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.

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.

Occurrence of emerging contaminants, priority substances (2008/105/CE) and heavy metals in treated wastewater and groundwater at Depurbaix facility (Barcelona, Spain).

The presence of 170 pharmaceuticals, personal care products, priority substances according to the 2008/105EU Directive and four metals (Cd, Ni, Hg, Pb) have been investigated at the Llobregat delta, south of Barcelona (Spain). In the area, reclaimed water is destined to satisfy environmental uses, irrigation and the construction of a hydraulic barrier against seawater intrusion in the deep aquifer of the delta. A monitoring survey was undertaken of water samples from a tertiary wastewater treatment plant (Depurbaix), treated waste water with an additional treatment of ultrafiltration, reverse osmosis, and UV disinfection (WWATP, for the hydraulic barrier injection). Groundwater samples from the aquifer receiving recharge were also investigated. The pharmaceutical group of substances was detected in sampled waters at concentrations rarely exceeding a few microg/L, among the compounds Caffeine, Nicotine and Galaxolide (musk fragrance) were found to be present in more than 60% of the samples. Diuron was the only priority substance detected. The four metals were always present in a variable concentration. After the WWATP treatment the majority of analytes are removed from tertiary treated wastewater or their concentration is reduced below 0.1 microg/L. Monitoring revealed a widespread occurrence of analysed compounds in groundwater. Among them Codeine (analgesic), Ibuprofen (anti-inflammatory), Iopamidol, Iopromide (contrast agent) and Paraxanthine (metabolite of caffeine) have only been detected in groundwater, and are not present in water currently being injected in the deep aquifer.