International audience | From 1899 to 2002, sandy Luvisol in the Paris region has been intensively irrigated with raw wastewater, resulting in major soil pollution by metallic trace elements (MTE). To identify the soil phases implicated in retaining these metals, sequential extractions were performed on a solum irrigated with untreated wastewater and another reference solum. The endogenous and exogenous fractions of MTE in the contaminated soil were discriminated using correlations between MTE and major elements defined from unpolluted soils of the area. In the contaminated soil no exogenous lead and chromium are present below the surface horizon, whereas exogenous zinc and copper are found down to the base of the solum. The endogenous MTE are mainly found in the residual fraction. Exogenous MTE appear to be associated with organic matter in the surface horizon, and exogenous zinc seems to be readsorbed on iron and manganese oxyhydroxides in the underlying horizons. After 100 years of intensive irrigation with wastewater, no exogenous Pb and Cr are found in the subsoil, while exogenous Zn and Cu are found down to the base of the solum, mostly readsorbed.

The presence of phenols, such as nonylphenol (NP), bisphenol (BPA), and octylphenol (OP), in the environment have been receiving increased attention due to their potential risks to human health and environment. The use of reclaimed water for irrigation may be one of the sources of these phenols in the agricultural system. A field experiment was conducted to assess the effects of reclaimed water irrigation on phenol contamination of agricultural topsoil and products in the North China Plain between 2015 and 2016. Three irrigation treatments were applied to all crops: reclaimed water irrigation, groundwater irrigation and alternative irrigation with reclaimed water and groundwater (1:1, v/v). The results showed that the concentrations of NP, BPA, and OP in the topsoil were 0.02–0.54, 0.004–0.06, and ND–9.9 × 10⁻³ mg/kg, respectively; the corresponding values in agricultural products were 0.007–0.70, 0.004–0.24, and ND–1.08 mg/kg, respectively. The concentration of NP in the topsoil and agricultural products and that of BPA in the agricultural products were all less than the recommended limits. The yields of wheat, maize, vegetables were 4.35–7.08, 1.03–6.46, and 10.9–67.0 t/ha, respectively. The bioaccumulation factors (BCFs) of OP, NP, and BPA for cereals were 0.7–4.77, 0.16–4.59, and 1.3–23.9, respectively; the corresponding values in vegetables were 0.0–4.53 (except cucumber and eggplant), 0.38–12.6, and 0.57–24.3, respectively. No significant differences in phenol concentrations, BCFs, or yields of wheat and vegetables were observed among the three irrigation treatments. In conclusion, compared with groundwater irrigation, reclaimed water irrigation in this experiment did not significantly affect phenol concentrations in the topsoil and agricultural products as well as BCFs and yields of wheat and vegetables. However, because the quality of reclaimed water may vary across collected areas, additional experiments are warranted to analyze the effects of reclaimed water irrigation on the risk of phenol contamination.

Pharmacologically active compounds found in reclaimed wastewater irrigation or animal manure fertilizers pose potential risks for agriculture. The mechanism underlying the effects of ketoprofen on rice (Oryza sativa L.) seedlings was investigated. The results showed that low concentrations (0.5 mg L⁻¹) of ketoprofen slightly stimulate growth of rice seedlings, while high concentrations can significantly inhibit growth by reducing biomass and causing damage to roots. Ketoprofen affects photosynthetic pigment content (Chla, Chlb, and carotenoids) and chlorophyll synthesis gene (HEMA, HEMG, CHLD, CHLG, CHLM, and CAO) expression. Fluorescence parameters such as minimum fluorescence (F₀), maximum fluorescence (Fₘ), variable fluorescence (Fᵥ), potential photosynthetic capacity (Fᵥ/F₀), maximum quantum efficiency of PSII photochemistry (Fᵥ/Fₘ), electron transfer rate (ETR), and Y(II), Y(NPQ), Y(NO) values were affected, showing photosynthetic electron transfer was blocked. Active oxygen radical (O₂•−and H₂O₂), malondialdehyde and proline content increased. Superoxide dismutase, catalase and ascorbate peroxidase activities, glutathione content and antioxidant-related gene (FSD1, MSD1, CSD1, CSD2, CAT1, CAT2, CAT3, APX1, APX2) expression were induced. Higher integrated biomarker response values of eight oxidative stress response indexes were obtained at higher ketoprofen concentrations. Ultrastructure observation showed that ketoprofen causes cell structure damage, chloroplast swelling, increase in starch granules, and reduction in organelles. This study provides some suggested toxicological mechanisms and biological response indicators in rice due to stress from pharmacologically active compounds.

Propylparaben is widely used as a preservative in pharmaceuticals and personal care products and is ultimately excreted by the human body. Thus, propylparaben reaches sewage and enters the soil environment by sludge fertilization and wastewater irrigation. However, there are few existing studies on the toxicity and risks of such chemicals in terrestrial environments. In this study, a multispecies bioassay for propylparaben was performed and protective concentrations (PCs) were derived based on toxicity values by probabilistic ecological risk assessment. Acute and chronic bioassays were conducted on 11 species in eight taxonomic groups (Magnoliopsida, Liliopsida, Clitellata, Entognatha, Entomobryomorpha, Chromadorea, Chlorophyceae, Trebouxiophyceae). Based on the toxicity values calculated, the PC₉₅ values for acute and chronic SSDs were 13 and 6 mg/kg dry soil, respectively. Toxicity varied among taxa, with soil algae emerging as the most sensitive to propylparaben. This may be attributable to differences in exposure pathways among species. The exposure pathway of propylparaben can be altered by adsorption to soil particles. As parabens are presently under-regulated globally in terms of their environmental effects, our findings can serve as the basis to propose standard values for environmental protection.

With increasing demand for recycled wastewater for irrigation purposes, there is a need to evaluate the potential for manufactured nanomaterials in waste water to impact crop production and agroecosystems. Copper oxide nanoparticles (CuO NPs) have previously been shown to negatively impact the growth of duckweed (Landoltia punctata) a model aquatic plant consumed by water fowl and widely found in agricultural runoff ditches in temperate climates. However, prior studies involving CuO NP toxicity to duckweed have focused on systems without the presence of dissolved organic matter (DOM). In the current study, duckweed growth inhibition was shown to be a function of aqueous Cu²⁺ concentration. Growth inhibition was greatest from aqueous CuCl₂ and, for particles, increased with decreasing CuO particle size. The dissolution of CuO NPs in ½ Hoagland's solution was measured to increase with decreasing particle size and in the presence of Suwannee river humic and fulvic acids (HA; FA). However, the current results suggest that HA, and to a lesser extent, FA, decrease the toxicity of both CuO NPs and free ionized Cu to duckweed, likely by inhibiting Cu availability through Cu-DOM complex formation. Such results are consistent with changes to Cu speciation as predicted by speciation modeling software and suggest that DOM changes Cu speciation and therefore toxicity in natural systems.

The use of reclaimed wastewater for irrigation is foreseen as a possible strategy to mitigate the pressure on water resources in dry regions. However, there is the risk of potential accumulation of contaminants of emerging concern (CECs) in the edaphic environment, their percolation and consequently contamination of aquifers. In the present study, we measured the levels of a wide range of commonly used pharmaceutically active compounds (PhACs) in sewage from a local wastewater treatment plant (WWTP) and in soils irrigated with treated wastewater. Analysis of target compounds showed total concentrations between 73 and 372 μg L⁻¹ in WWTP influents, and from 3 to 41 μg L⁻¹ in effluents. The total concentrations of PhACs detected in surface soil samples were in the range of 2 and 15 ng g⁻¹, with predominance of analgesics and anti-inflammatories (maximum concentration = 10.05 ng g⁻¹), followed by antibiotics and psychiatric drugs (maximum concentration = 5.45 ng g⁻¹ and 3.78 ng g⁻¹, respectively). Both effluent samples and irrigated soils shared similar compositional patterns, with compounds such as hydrochlorothiazide and diclofenac being predominant. Additionally, PhACs were also detected in soil samples at a depth of 150 cm, indicating that these chemical undergo leaching associated with heavy-rain episodes. Their occurrence in soils was affected by temperature too, as maximum concentrations were measured in colder months (up to 14 ng g⁻¹), indicating higher persistence at lower temperatures. Finally, the ecotoxicological risk of PhACs in soil was evaluated by calculating their risk quotients (RQs). The risk was very low as RQ values ranged between <0.01 and 0.07. However, this initial assessment could be improved by future works on toxicity using specific terrestrial organisms.

The effects of wastewater irrigation and sewage sludge on the dissipation behavior of the fungicide benalaxyl and its primary metabolite benalaxyl acid in soil were studied on an enantiomeric level during a 148-day exposure experiment. Chiral separation and analysis of the two pairs of enantiomers were achieved using HPLC-MS/MS with a chiralpak IC chiral column. Benalaxyl decreased with half-life of 16.1 days in soil under tap water irrigation with preferential residue of S-benalaxyl. Benalaxyl acid was formed with great preference of R-enantiomer before 21 days while enriched in S-enantiomer afterwards. The degradation of benalaxyl was restrained by both wastewater and treated wastewater irrigation, but the enantioselectivity in S-benalaxyl residue was enhanced. Benalaxyl acid was also formed with similar enantioselectivity as in tap water irrigation. Sewage sludge could accelerate benalaxyl degradation with shorter half-life. Surprisingly, the enantioselectivity with preference degradation of S-enantiomer in sewage sludge was opposite to that in soil. More benalaxyl acid was generated with EF values always lower than 0.5 and remained longer in sewage sludge than in soil. A sterilization experiment indicated that the conversion of benalaxyl to benalaxyl acid and the enantioselectivity were determined by the microorganisms in soil or sewage sludge. Farming practices like wastewater irrigation and sewage sludge application might not only influence the fate of pesticide, but also the enantioselectivity of chiral pesticide enantiomers and thus the risks of pesticide residues posed to the environment.

Antibiotics are added to agricultural fields worldwide through wastewater irrigation or manure application, resulting in antibiotic contamination and elevated environmental risks to terrestrial environments and humans. Most studies focused on antibiotic detection in different matrices or were conducted in a hydroponic environment. Little is known about the transfer of antibiotics from antibiotic-contaminated irrigation wastewater and animal manure to agricultural soil and edible crops. In this study, we evaluated the transfer of five different antibiotics (tetracycline, sulfamethazine, norfloxacin, erythromycin, and chloramphenicol) to different crops under two levels of antibiotic-contaminated wastewater irrigation and animal manure fertilization. The final distribution of tetracycline (TC), norfloxacin (NOR) and chloramphenicol (CAP) in the crop tissues under these four treatments were as follows: fruit > leaf/shoot > root, while an opposite order was found for sulfamethazine (SMZ) and erythromycin (ERY): root > leaf/shoot > fruit. The growth of crops could accelerate the dissipation of antibiotics by absorption from contaminated soil. A higher accumulation of antibiotics was observed in crop tissues under the wastewater treatment than under manure treatment, which was due to the continual irrigation that increased adsorption in soil and uptake by crops. The translocation of antibiotics in crops mainly depended on their physicochemical properties (e.g. log Kow), crop species, and the concentrations of antibiotics applied to the soil. The levels of antibiotics ingested through the consumption of edible crops under the different treatments were much lower than the acceptable daily intake (ADI) levels.

The use of wastewater for irrigation may introduce antimicrobials and human pathogens into the food supply through vegetative uptake. The objective of this study was to investigate the uptake of three antimicrobials and Salmonella in two lettuce cultivars. After repeated subirrigation with synthetic wastewater, lettuce leaves and soil were collected at three sequential harvests. The internalization frequency of Salmonella in lettuce was low. A soil horizon-influenced Salmonella concentration gradient was determined with concentrations in bottom soil 2 log CFU/g higher than in top soil. Lincomycin and sulfamethoxazole were recovered from lettuce leaves at concentrations as high as 822 ng/g and 125 ng/g fresh weight, respectively. Antimicrobial concentrations in lettuce decreased from the first to the third harvest suggesting that the plant growth rate may exceed antimicrobial uptake rates. Accumulation of antimicrobials was significantly different between cultivars demonstrating a subspecies level variation in uptake of antibiotics in lettuce.

Sewage impacted soil, sludge and water samples were studied to understand the occurrence and formation of thiosteranes and to determine the relevance of these compounds as tracers for sewage input into the environment. Soils were collected from wastewater irrigation fields (Wroclaw, Poland), water from the Nexapa River Basin (Mexico), which also received wastewater and wastewater treatment plant (WWTP) effluent, and water and sludge from the Norman WWTP (USA) at different treatment stages. Thiosteranes represented a high proportion of the steroid fraction in the Wroclaw irrigation field and the Nexapa River Basin samples. Small amounts of thiosteranes were found in anaerobically digested sludge from the Norman WWTP. A good correlation between coprostanone and thiosterane concentrations suggests thiosteranes were produced by stanone sulphurization under anoxic conditions. Thiosterane stability under anoxic and suboxic conditions indicates their potential use as tracers for environmental input of sewage products or land application of sewage sludge.