Selection of pharmaceuticals of concern in reclaimed water for crop irrigation in the Mediterranean area.

The reuse of reclaimed water in agriculture is being fostered in areas suffering from water scarcity. However, water pollutants can compromise food safety and pose a risk for the environment. This study aims to select the pharmaceutical compounds worth monitoring and investigating when reclaimed water is used for tomato and lettuce irrigation. A comprehensive study was first conducted to identify the pharmaceuticals frequently detected in secondary wastewater effluents in Catalonia (Northeast Spain). Priority pharmaceuticals were further selected based on their occurrence in secondary effluents, persistence (removal in conventional treatment), bioaccumulation potential, toxicity for aquatic organisms, and the risks they pose to the terrestrial environment and human health (through the consumption of crops). Out of the 47 preselected priority compounds, six could pose a risk to organisms living in soil irrigated with reclaimed water and seven could be potentially taken up by the crops. Nonetheless, no risk for human consumption was foreseen.

Selection of indicator contaminants of emerging concern when reusing reclaimed water for irrigation - A proposed methodology.

Organic and microbial contaminants of emerging concern (CECs), even though not yet regulated, are of great concern in reclaimed water reuse projects. Due to the large number of CECs and their different characteristics, it is useful to include only a limited number of them in monitoring programs. The selection of the most representative CECs is still a current and open question. This study presents a new methodology for this scope, in particular for the evaluation of the performance of a polishing treatment and the assessment of the risk for the environment and the irrigated crops. As to organic CECs, the methodology is based on four criteria (occurrence, persistence, bioaccumulation and toxicity) expressed in terms of surrogates (respectively, concentrations in the secondary effluent, removal achieved in conventional activated sludge systems, Log Kow and predicted-no-effect concentration). It consists of: (i) development of a dataset including the CECs found in the secondary effluent, together with the corresponding values of surrogates found in the literature or by in-field investigations; (ii) normalization step with the assignment of a score between 1 (low environmental impact) and 5 (high environmental impact) to the different criteria based on threshold values set according to the literature and experts' judgement; (iii) CEC ranking according to their final score obtained as the sum of the specific scores; and (iv) selection of the representative CECs for the different needs. Regarding microbial CECs, the selection is based on their occurrence and their highest detection frequency in the secondary effluent and in the receiving water, the antibiotic consumption patterns, and recommendations by national and international organisations. The methodology was applied within the ongoing reuse project SERPIC resulting in a list of 30 indicator CECs, including amoxicillin, bisphenol A, ciprofloxacin, diclofenac, erythromycin, ibuprofen, iopromide, perfluorooctane sulfonate (PFOS), sulfamethoxazole, tetracycline, Escherichia coli, faecal coliform, 16S rRNA, sul1, and sul2.

A review of the occurrence of selected micropollutants and microorganisms in different raw and treated manure - Environmental risk due to antibiotics after application to soil.

This study consists of a review based on 104 papers published between 1980 and 2019, which dealt with the occurrence of pharmaceuticals, hormones and a selection of microorganisms in raw and treated manure from different types of animal farms. The selected pharmaceuticals and hormones are those regularly administered to livestock for treating and preventing diseases. Worldwide, manure is commonly spread on soil as a fertilizer due to its nutrient content. However, this practice also represents a potential pathway for micropollutant release into the environment. In this context, this study evaluates the predicted concentrations of some antibiotics in soil after the application of swine slurry on soil and compares them with corresponding measured concentrations found in the literature. Enrofloxacin, oxytetracycline and chlortetracycline were the antibiotics with the highest concentrations that were found in raw and treated manure and that showed a high risk together with sulfamethazine. Future research should focus on monitoring other pathogens, parent compounds and their main metabolites in raw and treated manure, studying the spread and development of antibiotic resistance genes in the environment due to residues of antibiotics in manure applied to soil, and evaluating predicted no effect concentrations of pharmaceuticals and hormones commonly administered to livestock with regard to terrestrial organisms.

A review of selected microcontaminants and microorganisms in land runoff and tile drainage in treated sludge-amended soils.

The objective of this study is to provide a snapshot of the quality of surface runoff and tile drainage in sludge-amended soil in terms of 57 microcontaminants, including pharmaceuticals, hormones and fragrances, and 5 different species of bacteria. It also discusses the main factors affecting their occurrence (soil characteristics, applied sludge load and rate, sludge application method, rain intensity and frequency). It is based on 38 investigations carried out by different research groups in Canada, Australia, the USA and Ireland. The most frequently investigated compounds were hormones, the antiseptics triclosan and triclocarban, the analgesics and anti-inflammatories acetaminophen, ibuprofen and naproxen, the antibiotic sulfamethoxazole, the lipid regulator gemfibrozil and the psychiatric drug carbamazepine. Of all the bacteria, E. coli was the most monitored species. It was found that concentrations of the studied pollutants in surface runoff and tile drainage may vary, depending on many factors. They are generally lower than those observed in the secondary municipal effluent and in surface water, but their contribution to the deterioration of surface water quality might be relevant, mainly in wide rural areas. In this context, the reported data or their ranges represent an attempt to provide reference thresholds and bands of observed concentrations for a rough estimation of the contribution made by the release of the selected pollutants into surface water bodies via surface runoff and tile drainage.

Contributions of combined sewer overflows and treated effluents to the bacterial load released into a coastal area.

The impact of combined sewer overflow (CSO) on the receiving water body is an issue of increasing concern, as it may lead to restrictions in the use and destination of the receiving body, such as bathing or recreational area closures, fish and shellfish consumption restrictions, and contamination of drinking water resources. Recent investigations have mainly referred to the occurrence and loads of suspended solids, organic compounds and, in some cases, micropollutants. Attempts have been made to find correlations between the discharged load and the size and characteristics of the catchment area, climate conditions, rainfall duration and intensity. This study refers to a touristic coastal area in the north-east of Italy, which is characterized by a combined sewer network including 5 CSO outfalls which, in the case of heavy rain events, directly discharge the exceeding water flow rate into channels which, after a short distance, reach the Adriatic Sea. The study analyzed: i) rainfall events during the summer period in 2014 which led to overflow in the different outfalls, ii) the inter- and intra-event variability with regard to E. coli, Enterococci and conductivity, and iii) the hydraulic and pollutant (E. coli and Enterococci) loads discharged by the local wastewater treatment plant and by all the CSO outfalls. Finally, it estimated the contribution of each source to the released hydraulic and pollutant loads into the receiving water body. Moreover, it was also found that the modest water volume discharged by all CSO outfalls (only 8% of the total volume discharged by the area) contains >90% of the microbial load.

Pharmaceuticals and personal care products in untreated and treated sewage sludge: Occurrence and environmental risk in the case of application on soil - A critical review.

This review is based on 59 papers published between 2002 and 2015, referring to about 450 treatment trains providing data regarding sludge concentrations for 169 compounds, specifically 152 pharmaceuticals and 17 personal care products, grouped into 28 different classes. The rationale of the study is to provide data to evaluate the environmental risk posed by the spreading of treated sludge in agriculture. Following discussion of the legislative scenario governing the final disposal of treated sludge in European countries and the USA, the study provides a snapshot of the occurrence of selected compounds in primary, secondary, mixed, digested, conditioned, composted and dried sludge originating in municipal wastewater treatment plants fed mainly with urban wastewater as well as in sludge-amended soil. Not only are measured values reported, but also predicted concentrations based on Kd values are reported. It emerges that in secondary sludge, the highest concentrations were found for fragrances, antiseptics and antibiotics and an attenuation in their concentrations occurs during treatment, in particular anaerobic digestion and composting. An in-depth literature survey of the (measured and predicted) Kd values for the different compounds and treated sludge are reported and an analysis of the influence of pH, redox conditions, sludge type was carried out. The data regarding measured and predicted concentrations of selected compounds in sludge-amended soil is then analyzed. Finally an environmental risk assessment posed by their occurrence in soil in the case of land application of sludge is examined, and the results obtained by different authors are compared. The most critical compounds found in the sludge-amended soil are estradiol, ciprofloxacin, ofloxacin, tetracycline, caffeine, triclosan and triclocarban. The study concludes with a focus on the main issues that should be further investigated in order to refine the environmental risk assessment.

What have we learned from worldwide experiences on the management and treatment of hospital effluent? - an overview and a discussion on perspectives.

This study overviews lessons learned from experimental investigations on dedicated treatment systems of hospital effluent carried out worldwide in the last twenty years. It includes 48 peer reviewed papers from 1995 to 2015 assessing the efficacy of different treatment levels (preliminary, primary, secondary and polishing) of hospital wastewater in removing a wide spectrum of pharmaceutical compounds as well as conventional contaminants. Moreover, it highlights the rationale and the reasons for each study: reducing the discharge of micropollutants in surface water, improving existing wastewater treatment technologies and reducing the risk of spread of pathogens causing endemic diseases and finally, it offers a critical analysis of the conclusions and suggestions of each study. The most investigated technologies are membrane bioreactors equipped with ultrafiltration membranes in the secondary step, ozonation followed by activated carbon filtration (in powder and in granules) in the polishing step. Interesting research projects deal with photo-Fenton processes acting as primary treatments to enhance biodegradation before biological treatment, and as a polishing step, thus further reducing micro-contaminant occurrence. Investment and operational costs are also presented and discussed for the different treatment technologies tested worldwide, in particular membrane bioreactors and various advanced oxidation processes. This study also discusses the need for further research to evaluate toxicity resulting from advanced oxidation processes as well as the need to develop an accurate feasibility study that encompasses technical, ecotoxicological and economic aspects to identify the best available treatment in the different situations from a global view point.

Comparison of measured and predicted concentrations of selected pharmaceuticals in wastewater and surface water: a case study of a catchment area in the Po Valley (Italy).

The aim of this study is to compare measured and predicted concentrations of 11 antibiotics and the antiepileptic carbamazepine in wastewater and surface water and to discuss the accuracy and usefulness of applied predictive models in assessing their concentrations. The occurrence (exposure assessment) of the target compounds was monitored in the influent and effluent of a large municipal wastewater treatment plant, and in its receiving water body, situated in the Po Valley, Italy. Information on the consumption and sales of pharmaceuticals in Italy, along with data related to their excretion and removal during wastewater treatment, were used to predict the concentrations of the selected pharmaceuticals for the studied site. The measured and predicted concentrations were compared for all three sampling points, and according to a criterion available in literature and already adopted in similar studies, the prediction was considered "acceptable" when the ratio of predicted and measured concentrations was between 0.5 and 2. The results show that the concentrations were accurately predicted for ciprofloxacin in wastewaters, and for azithromycin, trimethoprim and carbamazepine in surface water. For all the other compounds and sampling points, the difference between the measured and the predicted concentrations was very high. Possible reasons for these discrepancies are discussed and the main potential factors that influence both measured and predicted concentrations are identified by means of an assessment of the uncertainties in the measured values and sensitivity of all the parameters required for predicting concentration ones. The potential factors are sampling mode for measured values and dilution factor, removal and excretion for predicted ones.

Removal of selected pharmaceuticals from domestic wastewater in an activated sludge system followed by a horizontal subsurface flow bed - analysis of their respective contributions.

Seventy-three commonly administered pharmaceuticals from twelve different therapeutic classes were investigated at a municipal wastewater treatment plant in northern Italy featuring a conventional activated sludge system (full-scale) and a polishing horizontal subsurface flow bed (pilot plant). Removal of these micro-pollutants by the two systems was assessed in order to evaluate their respective contributions. Mean concentrations and standard deviations were calculated and found to differ for the compounds detected, ranging from few ng/L to over 1,165 ng/L in the secondary effluent and from 11 to 533 in the polished effluent. Eighteen compounds were consistently below the detection limit and the remaining 55 compounds were found at a minimum of one sampling point. Average removal efficiencies of both treatment steps and in treatment train as a whole are evaluated and discussed, highlighting the difficulties in predicting the fate of pharmaceuticals in both an activated sludge system and a horizontal subsurface flow bed. Comparison between the observed average removal efficiencies and those reported in the literature was also carried out for the pharmaceuticals of interest, and the discrepancies that emerged are discussed. The investigated constructed wetland did show efficacy in removing some of these compounds, and it contributed to the overall removal efficiency of each therapeutic class. Indeed, evaluation of the specific mass loadings of each class of PhC detected in the raw wastewaters, secondary and polished effluent evidences that the investigated constructed wetland is able to further reduce the load of micropollutants, which could become a necessity, especially where the receiving water body is an effluent-dominant river and mitigation measures of the discharge impact are required to protect and safeguard the aquatic environment.

Monitoring release of pharmaceutical compounds: occurrence and environmental risk assessment of two WWTP effluents and their receiving bodies in the Po Valley, Italy.

This study describes an investigation on the occurrence of 27 pharmaceutical compounds, belonging to different classes, in the effluent from two wastewater treatment plants (WWTPs) and their receiving water bodies in the sensitive area of the Po Valley (northern Italy). These canals were monitored upstream and downstream of the effluent discharge points in order to evaluate the effluent impact on the quality of surface waters, commonly used for irrigation. An environmental risk assessment was also conducted by calculating the risk quotient, i.e. the ratio between measured concentration and predicted no effect concentration. Collected data show that, although average values of the selected compounds were in general higher in the effluent than in the surface waters, some compounds not detected in the WWTP effluent were detected in the receiving water (upstream as well as downstream), indicating that sources other than treated effluents are present as contaminations during extraction and analysis have to be excluded. The most critical compounds for the environment were found to be the antibiotics sulfamethoxazole, clarithromycin and azithromycin. The study shows that the potential toxicological effects of persistent micropollutants can be mitigated to some extent by a high dilution capacity, i.e. a high average flow rate in the receiving water body with respect to the effluent.

Hospital effluent: investigation of the concentrations and distribution of pharmaceuticals and environmental risk assessment.

A study was conducted in an area in north, Italy, on the effluent of two different sized hospitals and the influent and effluent of the receiving municipal treatment plant of one of the examined hospitals. The aim was to investigate 73 selected pharmaceuticals, belonging to twelve different classes, comparing their occurrence in the effluent directly exiting the hospital with that, mixed with the local urban effluent, at the point of its entry and exit from the treatment plant. Consistent differences were found in the concentrations of some antibiotics, analgesics and lipid regulators in the two wastewaters, confirming that hospital effluents should not be considered as possessing the same pollutant nature as urban wastewater. Furthermore, analysis of percentage contributions of the hospital to the treatment plant influent evidences that hospitals represent one of the main sources of pollutants, in particular antibiotics, receptor antagonists and lipid regulators. Hence, an environmental risk assessment, performed on the effluent from the hospital and the influent and effluent from the treatment plant, revealed a high risk for 9 pharmaceuticals in hospital effluent and for 4 of the 9 substances in the treatment plant influent and effluent, with antibiotics being the most critical compounds in terms of contribution and potential environmental risk for the hospital.

Occurrence of pharmaceutical compounds in urban wastewater: removal, mass load and environmental risk after a secondary treatment--a review.

This review focuses on 118 pharmaceuticals, belonging to seventeen different therapeutic classes, detected in raw urban wastewater and effluent from an activated sludge system, a usual treatment adopted for urban wastewaters worldwide prior to final discharge into surface water bodies. Data pertaining to 244 conventional activated sludge systems and 20 membrane biological reactors are analysed and the observed ranges of variability of each selected compound in their influent and effluent reported, with particular reference to the substances detected most frequently and in higher concentrations. A snapshot of the ability of these systems to remove such compounds is provided by comparing their global removal efficiencies for each substance. Where possible, the study then evaluates the average daily mass load of the majority of detected pharmaceuticals exiting the secondary treatment step. The final part of the review provides an assessment of the environmental risk posed by their presence in the secondary effluent by means of the risk quotient that is the ratio between the average pharmaceutical concentration measured in the secondary effluent and the predicted no-effect concentration. Finally, mass load rankings of the compounds under review are compared with those based on their risk level. This analysis shows that the highest amounts discharged through secondary effluent pertain to one antihypertensive, and several beta-blockers and analgesics/anti-inflammatories, while the highest risk is posed by antibiotics and several psychiatric drugs and analgesics/anti-inflammatories. These results are reported with a view to aiding scientists and administrators in planning measures aiming to reduce the impact of treated urban wastewater discharge into surface water bodies.

Improvement in the removal of micropollutants at Porto Marghera industrial wastewaters treatment plant by MBR technology.

This paper deals with the case of one of the most important industrial application of membrane technology in the world: the upgrading of the main industrial wastewater treatment plant (WWTP) of the petrochemical site of Porto Marghera, Northern Italy, completed on December 2005 and tested on September 2006. It describes the principal interventions of the plant upgrading and it discusses the removal obtained during the test periods for conventional pollutants as well as for micropollutants. The plant upgrading consisted of a series of improvements of the existing industrial WWTP, in order to increase the removal efficiency of the total suspended solids and the associate removal of ten micropollutant compounds, the so called forbidden substances. The most important intervention was the conversion of the existing activated sludge section into a membrane biological reactor, in order to guarantee adherence to the severe limits imposed by the special law issued to protect the Venice Lagoon, with particular reference to the mentioned 10 forbidden compounds. The experimental results and the numerous test-runs conducted confirmed the respect of the legal limits for the pollutants in the final effluent as well of the required removal rates for the different parameters. Therefore, the upgraded treatment plant was declared agreeing with the approved design.