Analysis of microplastics in the environment: Identification and quantification of trace levels of common types of plastic polymers using pyrolysis-GC/MS.

This work describes the development of analytical workflows based on pyrolysis coupled with gas chromatography-mass spectrometry (Pyr-GC/MS) for the qualitative and quantitative analysis of 12 of the most common plastic polymers in environmental samples. The most suitable characteristic pyrolyzate compounds and respective indicator ions were selected for each polymer in order to obtain the most appropriate response for analytical purposes. Additionally, commercial pyrolyzates and polymers libraries were used to confirm the identity of the detected microplastics. The method was validated, showing a good linearity for all the plastic polymers (R2 > 0.97) and limits of detection between 0.1 (polyurethane) to 9.1 µg (polyethylene). The developed methodology was successfully applied for the analysis of plastic polymers in environmental microplastic samples collected in three Mediterranean beaches (NE Spain).•Fast and reproducible Pyr-GC/MS method for the analysis of the 12 most common plastic polymers in a single GC/MS run•Straightforward analytical workflows using pyrolyzates and polymers libraries enable a fast identification and quantification of microplastics in environmental samples.

Optimal design of water reuse networks in cities through decision support tool development and testing.

Water scarcity and droughts are an increasing issue in many parts of the world. In the context of urban water systems, the transition to circularity may imply wastewater treatment and reuse. Planning and assessment of water reuse projects require decision-makers evaluating the cost and benefits of alternative scenarios. Manual or semi-automatic approaches are still common practice for planning both drinking and reclaimed water distribution networks. This work illustrates a decision support tool that, based on open data sources and graph theory coupled to greedy optimization algorithms, is able to automatically compute the optimal reclaimed water network for a given scenario. The tool provides not only the maximum amount of served reclaimed water per unit of invested cost, but also the length and diameters of the pipes required, the location and size of storage tanks, the population served, and the construction costs, i.e., everything under the same architecture. The usefulness of the tool is illustrated in two different but complementary cities in terms of size, density, and topography. The construction cost of the optimal water reclaimed network for a city of approximately 100,000 inhabitants is estimated to be in the range of €0.17-0.22/m3 (for a payback period of 30 years).

Second-Generation Magnesium Phosphates as Water Extractant Agents in Forward Osmosis and Subsequent Use in Hydroponics.

The recovery of nutrients from wastewater streams for their later use in agricultural fertilization is an interesting approach. Wastewater recovered magnesium phosphate (MgP) salts were used in a forward osmosis (FO) system as draw solution in order to extract water and to produce a nutrient solution to be used in a hydroponic system with lettuces (Lactuca sativa, L.). Owing to the low solubility of the MgP salts (i.e., struvite, hazenite and cattiite) in water, acid dissolution was successfully tested using citric and nitric acids to reach pH 3.0. The dilution by FO of the dissolved salts reached levels close to those needed by a hydroponic culture. Ion migration through the membrane was medium to high, and although it did not limit the dilution potential of the system, it might decrease the overall feasibility of the FO process. Functional growth of the lettuces in the hydroponic system was achieved with the three MgP salts using the recovered water as nutrient solution, once properly supplemented with nutrients with the desired concentrations. This is an innovative approach for promoting water reuse in hydroponics that benefits from the use of precipitated MgP salts as a nutrient source.

Modelling and prediction of the effect of operational parameters on the fate of contaminants of emerging concern in WWTPs.

Wastewater treatment plants (WWTPs) provide a barrier against the discharge of contaminants of emerging concern (CECs) into the environment. The removal of CECs is highly WWTP-specific and the underlying mechanisms are still poorly understood, hampering the optimization of biological treatment steps for their removal. To fill this knowledge gap, we assessed the influence of four operational parameters of activated sludge biological treatment, namely total suspended solids, temperature, pH and redox conditions, on the sorption and biodegradation of four CECs under controlled laboratory conditions. Design of Experiments was used to better address the factors influencing CECs removal and interactions among operational parameters. The derived statistical models showed results in concordance with previous studies and indicated how sorption and biodegradation of the investigated CECs depend on most tested parameters and few of their interactions. The predictions of the developed models have been compared with literature values, indicating how the tested parameters are responsible for most of the variability of sorption, while they could not reliably generalize biodegradation rates. The developed models were also implemented as an extension of a mechanistic biological treatment model, successfully describing the dynamic behaviour of a large-scale WWTP, which was observed during a three-day continuous monitoring campaign. Compared to a traditional modelling approach, the one including the developed models showed on average almost a three-fold uncertainty reduction, favouring its use to aid WWTP managers and regulators for improved assessment of CEC fate and removal. Finally, the models highlighted that, while higher temperatures and solids concentrations generically favoured CECs removal, removal efficiency vary significantly due to operational parameters and no globally optimum conditions for CECs removal exist. The use of these models opens the door to the combined dynamic management of both traditional contaminants and CECs in WWTPs.

Performance of TiO2/UV-LED-Based Processes for Degradation of Pharmaceuticals: Effect of Matrix Composition and Process Variables.

Ultra-violet light-emitting diode (UV-LED)-based processes for water treatment have shown the potential to surpass the hurdles that prevent the adoption of photocatalysis at a large scale due to UV-LEDs' unique features and design flexibility. In this work, the degradation of five EU Watch List 2020/1161 pharmaceutical compounds was comprehensively investigated. Initially, the UV-A and UV-C photolytic and photocatalytic degradation of individual compounds and their mixtures were explored. A design of experiments (DoE) approach was used to quantify the effects of numerous variables on the compounds' degradation rate constant, total organic carbon abatement, and toxicity. The reaction mechanisms of UV-A photocatalysis were investigated by adding different radical scavengers to the mix. The influence of the initial pH was tested and a second DoE helped evaluate the impact of matrix constituents on degradation rates during UV-A photocatalysis. The results showed that each compound had widely different responses to each treatment/scenario, meaning that the optimized design will depend on matrix composition, target pollutant reactivity, and required effluent standards. Each situation should be analyzed individually with care. The levels of the electrical energy per order are still unfeasible for practical applications, but LEDs of lower wavelengths (UV-C) are now approaching UV-A performance levels.

Exploring the limitations of forward osmosis for direct hydroponic fertigation: Impact of ion transfer and fertilizer composition on effective dilution.

There is a need for water reuse technologies and applications to minimize the imminent water crisis, caused by the world population growth, the reduction of freshwater resources and the increasing water pollution. Fertilizer-drawn forward osmosis (FDFO) is a promising process capable of simultaneously extracting fresh water from low-quality sources as feed water (e.g., wastewater or greywater), while diluting fertilizer solutions for direct fertigation, avoiding the demand for freshwater for irrigation. Achieving an adequate level of dilution for direct fertigation is a key element to be evaluated for the implementation of FDFO. This study assessed the performance of the forward osmosis process to dilute fertilizer solutions to be applied directly in hydroponic systems. Experiments were carried out under conditions close to osmotic equilibrium to evaluate the process performance up to the maximum dilution point. Tests were carried out with individual and blended fertilizers (i.e., (NH4)2HPO4 or DAP, and KNO3) used as draw solution (DS) and with deionized water or individual salts (NaCl, MgCl2, Na2SO4, MgSO4) in the feed solution (FS). Water fluxes and reverse salt fluxes indicated that both fertilizer DS composition and concentrations play a fundamental role in the process. Suitable nutrient concentrations to be directly applied without further dilution for N, P and K (119, 40, 264 mg.L-1 respectively) were obtained with deionized water as FS and blended DAP (0.025 M) and KNO3 (0.15 M) as DS. However, important fertilizer losses from DS to FS were observed, being the highest for NO3- (33-70% losses from DS to FS). The presence of salts in FS decreased the water fluxes and the DS dilution due to the osmotic equilibrium caused by a greater loss of nutrients from DS to FS (up to 100%), compared with tests using just deionized water as FS. This study points out the potential limitations of the FDFO process, due to the high solute fluxes and low water fluxes in conditions close to osmotic equilibrium.

Feasibility of vertical ecosystem for sustainable water treatment and reuse in touristic resorts.

To counteract increasing water scarcity in the Mediterranean region, this study provides data on the efficiency of a decentralized, nature-based solution for hotel greywater (GW) treatment and reuse. A pilot plant of a constructed wetland called Vertical Ecosystem (vertECO), installed in a large hotel with GW separation, was operated continuously for 12 months. vertECO achieved a removal efficiency higher than 84.0% for COD and TSS and higher than 95.4% for turbidity and BOD5. The monitored physicochemical parameters in the effluent meet the requirements for many reuse purposes restricted in the water reuse legislation. Based on the pilot operation, an economic model was set to estimate its economic feasibility (CAPEX, OPEX and payback period of investment) at several treated volumes. The payback was calculated, at the water and energy prices of Spain and other countries, with a planned operation period of 20 years. The higher the water price, the lower was the payback period. Treated GW volumes of 10.5 and 20 m3/day correspond to payback periods for Spain of 10.1 years and 9.0 years, respectively. Finally, co-benefits of vertECO have been considered alongside economic terms, and compared with another intensive technology (i.e., membrane bioreactor).

Microalgae-based removal of contaminants of emerging concern: Mechanisms in Chlorella vulgaris and mixed algal-bacterial cultures.

Incomplete removal of contaminants of emerging concern (CECs) has been reported for conventional wastewater treatment technologies. Microalgae-based treatment has recently gained interest thanks to simultaneous removal capacity of organic and inorganic compounds and potentially CECs. In this study, a lab-scale monoculture of Chlorella vulgaris and mixed microalgal-bacterial culture were compared in terms of removal of 28 CECs (bisphenols, 2018 EU Watch List substances, including neonicotinoids, pharmaceuticals, selected transformation products). The removal pathways in light and dark abiotic controls were also studied. Batch photobioreactors were run at hydraulic retention times of 11-12 days and CECs spiked at environmentally relevant concentrations (1-20 µg L-1). The mixed culture was better at removing bisphenols, compared to C. vulgaris. Bisphenols' log Kow was significant in removal pathways, where bisphenols with high log Kow were removed abiotically while bisphenols with low log Kow were mainly biodegraded. The removal degrees and the pathways of pharmaceuticals and EU Watch List substances were comparable between both cultures, showing no impact of log Kow for most compounds; however, the removal with C. vulgaris was faster for some. High log Kow was associated with high removal of estradiol in abiotic controls, showing the importance of adsorption onto biomass and suspended matter.

Prospects on coupling UV/H2O2 with activated sludge or a fungal treatment for the removal of pharmaceutically active compounds in real hospital wastewater.

Conventional active sludge (AS) process at municipal centralized wastewater treatment facilities may exhibit little pharmaceuticals (PhACs) removal efficiencies when treating hospital wastewater (HWW). Therefore, a dedicated efficient wastewater treatment at the source point is recommended. In this sense, advanced oxidation processes (AOPs) and fungal treatment (FG) have evidenced promising results in degrading PhACs. The coupling of the AOP based on UV/H2O2 treatment with biological treatment (AS or FG) treating a real non-sterile HWW, was evaluated in this work. In addition, a coagulation-flocculation pretreatment was applied to improve the efficiency of all approaches. Twenty-two PhACs were detected in raw HWW, which were effectively removed (93-95%) with the combination of any of the biological treatment followed by UV/H2O2 treatment. Similar removal results (94%) were obtained when placing UV/H2O2 treatment before FG, while a lower removal (83%) was obtained in the combination of UV/H2O2 followed by AS. However, the latest was the only treatment combination that achieved a decrease in the toxicity of water. Moreover, deconjugation of conjugated PhACs has been suggested for ofloxacin and lorazepam after AS treatment, and for ketoprofen after fungal treatment. Monitoring of carbamazepine and its transformation products along the treatment allowed to identify the same carbamazepine degradation pathway in UV/H2O2 and AS treatments, unlike fungal treatment, which followed another degradation route.

State-of-the-art and current challenges for TiO2/UV-LED photocatalytic degradation of emerging organic micropollutants.

The development of ultraviolet light-emitting diodes (UV-LED) opens new possibilities for water treatment and photoreactor design. TiO2 photocatalysis, a technology that has been continuously drawing attention, can potentially benefit from LEDs to become a sustainable alternative for the abatement of organic micropollutants (OMPs). Recently reported data on photocatalytic degradation of OMPs and their parameters of influence are here critically evaluated. The literature on OMP degradation in real water matrices, and at environmentally relevant concentrations, is largely missing, as well as the investigations of the impact of photoreactor design in pollutant degradation kinetics. The key factors for reducing UV-LED treatment technology costs are pointed out, like the increase in external quantum and wall-plug efficiencies of UV-LEDs compared to other technologies, as well as the need for an appropriate design optimizing light homogeneity in the reactor. Controlled periodic illumination, wavelength coupling and H2O2 addition are presented as efficiency enhancement options. Although electrical energy per order (EEO) values for UV-LED photocatalysis have decreased to the range of traditional mercury lamps, values are still not low enough for practical employment. Moreover, due to the adoption of high initial OMP concentration in most experiments, it is likely that most literature EEO values are overestimated. Given the process characteristics, which are favoured by translucent matrices and small diameters for more homogenous light distribution and better transportation of radicals, innovative reactor designs should explore the potential of point-of-use applications to increase photocatalysis applicability at large scale.

How do WWTPs operational parameters affect the removal rates of EU Watch list compounds?

This work aims at achieving a better understanding of the mechanisms and the operative conditions regulating the removal of a set of relevant micropollutants in conventional activated sludge (CAS) systems to maximize their removal and, if possible, biodegradation. Eight compounds from the EU Watch list (clothianidin, thiacloprid, methiocarb, E1, E2, EE2, diclofenac and erythromycin) were spiked at 2 µg/L in CAS systems and their behaviour was studied in 6-h batch tests. The role of sorption was also investigated. Information on the removal of the pesticides clothianidin, thiacloprid and methiocarb is here presented for the first time to the best of the authors' knowledge. With the aim of enhancing the removal of the selected compounds in wastewater treatment, four parameters were explored: biomass concentration, temperature, pH and redox conditions. For each parameter, a low and a high value were chosen, based on the ranges usually applied in wastewater treatment plants (WWTPs). Results show that biomass concentration is the most relevant parameter among the ones investigated, followed by the redox conditions. The operational conditions that maximized removal rates were: 5 g/L of biomass, aerobic conditions, 25 °C and pH 7.5. High variability in removal rates was observed for compounds such as E1, erythromycin and methiocarb. The pesticides clothianidin and thiacloprid did not prove to be easily degradable. The highest removal rates were recorded for the hormones, particularly E2, with a transformation rate of at least 96% under all conditions. Sorption proved to be a relevant removal route for EE2, for which the highest sorption rates were recorded, and diclofenac, where the adsorption mechanisms was hypothesised for its prevalence at lower pH values.

Metoprolol and metoprolol acid degradation in UV/H2O2 treated wastewaters: An integrated screening approach for the identification of hazardous transformation products.

Advancements on analytical strategies to determine the chemicals present in treated wastewater are necessary to clearly link their occurrence with the ecotoxicity of such effluents. This study describes the development of an integrated screening approach to determine the highest number of pharmaceutical transformation products (TPs) in a single run. The identification of TPs was based on the comparison of detected features with literature sources, compound prediction tools, in-house libraries and reference standards using high-resolution mass spectrometry (HRMS). This integrated approach allowed a better estimation (in silico) of the ecotoxicological contribution of the individual TPs identified. As a proof of concept, this methodology was applied for identification of the TPs generated from metoprolol and its main human metabolite (metoprolol acid) in pure water, hospital wastewater and industrial wastewater treated by UV/H2O2. Twenty-four TPs with potential ecotoxicological implications were identified and their presence was pinpointed as a function of the treated wastewater. An integrated screening approach has been developed using four different screening methodologies in the same run. Additionally, the metabolite MTPA has been considered as a target pollutant in UV/H2O2 experiments.

The EU watch list compounds in the Ebro delta region: Assessment of sources, river transport, and seasonal variations.

The presence of xenobiotics in the aquatic environment has drawn scientific concern due to possible detrimental effects on the ecosystems. With EU Decision 2015/495, a first Watch list of compounds that could potentially represent a threat for the environment was created, with the objective of gathering high quality monitoring data and support their prioritization. Literature data are still very scarce and the presence of many of the compounds has not been investigated thoroughly. In this study, all the 17 compounds of the EU Watch list 2015/495 were monitored in 14 sampling locations, comprised of freshwater and, for the first time, wastewater. The study was carried out in the Ebro delta, in the north east of Spain, a representative and crucial area not only for its environmental and naturalistic significance, but also for Spain's productivity, especially as regards rice agriculture. Results show that contamination originates both from wastewater treatment plants (WWTPs) and agricultural activities. High levels of pharmaceuticals were detected in wastewater, with azithromycin and diclofenac present at mean concentrations of 1.65 µg/L and 636  ng/L respectively. In freshwater samples, besides antibiotics and diclofenac, substantial contamination by pesticides was reported, with oxadiazon reaching up to 591 ng/L and imidacloprid being present in 93% of samples. Moreover, the study provided insight into the origin of the selected contaminants. The removal of the studied micropollutants in WWTPs was low to moderate. The assessment of risk quotients, calculated based on the available PNECs, demonstrated that the concentrations recorded for these compounds may pose a significant risk in most sampling sites.

Recycled corrugated wire hose cover as biological carriers for greywater treatment in a sequential batch biofilm reactor.

Greywater treatment and reuse can be considered a promising option, in particular in water scarcity affected areas. In this work a waste material, namely recycled corrugated wire hose cover, was applied as an alternative and cheap carrier in a sequencing batch biofilm reactor (SBBR) for greywater treatment. The bioreactor performance was studied in terms of organic matter, nitrogen and micropollutant removal. Four operational stages were investigated: i) inoculation of the carriers; ii) greywater treatment with suspended biomass; iii) synthetic and iv) real greywater treatment with inoculated carriers in the SBBR. The SBBR could treat real greywater showing high removal efficiencies for COD (86.5 ±â€¯5.8%), ammonium (98.4 ±â€¯1.4%) and total nitrogen (71.4 ±â€¯8.2%). The obtained efficiencies were similar to the ones obtained with commercial carriers and to other treatments such as MBBR or MBR. In terms of micropollutants, 7 out of 13 detected micropollutants were highly removed (efficiency higher than 85%) while 5 of them (ofloxacin, metoprolol acid, venlafaxine, iopromide and hydrochlorothiazide) were found to be highly recalcitrant to the treatment.

Comparative assessment of endocrine disrupting compounds removal in heterotrophic and enriched nitrifying biomass.

Despite the number of studies that have investigated the fate of endocrine disrupting compounds (EDCs), to date results are still contradictory and more research is required to evaluate the contribution of the microbial communities present in different engineered treatment systems. Thus, autotrophic and heterotrophic types of biomass were here compared in terms of efficiency in the removal of estrone (E1), 17ß-estradiol (E2), estriol (E3), 17α-ethynilestradiol (EE2) and bisphenol A (BPA). Experiments were performed with enriched nitrifying activated sludge (NAS) and enriched ammonia oxidizing bacteria (AOB) sludge cultivated at lab-scale, as well as with conventional activated sludge (CAS) from a full-scale wastewater treatment plant. Both enriched NAS and AOB demonstrated a negligible degrading capacity. In both cases, the studied EDCs exhibited low removals (<14%) and showed no correlation with the increasing nitrification rates contradicting some of the hypothesis present in literature. Contrariwise, the biodegradation capabilities of the heterotrophic fraction of CAS were highlighted. E2 and E3 were removed by up to 100% and 78%, respectively. E1 was found to be the main transformation product of E2 (almost quantitative oxidation) and it was also highly eliminated. Finally, EE2 and BPA were more persistent biologically with removals ranging from 10% to 39%. For these two compounds similar removals were obtained during experiments with heat-inactivated biomass suggesting that sorption could be a relevant route of elimination.

Application of UVOX Redox® for swimming pool water treatment: Microbial inactivation, disinfection byproduct formation and micropollutant removal.

Alternative disinfection technologies may overcome some of the limitations of conventional treatment applied in swimming pools: chlorine-resistant pathogens (e.g. Cryptosporidium oocysts and Giardia cysts) and the formation of chlorinated disinfection byproducts. In this paper, results of full scale validation of an alternative disinfection technology UVOX Redox® (hereinafter referred to as UVOX) that combines ozonation and UV irradiation are presented. The performance was assessed in terms of microbial inactivation, disinfection byproduct formation and micropollutant removal. UVOX was able to achieve 1.4-2.7 log inactivation of Bacillus subtilis spores at water flows between 20 and 76 m³/h. Lower formation of trichloromethane and dichloroacetic acid was observed with UVOX followed by chlorination when compared to chlorination alone. However, due to the use of ozone and the presence of bromide in the pool water, the formation of trihalomethanes and haloacetic acids shifted to more brominated byproducts. Chlorine alone was able to remove the target micropollutants: acetaminophen, atenolol, caffeine, carbamazepine, estrone, estradiol, and venlafaxine (>97% removal) after 24 h, with the exception of ibuprofen (60% removal). The application of UVOX in chlorinated water enhanced the removal of ibuprofen. The application of UVOX could lower the usage of chlorine to the level that provides an adequate residual disinfection effect.

Unraveling the potential of a combined nitritation-anammox biomass towards the biodegradation of pharmaceutically active compounds.

In the past few years, anaerobic ammonium oxidation-based processes have attracted a lot of attention for their implementation at the mainstream line of wastewater treatment plants, due to the possibility of leading to energy autarky if combined with anaerobic digestion. However, little is known about the potential degradation of micropollutants by the microbial groups responsible of these processes and the few results available are inconclusive. This study aimed to assess the degradation capability of biomass withdrawn from a combined nitritation/anaerobic ammonium oxidation (combined N/A) pilot plant towards five pharmaceutically active compounds (ibuprofen, sulfamethoxazole, metoprolol, venlafaxine and carbamazepine). Batch experiments were performed under different conditions by selectively activating or inhibiting different microbial groups: i) regular combined N/A operation, ii) aerobic (optimal for nitrifying bacteria), iii) aerobic with allylthiourea (an inhibitor of ammonia monooxygenase, enzyme of ammonia oxidizing bacteria), iv) anoxic (optimal for anaerobic ammonium oxidizing bacteria), v) aerobic with acetate (optimal for heterotrophic bacteria) and vi) anoxic with acetate (optimal for heterotrophic denitrifying bacteria). Ibuprofen was the most biodegradable compound being significantly degraded (49-100%) under any condition except heterotrophic denitrification. Sulfamethoxazole, exhibited the highest removal (70%) under optimal conditions for nitrifying bacteria but in the rest of the experiments anoxic conditions were found to be slightly more favorable (up to 58%). For metoprolol the highest performance was obtained under anoxic conditions favoring anammox bacteria (62%). Finally, carbamazepine and venlafaxine were hardly removed (≤10% in the majority of cases). Taken together, these results suggest the specificity of different microbial groups that in combination with alternating operational parameters can lead to enhanced removal of some micropollutants.

Optimized MBR for greywater reuse systems in hotel facilities.

Greywater is an important alternative water source, particularly in semi-arid, touristic areas, where the biggest water demand is usually in the dry period. By using this source wisely, tourist facilities can substantially reduce the pressure to scarce water resources. In densely urbanized touristic areas, where space has high value, compact solutions such as MBR based greywater reuse systems appear very appropriate. This research focuses on technical and economical evaluation of such solution by implementing a pilot MBR to a hotel with separated grey water. The pilot was operated for 6 months, with thorough characterisation of the GW performed, its operation was monitored and its energy consumption was optimized by applying a control system for the air scour. Based on the pilot operation a design and economic model was set to estimate the feasibility (CAPEX, OPEX, payback period of investment) of appropriate scales of MBR based GW systems, including separation of GW, MBR technology, clean water storage and disinfection. The model takes into account water and energy prices in Spain and a planning period of 20 years. The results demonstrated an excellent performance in terms of effluent quality, while the energy demand for air-scour was reduced by up to 35.2%, compared to the manufacturer recommendations. Economical evaluation of the entire MBR based GW reuse system shows its feasibility for sizes already at 5 m3/day (60 PE). The payback period of the investment for hotels like the demonstration hotel, treating 30 m3/day is 3 years.