Uptake and translocation of pharmaceutically active compounds by olive tree (Olea europaea L.) irrigated with treated municipal wastewater.

Introduction: The use of treated municipal wastewater (TWW) represents a relevant opportunity for irrigation of agricultural crops in semi-arid regions to counter the increasing water scarcity. Pharmaceutically active compounds (PhACs) are often detected in treated wastewater, posing a risk to humans and the environment. PhACs can accumulate in soils and translocate into different plant tissues, reaching, in some cases, edible organs and entering the food chain. Methods: This study evaluated the uptake and translocation processes of 10 PhACs by olive trees irrigated with TWW, investigating their accumulation in different plant organs. The experiment was conducted in southern Italy, in 2-year-old plants irrigated with three different types of water: freshwater (FW), TWW spiked with 10 PhACs at a concentration of 200 µg L-1 (1× TWW), and at a triple dose (3× TWW), from July to October 2021. The concentration of PhACs in soil and plant organs was assessed, collecting samples of root, stem, shoot, leaf, fruit, and kernel at 0 (T0), 50 (T1), and 107 (T2) days of irrigation. PhACs extraction from soil and plant organs was carried out using the QuEChERS method, and their concentrations were determined by high-resolution mass spectrometry coupled with liquid chromatography. Results: Results of uptake factors (UF) showed a different behavior between compounds according to their physicochemical properties, highlighting PhACs accumulation and translocation in different plant organs (also edible part) in 1× TWW and 3× TWW compared to FW. Two PhACs, carbamazepine and fluconazole, showed interactions with the soil-plant system, translocating also in the aerial part of the plant, with a translocation factor (TF) greater than 1, which indicates high root-to-leaf translocation. Discussion: Findings highlight that only few PhACs among the selected compounds can be uptaken by woody plants and accumulated in edible parts at low concentration. No effects of PhACs exposure on plant growth have been detected. Despite the attention to be paid to the few compounds that translocate into edible organs, these results are promising for adapting wastewater irrigation in crops. Increasing knowledge about PhACs behavior in woody plants can be important for developing optimized wastewater irrigation and soil management strategies to reduce PhACs accumulation and translocation in plants.

Uptake and accumulation of emerging contaminants in processing tomato irrigated with tertiary treated wastewater effluent: a pilot-scale study.

The reuse of treated wastewater for crop irrigation is vital in water-scarce semi-arid regions. However, concerns arise regarding emerging contaminants (ECs) that persist in treated wastewater and may accumulate in irrigated crops, potentially entering the food chain and the environment. This pilot-scale study conducted in southern Italy focused on tomato plants (Solanum lycopersicum L. cv Taylor F1) irrigated with treated wastewater to investigate EC uptake, accumulation, and translocation processes. The experiment spanned from June to September 2021 and involved three irrigation strategies: conventional water (FW), treated wastewater spiked with 10 target contaminants at the European average dose (TWWx1), and tertiary WWTP effluent spiked with the target contaminants at a triple dose (TWWx3). The results showed distinct behavior and distribution of ECs between the TWWx1 and TWWx3 strategies. In the TWWx3 strategy, clarithromycin, carbamazepine, metoprolol, fluconazole, and climbazole exhibited interactions with the soil-plant system, with varying degradation rates, soil accumulation rates, and plant accumulation rates. In contrast, naproxen, ketoprofen, diclofenac, sulfamethoxazole, and trimethoprim showed degradation. These findings imply that some ECs may be actively taken up by plants, potentially introducing them into the food chain and raising concerns for humans and the environment.

Uptake of different pharmaceuticals in soil and mycorrhizal artichokes from wastewater.

The irrigation with treated wastewater is among the main anthropogenic sources for the release of pharmaceuticals (PhACs) into the soils and their translocation into crops, with possible toxic and adverse effects on humans. The arbuscular mycorrhizal fungi (AMF) can be employed for the reduction of organic soil pollutants, even if their efficiency depends on the mycorrhizal fungi, the plant colonized, and the type and concentration of the contaminant. This study aimed to evaluate the uptake of PhACs from wastewaters of different qualities used for the irrigation of mycorrhizal artichoke plants, the presence in their edible parts and the role of the arbuscular mycorrhizal fungi. The research was carried out on artichoke plants not inoculated and inoculated with two different AMF and irrigated with treated wastewater (TW), groundwater (GW) or GW spiked with different and selected PhACs (SGW). The inocula were a crude inoculum of Septoglomus viscosum (MSE) and a commercial inoculum of Glomus intraradices and Glomus mosseae (MSY). The results of the present study showed that carbamazepine and fluconazole were found in the artichoke only with SGW irrigation. The mycorrhizal plants showed a reduction of the pharmaceutical's uptake, and within the AMF, MSE was more effective in preventing their absorption and translocation.

Life Cycle Assessment of UV-C based treatment systems for the removal of compounds of emerging concern from urban wastewater.

In the last decades particular attention is being paid to the efficient and effective removal of compounds of emerging concern (CECs) present in wastewater before their eventual reuse or disposal. Several technologies have been developed for the degradation of CECs in aqueous matrix, in this regard advanced oxidation processes (AOPs) represent a nascent technological solution developed on a laboratory scale with applications on a prototype scale. The experimental evidences have shown that AOPs processes can oxidize numerous organic compounds in a much faster and more efficient way than that of the most common disinfection processes. The most common AOPs processes are those that involve the use of H2O2/UV, O3/UV, H2O2/O3, H2O2/O3/UV, Fenton and photo-Fenton. The aim of this work is to illustrate the results of a comparative LCA study of a laboratory scale UV-C photoreactor for the tertiary treatment of urban wastewater of three treatment systems (UV-C, UV-C + H2O2 e UV-C + TiO2). In particular, the specific objective is to evaluate, from an environmental point of view, an innovative advanced oxidation system based on nanostructures TiO2 immobilized on a stainless steel mesh. Compared to the UV-C photolysis reference system, the addition of hydrogen peroxide reduces the total environmental impact of the system by almost 75 %, while the use of the stainless-steel mesh coated by the nanostructures titanium dioxide reduces the UV-C environmental impact by 30 %. These results are due to the lower energy consumption of these last treatments compared to photolysis alone. The main impacts of the three systems are related to the electric power consumption of the centrifugal pump (63-64 %) and of the UV-C lamp (32-33 %). The LCA applied to these systems has shown that TiO2 assisted photocatalysis is not yet advantageous from an environmental point of view and that, therefore, the efficiency of the system needs to be improved.

Use of constructed wetlands to prevent overloading of wastewater treatment plants.

The fluctuation in the number of people in tourist areas affects the wastewater quality and quantity. Constructed wetlands (CWs) aim to simulate physical, chemical, and biological processes occurring in natural environments for wastewater treatment and are considered a sustainable system. The current study aimed at evaluating the effectiveness of in-vessel CWs for supporting the wastewaters treatment plants in periods of overloading. Such approach can be quickly implementable, economic, and the CWs can be fast regenerated in the framework of sustainable good practices. Three pilot scale CWs were prepared in as many containers layering 10 cm of gravel, 60 cm of sand and 10 cm of gravel, and placing pieces of giant reed rhizomes in the upper layers. The bottom of each CW had a tap, and CWs were irrigated with a real municipal sewage three times a week. Before each new irrigation, the tap was opened, and the effluent collected for determining gross parameters, elemental composition, and contaminants of emerging concern (CECs). CWs significantly reduced almost all gross parameters considered and half the CECs, except for a couple of metabolites of corresponding parental compounds. With regards to the potentially toxic elements, all reduced their concentration from the influents to the effluents. The results of this study were promising and highlighted good efficiency of constructed wetlands as pre-treatment of real municipal sewage to reduce the overloading of the wastewater treatment plant.

Biodegradation and Metabolic Pathway of 17ß-Estradiol by Rhodococcus sp. ED55.

Endocrine disrupting compounds (EDCs) in the environment are considered a motif of concern, due to the widespread occurrence and potential adverse ecological and human health effects. The natural estrogen, 17ß-estradiol (E2), is frequently detected in receiving water bodies after not being efficiently removed in conventional wastewater treatment plants (WWTPs), promoting a negative impact for both the aquatic ecosystem and human health. In this study, the biodegradation of E2 by Rhodococcus sp. ED55, a bacterial strain isolated from sediments of a discharge point of WWTP in Coloane, Macau, was investigated. Rhodococcus sp. ED55 was able to completely degrade 5 mg/L of E2 in 4 h in a synthetic medium. A similar degradation pattern was observed when the bacterial strain was used in wastewater collected from a WWTP, where a significant improvement in the degradation of the compound occurred. The detection and identification of 17 metabolites was achieved by means of UPLC/ESI/HRMS, which proposed a degradation pathway of E2. The acute test with luminescent marine bacterium Aliivibrio fischeri revealed the elimination of the toxicity of the treated effluent and the standardized yeast estrogenic (S-YES) assay with the recombinant strain of Saccharomyces cerevisiae revealed a decrease in the estrogenic activity of wastewater samples after biodegradation.

The Geological Characteristics of the Vadose Zone Influence the Impact of Treated Wastewater on the Groundwater Quality (SCA.Re.S. Project 2019-2020).

This study evaluated whether some chemical and microbial contaminants in treated sewage effluents from two wastewater treatment plants (WWTP) reached the groundwater when they drained through a fractured karst vadose zone (WWTP-K) and a porous vadose zone (WWTP-P). Forty-five samples of sewage water (SW), treated water (TW), and monitoring well (MW), collected from WWTP-P (24) and WWTP-K (21), were analyzed for a range of microbiological and chemical properties. The E. coli and Salmonella counts were below the limits outlined in the Legislative Decree 152/06 in effluents from both types of WWTP. Enteric viruses were found in 37.5% and 12.5% of the SW and TW from WWTP-P, respectively. The percentages of Pepper mild mottle virus isolated were higher in TW (62.5% in WWTP-P, 85.7% in WWTP-K) than in SW and MW. The residual concentrations of contaminants of emerging concern (CEC) of each drug category were higher in the MW downstream of WWTP-K than of WWTP-P. Our results showed that the porous vadose zone was more effective at reducing the contaminant loads than the fractured karst one, especially the CEC, in the effluent. The legislation should include other parameters to minimize the risks from treated effluent that is discharged to soil.

Inter-laboratory mass spectrometry dataset based on passive sampling of drinking water for non-target analysis.

Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied approach for the detection of novel chemicals of emerging concern in complex environmental samples. NTA typically results in large and information-rich datasets that require computer aided (ideally automated) strategies for their processing and interpretation. Such strategies do however raise the challenge of reproducibility between and within different processing workflows. An effective strategy to mitigate such problems is the implementation of inter-laboratory studies (ILS) with the aim to evaluate different workflows and agree on harmonized/standardized quality control procedures. Here we present the data generated during such an ILS. This study was organized through the Norman Network and included 21 participants from 11 countries. A set of samples based on the passive sampling of drinking water pre and post treatment was shipped to all the participating laboratories for analysis, using one pre-defined method and one locally (i.e. in-house) developed method. The data generated represents a valuable resource (i.e. benchmark) for future developments of algorithms and workflows for NTA experiments.

Microbiological and Chemical Assessment of Wastewater Discharged by Infiltration Trenches in Fractured and Karstified Limestone (SCA.Re.S. Project 2019-2020).

This study investigated the environmental contamination of groundwater as a consequence of the discharge of treated wastewater into the soil. The investigation focused on a wastewater treatment plant located in an area fractured by karst in the Salento peninsula (Apulia, Italy). Water samples were collected at four sites (raw wastewater, treated wastewater, infiltration trench, and monitoring well), monthly from May to December 2019 (with the exception of August), and were tested for (1) panel of bacteria; (2) enteric viruses; and (3) chemical substances. A gradual reduction in the concentration of bacteria, viruses and contaminants of emerging concern was observed across the profile of soil fissured by karst. All monitored bacteria were absent from the monitoring well, except for Pseudomonas aeruginosa. Pepper mild mottle virus and adenovirus were detected at all sampling sites. Personal care products and X-ray contrast media showed the greatest decrease in concentration from infiltration trench to the monitoring well, while the highest residual concentrations in the monitoring well were found for anticonvulsants (78.5%), antimicrobials (41.3%), and antipsychotic drugs (38.6%). Our results show that parameters provided by current law may not always be sufficient to evaluate the sanitary risk relating to the discharge of treated wastewater to the soil.

Gold-Speckled SPION@SiO2 Nanoparticles Decorated with Thiocarbohydrates for ASGPR1 Targeting: Towards HCC Dual Mode Imaging Potential Applications.

Efforts are made to perform an early and accurate detection of hepatocellular carcinoma (HCC) by simultaneous exploiting multiple clinically non-invasive imaging modalities. Original nanostructures derived from the combination of different inorganic domains can be used as efficient contrast agents in multimodal imaging. Superparamagnetic iron oxide nanoparticles (SPIONs) and Au nanoparticles (NPs) possess well-established contrasting features in magnetic resonance imaging (MRI) and X-ray computed tomography (CT), respectively. HCC can be targeted by using specific carbohydrates able to recognize asialoglycoprotein receptor 1 (ASGPR1) overexpressed in hepatocytes. Here, two different thiocarbohydrate ligands were purposely designed and alternatively conjugated to the surface of Au-speckled silica-coated SPIONs NPs, to achieve two original nanostructures that could be potentially used for dual mode targeted imaging of HCC. The results indicated that the two thiocarbohydrate decorated nanostructures possess convenient plasmonic/superparamagnetic properties, well-controlled size and morphology and good selectivity for targeting ASGPR1 receptor.

Carbamazepine is degraded by the bacterial strain Labrys portucalensis F11.

The occurrence of pharmaceuticals in the environment is a topic of concern. Carbamazepine (CBZ) is a widespread antiepileptic drug and due to its physical-chemical characteristics minimal removal is achieved in conventional water treatments, and thus has been suggested as a molecular marker of wastewater contamination in surface water and groundwater. The present study reports the biotransformation of CBZ by the bacterial strain Labrys portucalensis F11. When supplied as a sole carbon source, a 95.4% biotransformation of 42.69 µM CBZ was achieved in 30 days. In co-metabolism with acetate, complete biotransformation was attained at a faster rate. Following a target approach, the detection and identification of 14 intermediary metabolites was achieved through UPLC-QTOF/MS/MS. Biotransformation of CBZ by the bacterial strain is mostly based on oxidation, loss of -CHNO group and ketone formation reactions; a biotransformation pathway with two routes is proposed. The toxicity of untreated and treated CBZ solutions was assessed using Vibrio Fischeri and Lepidium sativum acute toxicity tests and Toxi-Chromo Test. The presence of CBZ and/or its degradations products in solution resulted in moderate toxic effect on Vibrio Fischeri, whereas the other organisms were not affected. To the best of our knowledge this is the first report that proposes the metabolic degradation pathway of CBZ by a single bacterial strain.

Photocatalytic Degradation of Diclofenac by Hydroxyapatite⁻TiO2 Composite Material: Identification of Transformation Products and Assessment of Toxicity.

Diclofenac (DCF) is one of the most detected pharmaceuticals in environmental water matrices and is known to be recalcitrant to conventional wastewater treatment plants. In this study, degradation of DCF was performed in water by photolysis and photocatalysis using a new synthetized photocatalyst based on hydroxyapatite and TiO2 (HApTi). A degradation of 95% of the target compound was achieved in 24 h by a photocatalytic treatment employing the HApTi catalyst in comparison to only 60% removal by the photolytic process. The investigation of photo-transformation products was performed by means of UPLC-QTOF/MS/MS, and for 14 detected compounds in samples collected during treatment with HApTi, the chemical structure was proposed. The determination of transformation product (TP) toxicity was performed by using different assays: Daphnia magna acute toxicity test, Toxi-ChromoTest, and Lactuca sativa and Solanum lycopersicum germination inhibition test. Overall, the toxicity of the samples obtained from the photocatalytic experiment with HApTi decreased at the end of the treatment, showing the potential applicability of the catalyst for the removal of diclofenac and the detoxification of water matrices.

Biodegradation of Diclofenac by the bacterial strain Labrys portucalensis F11.

Diclofenac (DCF) is a widely used non-steroidal anti-inflammatory pharmaceutical which is detected in the environment at concentrations which can pose a threat to living organisms. In this study, biodegradation of DCF was assessed using the bacterial strain Labrys portucalensis F11. Biotransformation of 70% of DCF (1.7-34 µM), supplied as the sole carbon source, was achieved in 30 days. Complete degradation was reached via co-metabolism with acetate, over a period of 6 days for 1.7 µM and 25 days for 34 µM of DCF. The detection and identification of biodegradation intermediates was performed by UPLC-QTOF/MS/MS. The chemical structure of 12 metabolites is proposed. DCF degradation by strain F11 proceeds mainly by hydroxylation reactions; the formation of benzoquinone imine species seems to be a central step in the degradation pathway. Moreover, this is the first report that identified conjugated metabolites, resulting from sulfation reactions of DCF by bacteria. Stoichiometric liberation of chlorine and no detection of metabolites at the end of the experiments are strong indications of complete degradation of DCF by strain F11. To the best of our knowledge this is the first report that points to complete degradation of DCF by a single bacterial strain isolated from the environment.

Ultra-trace levels analysis of microcystins and nodularin in surface water by on-line solid-phase extraction with high-performance liquid chromatography tandem mass spectrometry.

An on-line solid phase extraction coupled with high-performance liquid chromatography in tandem with mass spectrometry (on-line SPE/HPLC/MS-MS) method for the determination of five microcystins and nodularin in surface waters at submicrogram per liter concentrations has been optimized. Maximum recoveries were achieved by carefully optimizing the extraction sample volume, loading solvent, wash solvent, and pH of the sample. The developed method was also validated according to both UNI EN ISO IEC 17025 and UNICHIM guidelines. Specifically, ten analytical runs were performed at three different concentration levels using a reference mix solution containing the six analytes. The method was applied for monitoring the concentrations of microcystins and nodularin in real surface water during a sampling campaign of 9 months in which the ELISA method was used as standard official method. The results of the two methods were compared showing good agreement when the highest concentration values of MCs were found. Graphical abstract An on-line SPE/HPLC/MS-MS method for the determination of five microcystins and nodularin in surface waters at sub µg L(-1) was optimized and compared with ELISA assay method for real samples.