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.

Enzyme activity indicates soil functionality affectation with low levels of trace elements.

The use of the soil can alter its functionality and influence the (bio)availability of any contaminants present. Our study considers two types of agricultural soils, rainfed and olive soils, managed according to conventional practices that apply contaminants directly to the soil (fertilizers, pesticides, fungicides, etc.) and receive contaminants from the atmosphere (traffic, industry, etc.); and a forest soil that is not subject to these agricultural practices. In this scenario, we consider a mixture of 16 trace elements (As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, Sb, Sn, V and Zn), since their interactions with the soil can produce synergistic and/or antagonistic effects that are not considered in most studies. We studied whether the content and (bio)availability of low concentrations of a mixture of trace elements affect the soil functionality in terms of the activity of some key enzymes We analysed the total, potentially and immediately available fractions, the soil parameters and soil enzyme activity. The results show that the functionality of the soils studied was affected despite the low concentrations of trace elements. The highest concentrations of total trace elements and available fractions were found in forest soils compared to the other two uses. Soil enzyme activity is best explained by the potentially available fraction of a mixture of trace elements and physico-chemical soil variables. In our study, pH, total nitrogen, organic carbon and fine mineral particles (silt and clay) had an influence on soil enzyme activity and the (bio)available fractions of trace elements.

Phytodesalinization potential of Typha angustifolia, Juncus maritimus, and Eleocharis palustris for removal of de-icing salts from runoff water.

Typha angustifolia, Juncus maritimus, and Eleocharis palustris were evaluated for de-icing salt removal from runoff water. Plants were exposed to a range of de-icing salt levels (0.2, 0.7, 4, 8, and 13 dS m(-1)) in laboratory-scale subsurface constructed wetlands (CWs) for 2 months under greenhouse conditions. Effluent characteristics, plant height, biomass, and Cl and Na removal rates and uptake were monitored. More water volume was retained in CWs of T. angustifolia (∼60 %) than of J. maritimus and E. palustris (∼37.5 %), which accounted for the electrical conductivity increase in effluents (1.3-1.9-fold). Based on the NaCl removal rate, T. angustifolia showed the greatest phytodesalinization ability (31-60 %) with the highest removal at the lowest salt levels (0.2-0.7 dS m(-1)), followed by J. maritimus (22-36 %) without differences in removal among levels, and E. palustris (3-26 %) presenting a removal rate highly decreased with increasing salt levels. Plant height and biomass were stimulated at low de-icing salt levels, but, at higher levels, T. angustifolia and E. palustris growth was inhibited (tolerance index ∼67 and 10 %, respectively, in the worst cases). Salt amounts in aboveground biomass in g m(-2) differed among levels and ranged as follows: 13.6-29.1 (Cl), 4.2-9.3 (Na; T. angustifolia); 7.0-12.0 (Cl), 2.7-6.4 (Na; J. maritimus); and 0.9-7.6 (Cl), 0.3-1.6 (Na; E. palustris). Chloride and Na translocation decreased with de-icing salt increase in T. angustifolia, while no significant differences were found in J. maritimus, which is interesting for harvesting purposes.

Impact of vineyard abandonment and natural recolonization on metal content and availability in Mediterranean soils.

Abandonment of vineyards after uprooting has dramatically increased in last decades in Mediterranean countries, often followed by vegetation expansion processes. Inadequate management strategies can have negative consequences on soil quality. We studied how the age and type of vegetation cover and several environmental characteristics (lithology, soil properties, vineyard slope and so on) after vineyard uprooting and abandonment contribute to the variation patterns in total, HAc (acetic acid-method, HAc) and EDTA-extractable (ethylenediaminetetraacetic acid-method) concentrations of Cd, Cu, Pb and Zn in soils. We sampled 141 points from vineyards and abandoned vineyard Mediterranean soils recolonized by natural vegetation in recent decades. The contribution of several environmental variables (e.g. age and type of vegetation cover, lithology, soil properties and vineyard slope) to the total and extractable concentrations of metals was evaluated by canonical ordination based on redundancy analysis, considering the interaction between both environmental and response variables. The ranges of total metal contents were: 0.01-0.15 (Cd), 2.6-34 (Cu), 6.6-30 (Pb), and 29-92mgkg(-1) (Zn). Cadmium (11-100%) had the highest relative extractability with both extractants, and Zn and Pb the lowest. The total and EDTA-extractable of Cd, Pb and Zn were positively related to the age of abandonment, to the presence of Agrostis castellana and Retama sphaerocarpa, and to the contents of Fe-oxides, clay and organic matter (OM). A different pattern was noted for Cu, positively related to vineyard soils. Soil properties successfully explained HAc-extractable Cd, Cu, Pb and Zn but the age and type of vegetation cover lost significance. Clay content was negatively related to HAc-extractable Cu and Pb; and OM was positively related to HAc-Cd and Zn. In conclusion, the time elapsed after vineyard uprooting, and subsequent land abandonment, affects the soil content and availability of metals, and this impact depended on the colonizing plant species and soil properties.

Improving the relationship between soil characteristics and metal bioavailability by using reactive fractions of soil parameters in calcareous soils.

The contribution of the nature instead of the total content of soil parameters relevant to metal bioavailability in lettuce was tested using a series of low-polluted Mediterranean agricultural calcareous soils offering natural gradients in the content and composition of carbonate, organic, and oxide fractions. Two datasets were compared by canonical ordination based on redundancy analysis: total concentrations (TC dataset) of main soil parameters (constituents, phases, or elements) involved in metal retention and bioavailability; and chemically defined reactive fractions of these parameters (RF dataset). The metal bioavailability patterns were satisfactorily explained only when the RF dataset was used, and the results showed that the proportion of crystalline Fe oxides, dissolved organic C, diethylene-triamine-pentaacetic acid (DTPA)-extractable Cu and Zn, and a labile organic pool accounted for 76% of the variance. In addition, 2 multipollution scenarios by metal spiking were tested that showed better relationships with the RF dataset than with the TC dataset (up to 17% more) and new reactive fractions involved. For Mediterranean calcareous soils, the use of reactive pools of soil parameters rather than their total contents improved the relationships between soil constituents and metal bioavailability. Such pool determinations should be systematically included in studies dealing with bioavailability or risk assessment.

Biological activity in metal-contaminated calcareous agricultural soils: the role of the organic matter composition and the particle size distribution.

Organic matter (OM) plays a key role in microbial response to soil metal contamination, yet little is known about how the composition of the OM affects this response in Mediterranean calcareous agricultural soils. A set of Mediterranean soils, with different contents and compositions of OM and carbonate and fine mineral fractions, was spiked with a mixture of Cd, Cu, Pb, and Zn and incubated for 12 months for aging. Microbial (Biolog Ecoplates) and enzyme activities (dehydrogenase, DHA; ß-galactosidase, BGAL; phosphatase, PHOS; and urease, URE) were assessed and related to metal availability and soil physicochemical parameters. All enzyme activities decreased significantly with metal contamination: 36-68 % (DHA), 24-85 % (BGAL), 22-72 % (PHOS), and 14-84 % (URE) inhibitions. Similarly, catabolic activity was negatively affected, especially phenol catabolism (∼86 % compared to 25-55 % inhibition for the rest of the substrates). Catabolic and DHA activities were negatively correlated with ethylenediaminetetraacetic acid (EDTA)-extractable Cd and Pb, but positively with CaCl2, NaNO3, and DTPA-extractable Cu and Zn. Soluble OM (water- and hot-water-soluble organic C) was positively related to enzyme and catabolic activities. Recalcitrant OM and fine mineral fractions were positively related to BGAL and PHOS. Conversely, catabolic activity was negatively related to clay and positively to silt and labile OM. Results indicate that the microbial response to metal contamination is highly affected by texture and OM composition.

Metal extractability patterns to evaluate (potentially) mobile fractions in periurban calcareous agricultural soils in the Mediterranean area-analytical and mineralogical approaches.

A set of periurban calcareous agricultural Mediterranean soils was spiked with a mixture of Cd, Cu, Pb and Zn at two levels within the limit values proposed by current European legislation, incubated for up to 12 months, and subjected to various one-step extraction procedures to estimate mobile (neutral salts) and potentially mobile metal fractions (complexing and acidic extraction methods). The results obtained were used to study metal extractability patterns according to the soil characteristics. The analytical data were coupled with mineralogical investigations and speciation modelling using the Visual Minteq model. The formation of soluble metal-complexes in the complexing extracts (predicted by the Visual Minteq calculations) led to the highest extraction efficiency with complexing extractants. Metal extractability patterns were related to both content and composition of carbonate, organic matter, Fe oxide and clay fractions. Potentially mobile metal fractions were mainly affected by the finest soil fractions (recalcitrant organic matter, active lime and clay minerals). In the case of Pb, scarce correlations between extractable Pb and soil constituents were obtained which was attributed to high Pb retention due to the formation of 4PbCO3·3PbO (corroborated by X-ray diffraction). In summary, the high metal proportion extracted with complexing agents highlighted the high but finite capacity to store potentially mobilizable metals and the possible vulnerability of these soils against environmental impact from metal accumulation.

Metal contamination disturbs biochemical and microbial properties of calcareous agricultural soils of the Mediterranean area.

Mediterranean climate characteristics and carbonate are key factors governing soil heavy-metal accumulation, and low organic matter (OM) content could limit the ability of microbial populations to cope with resulting stress. We studied the effects of metal contamination on a combination of biological parameters in soils having these characteristics. With this aim, soils were spiked with a mixture of cadmium, copper, lead, and zinc, at the two limit values proposed by current European legislation, and incubated for ≤12 months. Then we measured biochemical (phosphatase, urease, ß-galactosidase, arylsulfatase, and dehydrogenase activities) and microbial (fungal and bacterial DNA concentration by quantitative polymerase chain reaction) parameters. All of the enzyme activities were strongly affected by metal contamination and showed the following inhibition sequence: phosphatase (30-64 %) < arylsulfatase (38-97 %) ≤ urease (1-100 %) ≤ ß-galactosidase (30-100 %) < dehydrogenase (69-100 %). The high variability among soils was attributed to the different proportion of fine mineral fraction, OM, crystalline iron oxides, and divalent cations in soil solution. The decrease of fungal DNA concentration in metal-spiked soils was negligible, whereas the decrease of bacterial DNA was ~1-54 % at the lowest level and 2-69 % at the highest level of contamination. The lowest bacterial DNA decrease occurred in soils with the highest OM, clay, and carbonate contents. Finally, regarding the strong inhibition of the biological parameters measured and the alteration of the fungal/bacterial DNA ratio, we provide strong evidence that disturbance on the system, even within the limiting values of contamination proposed by the current European Directive, could alter key soil processes. These limiting values should be established according to soil characteristics and/or revised when contamination is produced by a mixture of heavy metals.