Antibiotic resistance (AR) is becoming a worldwide threat due to the increasing occurrence of antibiotic-resistant pathogenic bacterial strains. There is a general consensus about the potential ...implications of the use of antibiotics in livestock on the onset of antibiotic resistant bacteria (ARB), mainly through meat consumption. However, the ever-increasing use of reclaimed wastewater (RWW) in agriculture may also contribute significantly to the non-accounted exposure to antibiotics, ARB, and antibiotic resistance genes (ARGs). This position paper aims at evaluating the current knowledge concerning the occurrence of antibiotics, ARBs, and ARGs in edible parts of different common crops irrigated with RWW. We will discuss which regulations on the use of RWW may contribute to the minimization of the prevalence of these contaminants in crops, and provide recommendations on how to minimize the impact of these practices.
Environmental fate assessment of chemicals involves standardized simulation tests with isotope-labeled molecules to balance transformation, mineralization, and formation of nonextractable residues ...(NER). Methods to predict microbial turnover and biogenic NER have been developed, having limited use when metabolites accumulate, the chemicals are not the only C source, or provide for other macroelements. To improve predictive capability, we extended a recently developed method for microbial growth yield estimation to account for incomplete degradation and multiple-element assimilation and combined it with a dynamic model for fate description in soils and sediments. We evaluated the results against the unique experimental data of
C
-
N co-labeled glyphosate turnover with AMPA formation in water-sediment systems (OECD 308). Balancing
C- and
N- fluxes to biomass showed a pronounced shift of glyphosate transformation from full mineralization to AMPA formation. This may be explained by various hypotheses, for example, the limited substrate turnover inherent to the batch conditions of the test system causing microbial starvation or inhibition by P release. Modeling results indicate initial N overload due to the lower C/N ratio in glyphosate compared to average cell composition leading to subsequent C demand and accumulation of AMPA.
Background
The assessment of persistence, bioaccumulation and toxicity (PBT) is part of the regulation process of ionic organic compounds (IOCs) and a major challenge, as a commonly acknowledged ...approach for the estimation of the bioaccumulation potential of IOCs is still missing. The goal of the present study was, therefore, to experimentally determine the bioaccumulation of fully ionized compounds and to identify screening parameters that can indicate high bioaccumulation potential of IOCs. Three feeding studies with rainbow trout (
Oncorhynchus mykiss
) were carried out according to OECD TG 305. Separation of liver, gastrointestinal tract (GIT) and carcass allowed to further elucidate the tissue distribution of the individual test substances. The chemicals chosen had characteristics that made them suspect for high bioaccumulation, and included two cations (tetrabutylphosphonium bromide (TBP), trimethyloctadecyl ammonium chloride (TMOA)) and four anions (benzotriazole, tecloftalam, pentachlorophenol (PCP), MEE-phosphonate). Data on the dietary biomagnification of IOCs (strong acids) were also collected from published literature.
Results
The highest distribution factors were found for the GIT, followed by liver. However, none of the tested IOCs showed a distinct biomagnification potential, as kinetic biomagnification factors (BMF
k
) ranged between 0.001 and 0.05 g/g (median 0.009 g/g). Cations showed lower assimilation efficiency (α) than anions, except for tecloftalam. In contrast, anions showed a considerably faster depuration rate (half-life less than 0.5 days) compared to cations (half-life of around 5 days). Sixteen potential screening parameters for BMF were calculated with a chemical property estimation tool (ACD/i-Lab) and correlated with the BMF data from this study and from literature. The number of hydrogen bond donors (nHBD) showed the highest correlation to measured BMF, but the prediction is only based on two values (one or two nHBD), while the other descriptors were insignificantly correlated.
Conclusion
The suspected dietary bioaccumulation potential of the six IOCs could not be confirmed in the feeding studies with rainbow trout. The more than twenty screening parameters showed no particularly high correlation neither with the test results nor with the BMF values collected from literature. The results corroborate earlier findings that ionization lowers the tendency of a chemical for dietary bioaccumulation, compared to non-ionized chemicals. In addition to the lipophobicity of ionic molecule moieties, fast depuration seems to be a major reason for the observed low dietary bioaccumulation of ionic compounds, in particular anions. Fast depuration may happen due to rapid metabolism of charged compounds, and future studies should test this hypothesis.
Perfluoroalkyl acids (PFAAs) bioaccumulate in crops, with uptake being particularly high for short-chain PFAAs that are constantly transported with transpiration water to aerial plant parts. Due to ...their amphiphilic surfactant nature and ionized state at environmental pH, predicting the partitioning behavior of PFAAs is difficult and subject to considerable uncertainty, making experimental data highly desirable. Here, we applied a plant uptake model that combines advective flux with measured partition coefficients to reproduce the set of empirically derived plant uptake and soil-partitioning data for nine PFAAs in red chicory, in order to improve the mechanistic understanding and provide new insights into the complex uptake processes. We introduced a new parameter for retarded uptake (R) to explain the slow transfer of PFAA across biomembranes of the root epidermis, which has led to low transpiration stream concentration factors (TSCFs) presented in literature so far. We estimated R values for PFAAs using experimental data derived for red chicory and used the modified plant uptake model to simulate uptake of PFAA into other crops. Results show that this semi-empirical model predicted PFAAs transport to shoots and fruits with good accuracy based on experimental root to soil concentration factors (RCFdw) and soil to water partition coefficients (Kd) as well as estimated R values and plant-specific data for growth and transpiration. It can be concluded that the combination of rather low Kd with high RCFdw and the absence of any relevant loss are the reason for the observed excellent plant uptake of PFAAs.
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•Short-chain perfluoroalkyl acids (PFAAs) are highly bioaccumulative in edible crops.•Plant uptake model extended to interpret the uptake of nine PFAAs into red chicory.•New parameter R for slow transfer through root membranes estimated for red chicory.•The newly developed semi-empirical model was successfully applied for other crops.•High PFAA uptake in plants is the combination of persistence, low Kd and high RCF.
Direct reuse of reclaimed wastewater (RWW) in agriculture has recently received increasing attention as a possible solution to water scarcity. The presence of contaminants of emerging concern (CECs) ...in RWW can be critical, as these chemicals can be uptaken in irrigated crops and eventually ingested during food consumption.
In the present study, an integrated model was developed to predict the fate of CECs in water reuse systems where RWW is used for edible crops irrigation. The model was applied to a case study where RWW (originating from a municipal wastewater treatment plant) is discharged into a water channel, with subsequent irrigation of silage maize, rice, wheat and ryegrass. Environmental and human health risks were assessed for 13 CECs, selected based on their chemical and hazard characteristics. Predicted CEC concentrations in the channel showed good agreement with available measurements, indicating potential ecotoxicity of some CECs (estrogens and biocides) due to their limited attenuation. Plant uptake predictions were in good agreement with existing literature data, indicating higher uptake in leaves and roots than fruits. Notably, high uncertainties were shown for weakly acidic CECs, possibly due to degradation in soil and pH variations inside plants. The human health risk due to the ingestion of wheat and rice was assessed using the threshold of toxicological concern and the hazard quotient. Both approaches predicted negligible risk for most CECs, while sulfamethoxazole and 17α-ethinylestradiol exhibited the highest risk for consumers. Alternative scenarios were evaluated to identify possible risk minimization strategies (e.g., adoption of a more efficient irrigation system).
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•An integrated model was developed to describe CEC fate in irrigation systems.•Good agreement between predictions and in situ measurements and literature data.•Human health risk was predicted for four tested crops irrigated with reclaimed wastewater.•Health risk alert was shown for sulfamethoxazole and 17-α ethinylestradiol.
Many scientific studies present removal efficiencies for pharmaceuticals in laboratory-, pilot-, and full-scale wastewater treatment plants, based on observations that may be impacted by theoretical ...and methodological approaches used. In this Critical Review, we evaluated factors influencing observed removal efficiencies of three antibiotics (sulfamethoxazole, ciprofloxacin, tetracycline) in pilot- and full-scale biological treatment systems. Factors assessed include (i) retransformation to parent pharmaceuticals from e.g., conjugated metabolites and analogues, (ii) solid retention time (SRT), (iii) fractions sorbed onto solids, and (iv) dynamics in influent and effluent loading. A recently developed methodology was used, relying on the comparison of removal efficiency predictions (obtained with the Activated Sludge Model for Xenobiotics (ASM-X)) with representative measured data from literature. By applying this methodology, we demonstrated that (a) the elimination of sulfamethoxazole may be significantly underestimated when not considering retransformation from conjugated metabolites, depending on the type (urban or hospital) and size of upstream catchments; (b) operation at extended SRT may enhance antibiotic removal, as shown for sulfamethoxazole; (c) not accounting for fractions sorbed in influent and effluent solids may cause slight underestimation of ciprofloxacin removal efficiency. Using tetracycline as example substance, we ultimately evaluated implications of effluent dynamics and retransformation on environmental exposure and risk prediction.
Emerging organic contaminants (EOCs) undergoing incomplete removal during wastewater treatment may be found in treated wastewater (TWW) used for irrigation of agricultural products. Following uptake ...into edible plant parts, EOCs may eventually enter in the food chain, with associated human exposure. In the present study, we used a newly developed steady-state plant uptake model with added phloem transport to predict the uptake of four EOCs (carbamazepine, ibuprofen, ketoprofen and naproxen) into three varieties of lettuce. Input data were derived from an experimental study with vegetables grown in greenhouse and irrigated with TWW spiked with CBZ at 0, 30, 60, 120 and 210 µg/L in each variety of lettuce.
Predicted carbamazepine concentrations in leaves were on average 82% higher than in roots, with good agreement between measured and calculated data. We subsequently predicted the uptake of anti-inflammatory compounds ibuprofen, ketoprofen and naproxen, for which the chemical analysis could not provide concentrations above detection limit. These three substances are weak acids and predicted concentrations in roots were higher than in the edible leaves, mainly due to phloem transport downwards. The daily dietary intake of all four EOCs was estimated for consumption of leafy vegetables, being far below usual therapeutic doses.
•This study presents a model for plant uptake of EOCs in leaves and roots.•The model considers the adsorption to proteins and phloem transport of weak acids.•Input data were derived from an experimental study with lettuces spiked with CBZ.•The simulation of CBZ concentrations in lettuce showed a good prediction.•The prediction of IBP, KTP and NPX does not imply any risk to human health.
Solid-liquid partitioning is one of the main fate processes determining the removal of micropollutants in wastewater. Little is known on the sorption of micropollutants in biofilms, where molecular ...diffusion may significantly influence partitioning kinetics. In this study, the diffusion and the sorption of 23 micropollutants were investigated in novel moving bed biofilm reactor (MBBR) carriers with controlled biofilm thickness (50, 200 and 500 μm) using targeted batch experiments (initial concentration = 1 μg L−1, for X-ray contrast media 15 μg L−1) and mathematical modelling. We assessed the influence of biofilm thickness and density on the dimensionless effective diffusivity coefficient f (equal to the biofilm-to-aqueous diffusivity ratio) and the distribution coefficient Kd,eq (L g−1). Sorption was significant only for eight positively charged micropollutants (atenolol, metoprolol, propranolol, citalopram, venlafaxine, erythromycin, clarithromycin and roxithromycin), revealing the importance of electrostatic interactions with solids. Sorption equilibria were likely not reached within the duration of batch experiments (4 h), particularly for the thickest biofilm, requiring the calculation of the distribution coefficient Kd,eq based on the approximation of the asymptotic equilibrium concentration (t > 4 h). Kd,eq values increased with increasing biofilm thickness for all sorptive micropollutants (except atenolol), possibly due to higher porosity and accessible surface area in the thickest biofilm. Positive correlations between Kd,eq and micropollutant properties (polarity and molecular size descriptors) were identified but not for all biofilm thicknesses, thus confirming the challenge of improving predictive sorption models for positively charged compounds. A diffusion-sorption model was developed and calibrated against experimental data, and estimated f values also increased with increasing biofilm thickness. This indicates that diffusion in thin biofilms may be strongly limited (f ≪ 0.1) by the high biomass density (reduced porosity).
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•Diffusion-sorption of pharmaceuticals assessed in biofilms of different thicknesses.•Sorption significant only for eight positively ionized compounds.•Sorption coefficients increased with increasing biofilm thickness.•Several days necessary to reach partitioning equilibrium in thicker biofilms.•Effective diffusivity in biofilm negatively influenced by biofilm density.
In biofilm systems for wastewater treatment (e.g., moving bed biofilms reactors-MBBRs) biofilm thickness is typically not under direct control. Nevertheless, biofilm thickness is likely to have a ...profound effect on the microbial diversity and activity, as a result of diffusion limitation and thus substrate penetration in the biofilm. In this study, we investigated the impact of biofilm thickness on nitrification and on the removal of more than 20 organic micropollutants in laboratory-scale nitrifying MBBRs. We used novel carriers (Z-carriers, AnoxKaldnes) that allowed controlling biofilm thickness at 50, 200, 300, 400, and 500 μm. The impact of biofilm thickness on microbial community was assessed via 16S rRNA gene amplicon sequencing and ammonia monooxygenase (amoA) abundance quantification through quantitative PCR (qPCR). Results from batch experiments and microbial analysis showed that (i) the thickest biofilm (500 μm) presented the highest specific biotransformation rate constants (kbio, L g(-1) d(-1)) for 14 out of 22 micropollutants; (ii) biofilm thickness positively associated with biodiversity, which was suggested as the main factor for the observed enhancement of kbio; (iii) the thinnest biofilm (50 μm) exhibited the highest nitrification rate (gN d(-1) g(-1)), amoA gene abundance and kbio values for some of the most recalcitrant micropollutants (i.e., diclofenac and targeted sulfonamides). Although thin biofilms favored nitrification activity and the removal of some micropollutants, treatment systems based on thicker biofilms should be considered to enhance the elimination of a broad spectrum of micropollutants.