Although pollutants pose environmental and human health risks, the majority are not routinely monitored and regulated. Organic pollutants emanate from a variety of sources, and can be classified depending on their chemistry and environmental fate. Classification of pollutants is important because it informs fate processes and apposite removal technologies. The occurrence of emerging contaminants (ECs) in water bodies is a source of environmental and human health concern globally. Despite being widely reported, data on the occurrence of ECs in South Africa are scarce. Specifically, ECS in wastewater in the Northern Cape in South Africa are understudied. In this study, various ECs were screened in water samples collected from three wastewater treatment plants (WWTPs) in the province. The ECs were detected using liquid chromatography coupled to high resolution Orbitrap mass spectrometry following Oasis HLB solid-phase extraction. The main findings were: (1) there is a wide variety of ECs in the WWTPs, (2) physico-chemical properties such as pH, total dissolved solids, conductivity, and dissolved organic content showed reduced values in the outlet compared to the inlet which confirms the presence of less contaminants in the treated wastewater, (3) specific ultraviolet absorbance of less than 2 was observed in the WWTPs samples, suggesting the presence of natural organic matter (NOM) that is predominantly non-humic in nature, (4) most of the ECs were recalcitrant to the treatment processes, (5) pesticides, recreational drugs, and analgesics constitute a significant proportion of pollutants in wastewater, and (6) NOM removal ranged between 35 and 90%. Consequently, a comprehensive database of ECs in wastewater in Sol Plaatje Municipality was created. Since the detected ECs pose ecotoxicological risks, there is a need to monitor and quantify ECs in WWTPs. These data are useful in selecting suitable monitoring and control strategies at WWTPs.

The high global consumption of ibuprofen and its limited elimination by wastewater treatment plants (WWTPs), has led to the contamination of aquatic systems by this common analgesic and its metabolites. The potentially negative environmental and public health effects of this emerging contaminant have raised concerns, driving the demand for treatment technologies. The implementation of bacteria which mineralize organic contaminants in biopurification systems used to decontaminate water or directly in processes in WWTPs, is a cheap and sustainable means for complete elimination before release into the environment. In this work, an ibuprofen-mineralizing bacterial strain isolated from sediments of the River Elbe was characterized and assayed to remediate different ibuprofen-polluted media. Strain RW412, which was identified as Sphingopyxis granuli, has a 4.48 Mb genome which includes plasmid sequences which harbor the ipf genes that encode the first steps of ibuprofen mineralization. Here, we confirm that these genes encode enzymes which initiate CoA ligation to ibuprofen, followed by aromatic ring activation by a dioxygenase and retroaldol cleavage to unequivocally produce 4-isobutylcatechol and propionyl-CoA which then undergo further degradation. In liquid mineral salts medium, the strain eliminated more than 2 mM ibuprofen within 74 h with a generation time of 16 h. Upon inoculation into biopurification systems, it eliminated repeated doses of ibuprofen within a few days. Furthermore, in these systems the presence of RW412 avoided the accumulation of ibuprofen metabolites. In ibuprofen-spiked effluent from a municipal WWTP, ibuprofen removal by this strain was 7 times faster than by the indigenous microbiota. These results suggest that this strain can persist and remain active under environmentally relevant conditions, and may be a useful innovation to eliminate this emerging contaminant from urban wastewater treatment systems.

Chemical analysis of plasma samples of wild fish from the Sava River (Croatia) revealed the presence of 90 different pharmaceuticals/illicit drugs and their metabolites (PhACs/IDrgs). The concentrations of these PhACs/IDrgs in plasma were 10 to 1000 times higher than their concentrations in river water. Antibiotics, allergy/cold medications and analgesics were categories with the highest plasma concentrations. Fifty PhACs/IDrgs were identified as chemicals of concern based on the fish plasma model (FPM) effect ratios (ER) and their potential to activate evolutionary conserved biological targets. Chemicals of concern were also prioritized by calculating exposure-activity ratios (EARs) where plasma concentrations of chemicals were compared to their bioactivities in comprehensive ToxCast suite of in vitro assays. Overall, the applied prioritization methods indicated stimulants (nicotine, cotinine) and allergy/cold medications (prednisolone, dexamethasone) as having the highest potential biological impact on fish. The FPM model pointed to psychoactive substances (hallucinogens/stimulants and opioids) and psychotropic substances in the cannabinoids category (i.e. CBD and THC). EAR confirmed above and singled out additional chemicals of concern - anticholesteremic simvastatin and antiepileptic haloperidol. Present study demonstrates how the use of a combination of chemical analyses, and bio-effects based risk predictions with multiple criteria can help identify priority contaminants in freshwaters. The results reveal a widespread exposure of fish to complex mixtures of PhACs/IDrgs, which may target common molecular targets. While many of the prioritized chemicals occurred at low concentrations, their adverse effect on aquatic communities, due to continuous chronic exposure and additive effects, should not be neglected.

The use of reclaimed wastewater for irrigation is foreseen as a possible strategy to mitigate the pressure on water resources in dry regions. However, there is the risk of potential accumulation of contaminants of emerging concern (CECs) in the edaphic environment, their percolation and consequently contamination of aquifers. In the present study, we measured the levels of a wide range of commonly used pharmaceutically active compounds (PhACs) in sewage from a local wastewater treatment plant (WWTP) and in soils irrigated with treated wastewater. Analysis of target compounds showed total concentrations between 73 and 372 μg L⁻¹ in WWTP influents, and from 3 to 41 μg L⁻¹ in effluents. The total concentrations of PhACs detected in surface soil samples were in the range of 2 and 15 ng g⁻¹, with predominance of analgesics and anti-inflammatories (maximum concentration = 10.05 ng g⁻¹), followed by antibiotics and psychiatric drugs (maximum concentration = 5.45 ng g⁻¹ and 3.78 ng g⁻¹, respectively). Both effluent samples and irrigated soils shared similar compositional patterns, with compounds such as hydrochlorothiazide and diclofenac being predominant. Additionally, PhACs were also detected in soil samples at a depth of 150 cm, indicating that these chemical undergo leaching associated with heavy-rain episodes. Their occurrence in soils was affected by temperature too, as maximum concentrations were measured in colder months (up to 14 ng g⁻¹), indicating higher persistence at lower temperatures. Finally, the ecotoxicological risk of PhACs in soil was evaluated by calculating their risk quotients (RQs). The risk was very low as RQ values ranged between <0.01 and 0.07. However, this initial assessment could be improved by future works on toxicity using specific terrestrial organisms.

Effects of the common antibacterial agent triclosan on microbial communities and degradation of domestic xenobiotics were studied in simulated sewage-drain-field soil. Cultivable microbial populations decreased 22-fold in the presence of 4 mg kg⁻¹ of triclosan, and triclosan-resistant Pseudomonas strains were strongly enriched. Exposure to triclosan also changed the general metabolic profile (Ecoplate substrate profiling) and the general profile (T-RFLP) of the microbial community. Triclosan degradation was slow at all concentrations tested (0.33–81 mg kg⁻¹) during 50-days of incubation. Mineralization experiments (¹⁴C-tracers) and chemical analyses (LC–MS/MS) showed that the persistence of a linear alkylbenzene sulfonate (LAS) and a common analgesic (ibuprofen) increased with increasing triclosan concentrations (0.16–100 mg kg⁻¹). The largest effect was seen for LAS mineralization which was severely reduced by 0.16 mg kg⁻¹ of triclosan. Our findings indicate that environmentally realistic concentrations of triclosan may affect the efficiency of biodegradation in percolation systems.

Bank filtration (BF) has been employed for more than a century for the production of water with a better quality, and it has been showing satisfactory results in diclofenac attenuation. Considered the most administered analgesic in the world, diclofenac has been frequently detected in water bodies. Besides being persistent in the environment, this compound is not completely removed by the conventional water treatments, drinking water treatment plants (DWTPs) and wastewater treatment plant (WWTPs). BF has a high complexity, whose efficiency depends on the characteristics of the observed pollutant and on the environment where the system in installed, which is why this is a topic that has been constantly studied. Nevertheless, studies present the behavior of diclofenac during the BF process. In this context, this research performed the evaluation of the factors and the biogeochemical processes that influence the efficiency of the BF technique in diclofenac removal. The aerobic conditions, higher temperatures, microbial biomass density, hydrogen potential close to neutrality and sediments with heterogeneous fractions are considered the ideal conditions in the aquifer for diclofenac removal. Nonetheless, there is no consensus on which of these factors has the greatest contribution on the mechanism of attenuation during BF. Studies with columns in laboratory and modeling affirm that the highest degradation rates occur in the first centimeters (5–50 cm) of the passage of water through the porous medium, in the environment known as hyporheic zone, where intense biogeochemical activities occur. Research has shown 100% removal efficiency for diclofenac persistent to compounds not removed during the BF process. However, half of the studies had removal efficiency that ranged between 80 and 100%. Therefore, the performance of more in-depth studies on the degradation and mobility of this compound becomes necessary for a better understanding of the conditions and biogeochemical processes which act in its attenuation.

The current investigation of marine water from 30 sites adjacent to stormwater outlets across the entire Sydney estuary is the first such research in Australia. The number of analytes detected were: 8/59 pharmaceutical compounds (codeine, paracetamol, tramadol, venlafaxine, propranolol, fluoxetine, iopromide and carbamazepine), 7/38 of the pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), 3,4-dichloroaniline, carbaryl, diuron, 2-methyl-4-chlorophenoxyacetic acid (MCPA), mecoprop and simazine) and 0/3 of the personal care products (PCPs) analysed. An artificial sweetener (acesulfame) was detected, however none of the nine antibiotics analysed were identified. Sewage water is not discharged to this estuary, except infrequently as overflow during high-precipitation events. The presence of acesulfame (a recognised marker of domestic wastewater) and pharmaceuticals in water from all parts of the estuary after a dry period, suggests sewage water is leaking into the stormwater system in this catchment. The pesticides are applied to the environment and were discharged via stormwater to the estuary.

This paper deals with the detection and quantification of APIs and other priority substances in the Arade River estuary (Portugal) providing the usefulness of Polar Organic Compound Integrative Samplers (POCIS). Thirteen APIs were detected whose variation was site and time dependent. Caffeine was at the highest concentration (804±209ng/L) followed by theophylline (184±44ng/L). Other APIs were analgesic, anticonvulsant, non-steroidal anti-inflammatory drugs, anti-lipidemic, anxiolytic and antidepressants. Twenty pesticides comprising atrazine, diuron, isoproturon, terbutryn and simazine included in the Water Framework Directive priority list were also site and time dependent. Carbendazim occurred at the highest concentration (45±18ng/L at site 1) but atrazine, diuron, isoproturon and simazine levels were below the Environmental Quality Standards. Although the summer impact was unclear, the results highlighted POCIS suitability for profiling these contaminants. This is to our knowledge the first study concerning APIs and pesticides in this area.

As the knowledge on the joint effects of pharmaceuticals towards different non-target organisms is still limited, the aim of our study was to evaluate the toxicity of mixtures of pharmaceuticals, as well as their baseline toxicity towards three selected organisms, namely the bioluminescent bacteria Aliivibrio fischeri, the crustacean Daphnia magna, and the duckweed Lemna minor. Different mixtures composed of three up to five pharmaceuticals having the same or different mechanisms of action in terms of their therapeutic activity (non-steroidal anti-inflammatory drugs, opioid analgesic, antibacterial and anti-epileptic drugs) were investigated. The observed EC₅₀s were compared with those predicted using the concentration addition (CA) and independent action (IA) models. In general, the EC₅₀ values for mixtures predicted with the CA model were lower than those obtained with the IA model, although, in some cases, test predictions of these two models were almost identical. Most of the experimentally determined EC₅₀ values for the specific mixtures were slightly higher than those predicted with the CA model; hence, a less than additive effect was noted. Based on the obtained results, it might be concluded that the CA model assumes the worst-case scenario and gives overall closer predictions; therefore, it should be recommended also for modeling the mixture toxicity of pharmaceuticals with different modes of action.

The multi-template molecularly imprinted polymers reinforced with hybrid oxide nanoparticles were developed for the selective separation and determination of the trace level of naproxen (NPX), methocarbamol (MTH), and omeprazole (OMZ) simultaneously from biological and pharmaceutical samples. The polymers were constructed by magnetic core@shell molecularly imprinted polymer nanocomposite (Fe₃O₄/ZnO/CuO/MWCNT@MIP). An electrochemical sensor has been fabricated for this purpose. Fe₃O₄/ZnO/CuO/MWCNT nanocomposite was introduced to improve the electron transport capability and increase the sensor surface area, as well as enhance the electronic conductivity. The triple-template MIP-coated layer provides simultaneous selective identification of three analytes by using [Fe (CN)₆]³⁻/⁴⁻as the redox probe. Electrochemical behavior of MTH, NPX, and OMZ on the modified electrode (Fe₃O₄/ZnO/CuO/MWCNT@MIP) by various techniques such as cyclic voltammetry, differential pulse voltammetry, and chronoamperometry was examined. The morphology of the modified and unmodified carbon paste electrodes was performed by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The average crystal size for fabricated nanoparticles obtained by calculating the X-ray diffraction technique was 17 nm in the Scherer method. The particle size which was determined by SEM was 48 nm. Some electrochemical parameters such as the diffusion coefficient and electron transfer coefficient were determined. The effect of many variables such as the pH and scan rate was also investigated. Under optimal conditions, the sensor is designed in the linear range 5.0 nM-100 μM and 5.0 nM-100 μM and 1.0 nM-130 μM with a detection limit of 1.5 nM, 1.0 nM, and 0.7 nM for measurement OMZ, NPX, and MTH, respectively. The relative standard deviation (RSD) of the five measurements was 1.21%, 2.23%, and 2.56% for NPX, MTH, and OMZ. Finally, the designed sensor was successfully used for simultaneous detection of target analytes in the real samples; tablets, water samples, and biological samples.