Tackling climate change through wastewater reuse in agriculture: A prioritization methodology.

Water shortages, exacerbated by climate change, are posing a major global challenge, particularly impacting the agricultural sector. A growing interest is raised towards reclaimed wastewater (RWW) as an alternative irrigation source, capable of exploiting also the nutrient content through the fertigation practice. However, a prioritization methodology for selecting the most appropriate wastewater treatment plants (WWTPs) for implementing direct RWW reuse is currently missing. Such prioritization would benefit water utilities, often managing several WWTPs, and policymakers in optimizing economic asset allocation. In this work, a prioritization framework is proposed to evaluate WWTPs' suitability for implementing direct RWW reuse considering both WWTP and surrounding territory characteristics. This procedure consists of four key steps. Firstly, a techno-economic model was developed, in which monthly mass balances on water and nutrients are solved by matching crop requirements, rainfall conditions, and effluent characteristics. Economic suitability was quantified considering economic benefits due to savings in freshwater resource, mineral fertilizers and avoided greenhouse gases emissions, but also losses in crop yield due to RWW salinity content. Secondly, a classification procedure was coded to select representative WWTPs among a set of WWTPs, based on their size, presence of nutrient removal processes, and type of crops in their surroundings. The techno-economic model was then applied to these selected WWTPs. Thirdly, input parameters' relevance in determining WWTP suitability for RWW reuse was ranked. Finally, scenario analyses were conducted to study the influence of rainfall patterns and nutrient treatment removal on the RWW reuse feasibility. The type of crops surrounding the WWTPs and RWW salinity content resulted to be crucial elements in determining WWTPs suitability for RWW reuse implementation. The proposed methodology proved to be an effective support tool for policymakers and water utilities to assess the techno-economic feasibility of direct RWW reuse, generalizing results to several combinations of WWTPs and crops.

Adsorption on activated carbon combined with ozonation for the removal of contaminants of emerging concern in drinking water.

The presence of Contaminants of Emerging Concern (CECs) in drinking water is raising concern for potential negative effects on human health. Ozonation and adsorption on activated carbon are the most suitable processes for CECs removal in drinking water treatment plants (DWTPs). This study aims at evaluating the performance of ozonation and adsorption as in-series processes compared to those of the stand-alone processes, focusing on 18 compounds representative of various CECs families. No CECs spike was performed to evaluate the effectiveness of these processes towards CECs at their environmental concentrations. Adsorption isotherms were performed on water samples collected before and after the full-scale ozonation in a DWTP, testing different combinations of ozone and activated carbon doses. Generally, the combination of the two processes was beneficial (83% average removal) compared to adsorption and ozonation alone (71% and 34% average removal respectively). The effect of ozonation on adsorption depends on CECs reactivity with ozone, since ozonation improves the adsorption performance of poorly-oxidizable CECs, but worsens that of well-oxidizable compounds. The removal of organic matter, investigated by absorbance at 254 nm and fluorescence, by ozonation reduces competition for the subsequent CECs removal by adsorption (up to 20% increase of total CECs adsorption). Finally, the removal of both absorbance and fluorescence seems to be a good proxy variables for total CECs adsorption, with different relationships depending on the presence of ozonation. Conversely, it is not effective for ozonation, since the relationship depends on the reactivity of the specific CEC with ozone.

An integrated human health risk assessment framework for alkylphenols due to drinking water and crops' food consumption.

The increasing overexploitation and pollution of freshater resources are potential threats for public health, causing cross-contamination among the interconnected environmental compartments (freshwater, soil, crops). In particular, contaminants of emerging concern (CECs) originating from anthropic activities are not completely removed by wastewater treatments plants. This leads to their presence in drinking water (DW) sources, soil and crops intended for human consumption due to discharges of treated wastewater in surface waters and direct wastewater reuse practices. Currently, health risk assessments are limited to single exposure sources without considering the multiple exposure routes to which humans are subjected. For instance, among CECs, bisphenol A (BPA) and nonylphenol (NP), respectively, adversely affect immune and renal systems and have been frequently detected in DW and food, their major exposure sources for humans. Here, an integrated procedure is proposed to quantitatively assess health risk from CECs due to multiple exposure from the consumption of both DW and food, considering the relevant inter-connected environmental compartments. This procedure was applied to BPA and NP to calculate their probabilistic Benchmark Quotient (BQ), showing its potential in quantitatively apportioning the risk between contaminants and exposure sources, and its use as a decision support tool for prioritizing mitigation measures. Our results indicate that, even though the human health risk due to NP is not negligible, the estimated risk due to BPA is significantly higher, and the consumption of food from edible crops determines a higher risk compared to tap water. Hence, BPA is undoubtedly a contaminant to be prioritized, especially through mitigation actions aimed at its prevention and removal from food.

Quantitative chemical risk assessment for mixtures: Application to alkylphenol mixtures and phthalate mixtures in tap and bottled water.

The occurrence and hazard risks of mixtures of Contaminants of Emerging Concern (CECs) in drinking water (DW) lead to serious consideration regarding the possible impacts on public health. Consequently, there is ongoing research, development and empowerment of risk assessment procedures to get more toxicological insight. For instance, alkylphenols and phthalates have been frequently reported to be present both in bottled and tap water, affecting different human endpoints. Currently, deterministic chemical risk assessment (CRA) is used to evaluate the compounds' mixture health risk. However, CRA deals just qualitatively with sources of uncertainty, which may lead to erroneous assessment of risks. Here, a new procedure for quantitative chemical risk assessment of CEC mixtures (QCRAMIX) is proposed. Its potential is illustrated by a case study where the risks related to the presence of mixtures of alkylphenols or phthalates in tap versus bottled DW are compared. Uncertainties in both exposure and hazard assessment steps of the procedure are included to calculate a probabilistic mixture Benchmark Quotient (BQMIX). The QCRAMIX procedure highlighted the non-negligible health risks posed by those compounds in both DW sources based on overall water consumption. In fact, DW consumers' behaviour in 13 different countries, in terms of total DW consumption and fraction of bottled and tap water consumed, were considered to evaluate the influence on health risk. For alkylphenols, the total water consumption was found to be the most relevant factor in increasing the health risk, while for phthalates the risk was found to be mainly influenced by the percentage of bottled water consumed. Hence, the proposed QCRAMIX procedure can be a valuable tool for prioritization of CECs to be included in DW regulations which aim to minimize the overall risk, accounting for actual DW consumption.

Perfluoroalkyl substances (PFAS) adsorption in drinking water by granular activated carbon: Influence of activated carbon and PFAS characteristics.

Perfluoroalkyl substances (PFAS) persistence in the environment leads to their presence in drinking water, that is of high concern due to their potential human health risk. Adsorption onto activated carbon (AC) has been identified as an effective technique to remove PFAS. Adsorption isotherms and breakthrough curves, determined by rapid small-scale column tests (RSSCTs), were studied for eight PFAS and four granular ACs, characterized by different origins, porosities and numbers of reactivation cycles. Both batch and RSSCT results highlighted the strong interaction of AC and PFAS characteristics in adsorption capacity. The most important factor affecting AC performance is the surface charge: a positively-charged AC showed higher adsorption capacities with greater Freundlich constants (KF) and later 50% breakthroughs compared to the AC with neutral surface. Among the positively-charged ACs, a microporous AC demonstrated higher adsorption capacities for hydrophilic and marginally hydrophobic PFAS, while the mesoporous AC performed better for more hydrophobic PFAS, possibly due to lower pore blockage by organic matter. These results were confirmed at full-scale through a one-year monitoring campaign, in which samples were collected at the inlets and outlets of GAC systems in 17 drinking water treatment plants spread in a wide urban area, where the four analyzed ACs are used.

Bisphenol A leaching from epoxy resins in the drinking water distribution networks as human health risk determinant.

Monitoring and management of drinking water distribution networks (DWDNs), including possible leaching from materials in contact with drinking water, have been stressed as crucial to avoid re-contamination of drinking water leading to a potential increase of human health risk. Recent scientific studies and regulations clearly highlighted the leaching of bisphenol A (BPA) from plastic materials used to renovate DWDNs pipelines as one of the major hazardous source, resulting in severe consequences for human health. In this study, lab migration tests were performed on three commercial epoxy resins, designed with the Design of Experiments (DoE) method in order to build a BPA migration model as a function of water chemical stability, evaluated as aggressivity index (AI), and residual chlorine concentration. Tests lasted about 170 days to account for both short and long-term leaching. BPA migration over time was well described by a combination of two 1st-order kinetic models with an initial peak of leaching, a decrease and, then, a second increase due to resins' deterioration. Initial BPA concentration in the contact water and BPA integral migration over time showed inverse proportionality with both chlorine concentration and AI values. However, measurements of free BPA content in epoxy resins proved that this is due to BPA transformation, not to a reduced leaching. The validated BPA migration model was combined with the hydraulic model of the DWDN in an urban area, through EPANET-MSX software. The model allowed to simulate the propagation of BPA in the DWDN, after the execution of a relining intervention, identifying the most vulnerable areas and permitting to customize a site-specific monitoring and intervention plan to minimize the health risk for final consumers.

Development of a quantitative chemical risk assessment (QCRA) procedure for contaminants of emerging concern in drinking water supply.

The uncertainties on the occurrence, fate and hazard of Contaminants of Emerging Concern (CECs) increasingly challenge drinking water (DW) utilities whether additional measures should be taken to reduce the health risk. This has led to the development and evaluation of risk-based approaches by the scientific community. DW guideline values are commonly derived based on deterministic chemical risk assessment (CRA). Here, we propose a new probabilistic procedure, that is a quantitative chemical risk assessment (QCRA), to assess potential health risk related to the occurrence of CECs in DW. The QCRA includes uncertainties in risk calculation in both exposure and hazard assessments. To quantify the health risk in terms of the benchmark quotient probabilistic distribution, the QCRA estimates the probabilistic distribution of CECs concentration in DW based on their concentration in source water and simulating the breakthrough curves of a granular activated carbon (GAC) treatment process. The model inputs and output uncertainties were evaluated by sensitivity and uncertainty analyses for each step of the risk assessment to identify the most relevant factors affecting risk estimation. Dominant factors resulted to be the concentration of CECs in water sources, GAC isotherm parameters and toxicological data. To stress the potential of this new QCRA approach, several case studies are considered with focus on bisphenol A as an example CEC and various GAC management options. QCRA quantifies the probabilistic risk, providing more insight compared to CRA. QCRA proved to be more effective in supporting the intervention prioritization for treatment optimization to pursue health risk minimization.

A statistical assessment of micropollutants occurrence, time trend, fate and human health risk using left-censored water quality data.

In recent years, the presence of micropollutants in drinking water has become an issue of growing global concern. Due to their low concentrations, monitoring databases are usually rich in censored data (e.g. samples with concentrations reported below the limit of quantification, LOQ) which are typically eliminated or replaced with a value arbitrarily chosen between 0 and LOQ. These conventional methods have some limitations and can lead to erroneous conclusions on: presence of micropollutants in the source water, treatment efficiencies, produced water quality and associated human health risk. In this work, an advanced approach, based on Maximum Likelihood Estimation method for left-censored data (MLELC), was applied on monitoring data of 19 contaminants (metals, volatile organic compounds, pesticides and perfluorinated compounds) in 5362 groundwater (GW) and 12,344 drinking water (DW) samples, collected from 2012 to 2017 in 28 drinking water treatment plants in an urbanized area. This study demonstrates the benefits of MLELC method, especially for high percentages of censored data. Data are used to build statistical distributions which can be effectively used for several applications, such as the time trend evaluation of GW micropollutant concentrations and the estimation of treatment removal efficiency, highlighting the adequacy or the need for an upgrade. Moreover, the MLELC method has been applied to assess the human health risk associated with micropollutants, indicating the high discrepancy in the estimations obtained with conventional methods, whose results do not follow precautionary or sustainability criteria.