Amended Vegetation Filters as Nature-Based Solutions for the Treatment of Pharmaceuticals: Infiltration Experiments Coupled to Reactive Transport Modelling.

In small populations and scattered communities, wastewater treatment through vegetation filters (VFs), a nature-based solution, has proved to be feasible, especially for nutrient and organic matter removal. However, the presence of pharmaceuticals in wastewater and their potential to infiltrate through the vadose zone and reach groundwater is a drawback in the evaluation of VF performances. Soil amended with readily labile carbon sources, such as woodchips, enhances microbial activity and sorption processes, which could improve pharmaceutical attenuation in VFs. The present study aims to assess if woodchip amendments to a VF's soil are able to abate concentrations of selected pharmaceuticals in the infiltrating water by quantitatively describing the occurring processes through reactive transport modelling. Thus, a column experiment using soil collected from an operating VF and poplar woodchips was conducted, alongside a column containing only soil used as reference. The pharmaceuticals acetaminophen, naproxen, atenolol, caffeine, carbamazepine, ketoprofen and sulfamethoxazole were applied daily to the column inlet, mimicking a real irrigation pattern and periodically measured in the effluent. Ketoprofen was the only injected pharmaceutical that reached the column outlet of both systems within the experimental timeframe. The absence of acetaminophen, atenolol, caffeine, carbamazepine, naproxen and sulfamethoxazole in both column outlets indicates that they were attenuated even without woodchips. However, the presence of 10,11-epoxy carbamazepine and atenolol acid as transformation products (TPs) suggests that incomplete degradation also occurs and that the effect of the amendment on the infiltration of TPs is compound-specific. Modelling allowed us to generate breakthrough curves of ketoprofen in both columns and to obtain transport parameters during infiltration. Woodchip-amended columns exhibited Kd and µw values from one to two orders of magnitude higher compared to soil column. This augmentation of sorption and biodegradation processes significantly enhanced the removal of ketoprofen to over 96%.

Evaluation of contaminants of emerging concern attenuation through a vegetation filter managed using different operating conditions.

In wastewater treatment using Vegetation Filters (VFs), natural processes reduce contaminants present in water although some of them can reach the environment. In this study, 39 contaminants of emerging concern (CECs) are evaluated in a pilot VF under different operating conditions during almost four years. The use of woodchip amendments and the change from surface irrigation through furrows to drip irrigation (and from weekly to daily water application) provide CEC concentration reductions in the water infiltrating through the vadose zone. Biodegradation is the main process taking place and has been favoured mainly by woodchip soil amendments and the increased residence. Median attenuation percentages of the CECs most frequently detected with highest concentrations in applied wastewater vary between 52% and 100% at the end of the study (at 45 cm depth). Among targeted CECs, caffeine, and its transformation product paraxanthine are the most attenuated. Flecainide and venlafaxine show a persistent behaviour. However, their leaching concentrations are very low (< 31 ng/L). Concerning the underlying aquifer, the groundwater quality in terms of CEC concentrations is conditioned by the surrounding area rather than the operation of the VF. Levels in groundwater are always below those in wastewater and infiltrating water.

Pharmaceutical and transformation products during unplanned water reuse: Insights into natural attenuation, plant uptake and human health impact under field conditions.

In urban and periurban areas, agricultural soils are often irrigated with surface water containing a complex mixture of contaminants due to wastewater treatment plant (WWTP) effluent discharges. The unplanned water reuse of these resources for crop irrigation can represent a pathway for contaminant propagation and a potential health risk due to their introduction in the food chain. The aim of this study is to provide data about the magnitude of attenuation processes and plant uptake, allowing for a reliable assessment of contaminant transfer among compartments and of the human health risk derived from unplanned water reuse activities. Target compounds are 25 pharmaceuticals, including transformation products (TPs). The field site is an agricultural parcel where maize is irrigated by a gravity-fed surface system supplied by the Jarama river, a water course strongly impacted by WWTP effluents. Throughout the 3-month irrigation period, irrigation water and water infiltrating through the vadose zone were sampled. The agricultural soil was collected before and after the irrigation campaign, and maize was sampled before harvesting. All selected compounds are detected in irrigation water (up to 12,867 ng L-1). Metformin, two metamizole TPs and valsartan occur with the highest concentrations. For most pharmaceuticals, results demonstrate a high natural attenuation during soil infiltration (>60%). However, leached concentrations of some compounds can be still at concern level (>400 ng L-1). A persistent behavior is observed for carbamazepine, carbamazepine epoxide and sulfamethoxazole. Pharmaceutical soil contents are in the order of ng g-1 and positively ionized compounds accumulate more effectively. Results also indicate the presence of a constant pool of drugs in soils. Only neutral and cationic pharmaceuticals are taken up in maize tissues, mainly in the roots. There is an insignificant threat to human health derived from maize consumption however, additional toxicity tests are recommended for 4AAA and acetaminophen.

Sustainable soil amendments to improve nature-based solutions for wastewater treatment and resource recovery.

Vegetation Filters (VFs) can be a sustainable solution to treat wastewater and to recover resources such as nutrients, water and biomass from small municipalities and isolated dwellings. However, under certain conditions, the leakage of nutrients, especially of nitrate, can represent a limitation. The addition of two sustainable soil amendments, woodchips and biochar, has been tested as a strategy to improve nutrient attenuation in VFs increasing sorption sites and microbial activity. To this end, unsaturated infiltration and batch experiments have been carried out at laboratory scale. The systems for infiltration experiments contain natural soil, natural soil amended with woodchips and natural soil amended with biochar. To determine the sorption capacity of NH4+, batch tests were performed using an amendment/SWW ratio of 1:20 and an NH4+ initial concentration ranging from 30 to 600 mg L-1. Results from the infiltration experiments show a high attenuation (~95%) of total phosphorous (TP) independently of the amendments. Different behaviour is observed for total nitrogen (TN). The removal of this species is obtained only in the soil amended with woodchips (>85%) whereas the natural soil alone and the soil with biochar have no impact on TN attenuation. In these two porous media, all the NH4+ input concentration is transformed to NO3- that infiltrates without further reactions. According to batch experiment results, the potential role of biochar in the nutrient attenuation is limited to sorption processes (Kd (NH4+) = 21.37-193.18 L kg-1). Woodchips act primarily as a labile source of carbon promoting biodegradation, being more effective for nutrient attenuation than the sorption capacity of biochar.

Pharmaceuticals and trace metals in the surface water used for crop irrigation: Risk to health or natural attenuation?

The use of surface water impacted by wastewater treatment plant (WWTP) effluents for crop irrigation is a form of unplanned water reuse. Natural attenuation processes can buffer contamination spreading. However, this practice can promote the exposure of crops to contaminants of emerging concern, such as pharmaceuticals, trace metals (TMs) and metalloids, posing a risk to health. This research aimed to evaluate the presence of 50 pharmaceuticals, some transformation products, 7 TMs and a metalloid in the water-sediment-soil-plant system, and their potential to be bioaccumulated into edible parts of plants, as a result of the unplanned water reuse. The study site consists of an extensive agricultural land downstream Madrid city (Spain) where surface water, strongly impacted by WWTP effluents, is applied through gravity-based systems to cultivate mainly maize. Sampling campaigns were conducted to collect WWTP effluent, surface and irrigation water, river sediments, agricultural soils and maize fruits. Results demonstrate the ubiquitous presence of several pharmaceuticals. The concentration pattern in irrigation water did not resemble the pattern of contents in soils and plants. The pharmaceuticals included in the EU surface water watch lists were quantified in the lowest concentration range (macrolide antibiotics, ciprofloxacin) or were not detected (most of the hormones). Therefore, hormones do not represent an emerging risk in our scenario. The TMs and the metalloid in water and agricultural soils should not arise any concern. Whereas, their presence in the river sediments may have an adverse impact on aquatic ecosystems. Only acetaminophen, ibuprofen, carbamazepine, nicotine, Zn, Cu and Ni were quantified in corn grains. Calculated parameters to assess bioaccumulation and health risk indicate that neither pharmaceuticals nor TMs pose a threat to human health due to consumption of maize cultivated in the area. Results highlight the need to include different environmental matrices when assessing contaminant fate under real field-scale conditions.

Clinoptilolite and palygorskite as sorbents of neutral emerging organic contaminants in treated wastewater: Sorption-desorption studies.

Water reuse for aquifer recharge could be an important route for the introduction of emerging organic contaminants (EOCs) into the environment. The installation of a Horizontal Permeable Reactive Barrier (H-PRB) could constitute a tertiary treatment process to remove EOCs from treated domestic wastewater prior to recharge activities. The sorption-desorption behaviour of six neutral EOCs present in treated domestic wastewater (acetaminophen, caffeine, carbamazepine, cotinine, 4-acetamidoantipyrine (4-AAA) and 4-formylaminoantipyrine (4-FAA)) has been evaluated. Clinoptilolite and palygorskite have been studied as sorbents to be installed in the H-PRB. Batch tests were carried out using an EOC initial concentration ranging from 5 to 100 µg L-1. Apart from acetaminophen and caffeine, both materials showed a limited sorption capacity of neutral EOCs (Kd = 0.63-5.42 L kg-1). In general, the experimental results show that EOCs exhibit a higher sorption affinity for clinoptilolite than for palygorskite. With the exception of carbamazepine, the sorption of the compounds occurs mainly by interactions with mineral surfaces as indicated by the comparison of the partition coefficients into organic matter and into mineral surfaces. According to the molecular geometry of the compounds and the sorption sequences observed, it appears that the dimensions of the organic molecules play a key role in the sorption process. All the studied EOCs exhibit irreversible sorption and sorption-desorption hysteresis.

Investigating natural attenuation of pharmaceuticals through unsaturated column tests.

The growing consumption of pharmaceuticals together with their incomplete removal in wastewater treatment plants (WWTPs) implies the occurrence of these compounds in natural water resources. To investigate the natural attenuation of selected pharmaceuticals (caffeine, acetaminophen, sulfamethoxazole, naproxen and carbamazepine) during vadose zone infiltration, unsaturated column (L 26.67 cm, Ø 7.62 cm) experiments, filled with a sandy-loamy soil, were performed using two input concentrations (100 and 1000 µg L-1). The software Hydrus 1D was used to simulate experimental data. Caffeine and acetaminophen were never detected at the column outlet indicating a low environmental concern. On the other hand, attenuation of the detected pharmaceuticals could be reproduced by a combination of retardation and removal approaches. Carbamazepine is among the selected contaminants the most persistent. A dependence of removal rates on input concentrations was detected for sulfamethoxazole (µw from 2.78 d-1 to 1.16 d-1) and naproxen (µw from 1.16 d-1 to 0.63 d-1) attributed mainly to decreased metabolism of microorganisms when a higher input concentration is applied. Two transformation products (TPs) (N4-Acetylsulfamethoxazole and epoxycarbamazepine) derived from sulfamethoxazole and carbamazepine transformation, respectively, were detected during the experiment with the highest input concentration.

Soil amendment using poplar woodchips to enhance the treatment of wastewater-originated nutrients.

Vegetation filters, a nature based wastewater regeneration technology, have been reported as a feasible solution for small municipalities and scattered populations with limited access to sewage networks. However even when such a treatment is properly planned, the leaching of contaminants through the unsaturated zone may occur. The amendment of soil with a readily-labile source of carbon is supposed to ameliorate the removal of contaminants by stimulating microbial activity and enhancing sorption processes. In this study, lab-scale leaching column experiments were carried out to explore if the addition of woodchips to the soil could be a feasible strategy to be integrated in a vegetation filter. Two different types of arrangement of soil and woodchips layers were tested. The soil was collected from an operating vegetation filter treating wastewater of an office building characterised by a high nutrient load. Daily pulse of synthetic wastewater were applied into the columns and effluent samples were collected and analyzed for major ions, total nitrogen (NT), total phosphorous (PT) and chemical oxygen demand (COD). By the end of the experiment, NT, NO3-N and PT soil contents were also measured. Results indicate that amendments with woodchips enhance the elimination of wastewater-originated contaminants. NT removal in the columns with woodchips reaches a value of 99.4%. The main processes responsible for this elimination are NH4-N sorption and nitrification/denitrification. This latter fostered by the reduced redox conditions due to the enhanced microbial activity. High removal of PT (99%) is achieved independently of the woodchips presence due to retention and/or precipitation phenomena. The COD removal efficiency is not affected by the presence of the woodchips. The leaching of organic carbon occurs only during the experimental start-up period.

The role of sorption and biodegradation in the removal of acetaminophen, carbamazepine, caffeine, naproxen and sulfamethoxazole during soil contact: A kinetics study.

In countries like Spain, where water is a limited resource, reusing effluents from wastewater treatment plants may imply the introduction of incompletely eliminated pollutants into the environment. Therefore, this work identified the role of sorption and biodegradation in attenuating pharmaceutical compounds (acetaminophen, carbamazepine, caffeine, naproxen and sulfamethoxazole) in natural soil. It also determined which sorption and removal ("sorption+biodegradation") kinetics models describe the behaviour of these substances in the water-soil system. Presence of potential transformation products (TPs) as a result of pharmaceuticals biodegradation was also studied. To this end, serial batch-type experiments were performed with a soil:water ratio of 1:4 and an initial pharmaceutical concentration of 100µgL(-1). Despite results are dependent on soil characteristics, they revealed that, for those substances with a higher affinity to the soil used (loamy sand), sorption seems to play a key role during the first 48h of contact with soil, and gives way to biodegradation afterwards. The sorption of the pharmaceuticals studied follows a pseudo second-order kinetics. Caffeine and sulfamethoxazole displayed the fastest initial sorption velocities (h=2055 and h=228µgkg(-1)h(-1), respectively). The removal kinetics experiments, satisfactorily simulated by the first-order kinetics model, indicated the presence of potential microbial adaptation to degradation. Indeed, half-lives decreased from 1.6- to 11.7-fold with respect to initial values. The microbial capacity to degrade sulfamethoxazole could be a matter of concern if bacteria have developed resistance to this antibiotic. Caffeine, acetaminophen and sulfamethoxazole were mitigated to a greater extent, whereas the removal of naproxen and carbamazepine was more limited. The appearance of epoxy-carbamazepine and N4-acetyl-sulfamethoxazole as possible TPs of carbamazepine and sulfamethoxazole, respectively, indicated that biodegradation was incomplete and showed the capacity of soil microbes to transform these substances.

Emerging organic contaminants in surface water and groundwater: a first overview of the situation in Italy.

This paper provides the first review of the occurrence of 161 emerging organic compounds (EOCs) in Italian surface water and groundwater. The reported EOCs belong to the groups of industrials, pharmaceuticals, estrogens and illicit drugs. Occurrence of 137 pesticides was also reported. The reviewed research works have been published between 1997 and 2013. The majority of the studies have been carried out in Northern Italy (n. 30) and to a lower extent in Central Italy (n. 13). Only a limited number of research studies report EOC concentrations in water resources of Southern Italy. The EOCs that have been more frequently studied are in the following descending order, pesticides (16), pharmaceuticals (15), industrials (13), estrogens (7) and illicit drugs (2). Research activities investigating the EOC occurrence in surface water are more numerous than those in groundwater. This is consistent with the higher complexity involved in groundwater sampling and EOC detection. Among the reported EOCs, industrials and pesticides are those occurring in both surface water and groundwater with the highest concentrations (up to 15 × 10(6) and 4.78 × 0(5)ng L(-1), respectively). Concentrations of pharmaceuticals in surface water reach a maximum of 3.59 × 10(3)ng L(-1), whereas only the antimicrobial agent josamycin has been encountered in groundwater with a concentration higher than 100 ng L(-1). Both estrogens and illicit drugs appeared in surface water with concentrations lower than 50 ng L(-1). Groundwater concentrations for estrogens were measured to be below the detection limits, whereas illicit drugs have so far not been studied in groundwater. The present review reveals the serious contamination status of Italian surface water and groundwater especially by pesticides, industrials and to a lower extent by pharmaceuticals and the necessity to foster the research on EOC occurrence in Italian water resources, in particular in Southern Italy where a limited number of investigations currently exist.

Sorption/desorption of non-hydrophobic and ionisable pharmaceutical and personal care products from reclaimed water onto/from a natural sediment.

In the present work, the sorption of pharmaceutical and personal care products (PPCPs) (acetaminophen, atenolol, carbamazepine, caffeine, naproxen and sulphamethoxazole) onto the natural organic matter (NOM) and the inorganic surfaces of a natural sandy loam sediment was quantified separately. The quantification was based on the PPCP charge, their degree of ionisation, their octanol-water partitioning coefficient (KOW) and the sediment organic carbon fraction (ƒOC). PPCP desorption from the sediment was examined under conditions of infiltrating water containing a high concentration of inorganic ions (mimicking infiltrating reclaimed water), and a low concentration (and smaller diversity) of inorganic ions (mimicking rainwater infiltration). Batch tests were performed using a sediment/water ratio of 1:4 and a PPCP initial concentration ranging from 1 to 100 µg L(-1). The results showed the type and degree of PPCP ionisation to strongly influence the sorption of these compounds onto the sediment. The sorption of cationic species onto the sediment was higher than that of anionic species and mostly reversible; the sorption of neutral species was negligible. The anionic species sorbed less onto the sediment, but also desorbed less easily. More than 70% of the total sorption was due to interaction with mineral surfaces. This holds especially true for cationic species (atenolol and caffeine) which sorption was enhanced by the negative surface charge of the sediment. The presence of inorganic ions had no impact on the desorption of the PPCPs from the sediment. According to the calculated percentages of removal, the mobility followed the order: carbamazepine>acetaminophen>naproxen>atenolol>sulfamethoxazole>caffeine.

Fate of para-toluenesulfonamide (p-TSA) in groundwater under anoxic conditions: modelling results from a field site in Berlin (Germany).

This article reports on a field modelling study to investigate the processes controlling the plume evolution of para-toluenesulfonamide (p-TSA) in anoxic groundwater in Berlin, Germany. The organic contaminant p-TSA originates from the industrial production process of plasticisers, pesticides, antiseptics and drugs and is of general environmental concern for urban water management. Previous laboratory studies revealed that p-TSA is degradable under oxic conditions, whereas it appears to behave conservatively in the absence of oxygen (O2). p-TSA is ubiquitous in the aquatic environment of Berlin and present in high concentrations (up to 38 µg L(-1)) in an anoxic aquifer downgradient of a former sewage farm, where groundwater is partly used for drinking water production. To obtain refined knowledge of p-TSA transport and degradation in an aquifer at field scale, measurements of p-TSA were carried out at 11 locations (at different depths) between 2005 and 2010. Comparison of chloride (Cl(-)) and p-TSA field data showed that p-TSA has been retarded in the same manner as Cl(-). To verify the transport behaviour under field conditions, a two-dimensional transport model was setup, applying the dual-domain mass transfer approach in the model sector corresponding to an area of high aquifer heterogeneity. The distribution of Cl(-) and p-TSA concentrations from the site was reproduced well, confirming that both compounds behave conservatively and are subjected to retardation due to back diffusion from water stagnant zones. Predictive simulations showed that without any remediation measures, the groundwater quality near the drinking water well galleries will be affected by high p-TSA loads for about a hundred years.

Modelling the removal of p-TSA (para-toluenesulfonamide) during rapid sand filtration used for drinking water treatment.

A finite element model was set-up to determine degradation rate constants for p-TSA during rapid sand filtration (RSF). Data used for the model originated from a column experiment carried out in the filter hall of a drinking water treatment plant in Berlin (Germany). Aerated abstracted groundwater was passed through a 1.6m long column-shaped experimental sand filter applying infiltration rates from 2 to 6mh(-1). Model results were fitted to measured profiles and breakthrough curves of p-TSA for different infiltration rates using both first-order reaction kinetics and Michaelis-Menten kinetics. Both approaches showed that degradation rates varied both in space and time. Higher degradation rates were observed in the upper part of the column, probably related to higher microbial activity in this zone. Measured and simulated breakthrough curves revealed an adaption phase with lower degradation rates after infiltration rates were changed, followed by an adapted phase with more elevated degradation rates. Irrespective of the mathematical approach and the infiltration rate, degradation rates were very high, probably owing to the fact that filter sands have been in operation for decades, receiving high p-TSA concentrations with the raw water.