on hydraulic residence time. Biofilm reactors are thus efficient in removing micro-pollutants and could be considered as an option for advanced treatment in small wastewater treatment plants.

Biodegradation of pharmaceuticals in hospital wastewater by a hybrid biofilm and activated sludge system (Hybas)

Hospital wastewater contributes a significant input of pharmaceuticals into municipal wastewater. The combination of suspended activated sludge and biofilm processes, as stand-alone or as hybrid process (hybrid biofilm and activated sludge system (Hybas™)) has been suggested as a possible solution for hospital wastewater treatment. To investigate the potential of such a hybrid system for the removal of pharmaceuticals in hospital wastewater a pilot plant consisting of a series of one activated sludge reactor, two Hybas™ reactors and one moving bed biofilm reactor (MBBR) has been established and adapted during 10 months of continuous operation. After this adaption phase batch and continuous experiments were performed for the determination of degradation of pharmaceuticals. Removal of organic matter and nitrification mainly occurred in the first reactor. Most pharmaceuticals were removed significantly. The removal of pharmaceuticals (including X-ray contrast media, β-blockers, analgesics and antibiotics) was fitted to a single first-order kinetics degradation function, giving degradation rate constants from 0 to 1.49 h(-1), from 0 to 7.78 × 10(-1)h(-1), from 0 to 7.86 × 10(-1)h(-1) and from 0 to 1.07 × 10(-1)h(-1) for first, second, third and fourth reactors respectively. Generally, the highest removal rate constants were found in the first and third reactors while the lowest were found in the second one. When the removal rate constants were normalized to biomass amount, the last reactor (biofilm only) appeared to have the most effective biomass in respect to removing pharmaceuticals. In the batch experiment, out of 26 compounds, 16 were assessed to degrade more than 20% of the respective pharmaceutical within the Hybas™ train. In the continuous flow experiments, the measured removals were similar to those estimated from the batch experiments, but the concentrations of a few pharmaceuticals appeared to increase during the first treatment step. Such increase could be attributed to de-conjugation or formation from other metabolites.

Phytoremediation of imazalil and tebuconazole by four emergent wetland plant species in hydroponic medium.

Pollution from pesticide residues in aquatic environments is of increasing concern. Imazalil and tebuconazole, two commonly used systemic pesticides, are water contaminants that can be removed by constructed wetlands. However, the phytoremediation capability of emergent wetland plants for imazalil and tebuconazole, especially the removal mechanisms involved, is poorly understood. This study compared the removal of both pesticides by four commonly used wetland plants, Typha latifolia, Phragmites australis, Iris pseudacorus and Juncus effusus, and aimed to understand the removal mechanisms involved. The plants were individually exposed to an initial concentration of 10 mg/L in hydroponic solution. At the end of the 24-day study period, the tebuconazole removal efficiencies were relatively lower (25%-41%) than those for imazalil (46%-96%) for all plant species studied. The removal of imazalil and tebuconazole fit a first-order kinetics model, with the exception of tebuconazole removal in solutions with I. pseudacorus. Changes in the enantiomeric fraction for imazalil and tebuconazole were detected in plant tissue but not in the hydroponic solutions; thus, the translocation and degradation processes were enantioselective in the plants. At the end of the study period, the accumulation of imazalil and tebuconazole in plant tissue was relatively low and constituted 2.8-14.4% of the total spiked pesticide in each vessel. Therefore, the studied plants were able to not only take up the pesticides but also metabolise them.

Identification of Triclosan-O-Sulfate and other transformation products of Triclosan formed by activated sludge

Aerobic degradation experiments of Triclosan were performed in activated sludge to identify possible transformation products for this compound. During 7 days, the formation of biotransformation products such as 2,4-Dichlorophenol, 4-Chlorocatechol, 5-Hydroxy-Triclosan and other Monohydroxy-Triclosan derivatives as well as Dihydroxy-Triclosan-derivatives were observed. The structure of 5-Hydroxy-Triclosan was elucidated by NMR data for the first time in sludge degradation experiments. Additionally the production of a hitherto unknown transformation product in sludge, i.e., Triclosan-O-Sulfate was detected. During the incubations, the concentrations of this transformation product changed from zero to 330 μg L(-1). Based on the analysis of the biodegradation products, three types of reactions were identified: 1) chemical scission of ether bond to form phenols and catechols, 2) addition of OH moieties to the aromatic ring, and 3) adding of methyl or sulfate groups to the original hydroxyl group.

Removal of antibiotics during the anaerobic digestion of pig manure

Antibiotics are frequently used in animals to treat sickness and prevent infection especially in industrial meat production. Some of the antibiotics cannot be completely metabolized and, as an unavoidable result, are excreted and thus end up in manure which is then spread in the environment. Currently increasing amounts of manure is used in biogas production before spreading the residuals on agricultural fields. In this study, the removal patterns of sulfonamides (sulfadiazine, sulfamethizole, sulfamethoxazole) and macrolides (clarithromycin, erythromycin), as well as trimethoprim, were investigated during the anaerobic digestion of pig manure. Batch kinetic tests were conducted both at thermophilic and psychrophilic condition for 40 days. Some of the antibiotics (clarithromycin, sulfadiazine, sulfamethizole) were persistent in all experiments. Thus, no biodegradation was found for sulfadiazine and sulfamethizole in this study. From the studied compounds, only erythromycin was clearly removed and probably degraded during anaerobic digestion with 99% and 20% removal under thermophilic and psychrophilic condition. The removal of erythromycin was fitted to a single first-order kinetic reaction function, giving reaction rate constant of 0.29day-1 and 0.005day-1, respectively.

Analytical sample preparation strategies for the determination of antimalarial drugs in human whole blood, plasma and urine

Antimalarial drugs commonly referred to as antimalarials, include a variety of compounds with different physicochemical properties. There is a lack of information on antimalarial distribution in the body over time after administration, e.g. the drug concentrations in whole blood, plasma, and urine, which must be improved in order to advance curing the parasitic disease malaria. A key problem also lies in that pharmacokinetic studies not always are performed in patient groups that may benefit most of the treatment such as children, pregnancy and lower-weight ethnic populations. Here we review the available sample preparation strategies combined with liquid chromatographic (LC) analysis to determine antimalarials in whole blood, plasma and urine published over the last decade. Sample preparation can be done by protein precipitation, solid-phase extraction, liquid-liquid extraction or dilution. After LC separation, the preferred detection tool is tandem mass spectrometry (MS/MS) but other detection methods have been used e.g. UV, fluorescence and electrochemical detection. Major trends for sample preparation of the different groups of antimalarials for each matrix and its detection have been summarized. Finally, the main problems that the researchers have dealt with are highlighted. This information will aid analytical chemists in the development of novel methods for determining existing antimalarials and upcoming new drugs.

Removal of pharmaceuticals in pre-denitrifying MBBR – Influence of organic substrate availability in single- and three-stage configurations

Due to the limited efficiency of conventional biological treatment, innovative solutions are being explored to improve the removal of trace organic chemicals in wastewater. Controlling biomass exposure to growth substrate represents an appealing option for process optimization, as substrate availability likely impacts microbial activity, hence organic trace chemical removal. This study investigated the elimination of pharmaceuticals in pre-denitrifying moving bed biofilm reactors (MBBRs), where biofilm exposure to different organic substrate loading and composition was controlled by reactor staging. A three-stage MBBR and a single-stage reference MBBR (with the same operating volume and filling ratio) were operated under continuous-flow conditions (18 months). Two sets of batch experiments (day 100 and 471) were performed to quantify and compare pharmaceutical removal and denitrification kinetics in the different MBBRs. Experimental results revealed the possible influence of retransformation (e.g., from conjugated metabolites) and enantioselectivity on the removal of selected pharmaceuticals. In the second set of experiments, specific trends in denitrification and biotransformation kinetics were observed, with highest and lowest rates/rate constants in the first (S1) and the last (S3) staged sub-reactors, respectively. These observations were confirmed by removal efficiency data obtained during continuous-flow operation, with limited removal (<10%) of recalcitrant pharmaceuticals and highest removal in S1 within the three-stage MBBR. Notably, biotransformation rate constants obtained for non-recalcitrant pharmaceuticals correlated with mean specific denitrification rates, maximum specific growth rates and observed growth yield values. Overall, these findings suggest that: (i) the long-term exposure to tiered substrate accessibility in the three-stage configuration shaped the denitrification and biotransformation capacity of biofilms, with significant reduction under substrate limitation; (ii) biotransformation of pharmaceuticals may have occurred as a result of cometabolism by heterotrophic denitrifying bacteria.

Separation, isolation and stereochemical assignment of imazalil enantiomers and their quantitation in an in vitro toxicity test.

A simple method for the separation of the enantiomers of the fungicide imazalil was developed. Racemic imazalil was separated into its enantiomers with an enantiomeric purity of 99% using HPLC-UV with an enantioselective column (permethylated cyclodextrin) operated in reversed phase mode (water with 0.2% trimethylamine and 0.08% acetic acid and methanol). The absolute configuration of the separated enantiomers was assigned and unequivocally confirmed by optical rotation as well as by vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) combined with ab-initio calculations. The same enantioselective column was also used to develop an HPLC-MS/MS method for the quantification of imazalil enantiomers. The HPLC-MS/MS method reached limits of quantification (LOQs) of 0.025mg/mL with 5μL injections. This method was used to verify imazalil concentrations and enantiomeric fractions in samples from an in vitro test on effects on human steroidogenesis (H295R steroidogenesis assay). The quantification verified the stability of the enantiomers of imazalil during the in vitro tests.

Removal of ozonation products of pharmaceuticals in laboratory Moving Bed Biofilm Reactors (MBBRs)

The major pathway of pharmaceuticals from urban applications to urban surface waters is via wastewater treatment plants. Ozonation is able to remove pharmaceuticals from wastewater effluents. However, during that reaction, ozonation products are formed. Some ozonation products were found to be persistent and have adverse effect on the environment. Moving bed bio reactors (MBBRs) were tested for the removal of the ozonation products of macrolide antibiotics and diclofenac at two different concentration levels 1 μg/L and 10 μg/L in laboratory reactors. It was found that the MBBRs are capable of degrading these compounds without back-transformation into the parent compounds. However, reaction rate constants and the degradation kinetics varied for different compounds and different concentrations. Depending on compound and conditions, the degradation reaction kinetics was found to follow either i) zero order ii) first order or iii) lag phase succeeded by first order. The study has proven that MBBRs have the potential to be efficient in polishing post ozonation treatment.