Treated wastewater is an important source of water for irrigation. As a result, irrigated crops are chronically exposed to wastewater-derived pharmaceuticals, such as the anticonvulsant drug lamotrigine. Lamotrigine is known to be taken up by plants, but its plant-derived metabolites and their distribution in different plant organs are unknown. This study aimed to detect and identify metabolites of lamotrigine in cucumber plants grown for 35 days in a hydroponic solution by using LC-MS/MS (Orbitrap) analysis. Our data showed that 96% of the lamotrigine taken up was metabolized. Sixteen metabolites possessing a lamotrigine core structure were detected. Reference standards confirmed two; five were tentatively identified, and nine molecular formulas were assigned. The data suggest that lamotrigine is metabolized via N-carbamylation, N-glucosidation, N-alkylation, N-formylation, N-oxidation, and amidine hydrolysis. The metabolites LTG-N2-oxide, M284, M312, and M370 were most likely produced in the roots and were translocated to the leaves. Metabolites M272, M312, M314, M354, M368, M370, and M418 were dominant in leaves. Only a few metabolites were detected in the fruits. With an increasing exposure time, lamotrigine leaf concentrations decreased because of continuous metabolism. Our data showed that the metabolism of lamotrigine in a plant is fast and that a majority of metabolites are concentrated in the roots and leaves.

In response to the decline in natural water sources, treated wastewater (TWW) has been introduced into the water cycle as a new water source for irrigation. However, this practice exposes the agricultural environment to various contaminants of emerging concern (CECs). To better understand their fate in the soil and to effectively predict their bioavailability for plant uptake, there is a need to quantify their concentrations in soil solutions. In this study, we examined the concentration of TWW-derived CECs in soil solution under three scenarios: (1) shifting from irrigation with freshwater (FW) to TWW (FW→TWW), (2) long-term continuous irrigation with TWW (TWW→TWW), and (3) prolonged irrigation with TWW followed by FW (TWW→FW). Carbamazepine, 1H-benzotriazole, lamotrigine, venlafaxine, and thiabendazole were ubiquitous in the TWW (mean concentrations of 125, 945, 180, 3630, and 90 ng/L, respectively) and irrigated soils. Interestingly, their concentrations in the soil solutions were not similar (higher or lower) to the corresponding concentrations in the irrigation water. In both the FW→TWW and TWW→FW irrigation scenarios, lower CECs concentrations were observed in soil solutions compared to the TWW→TWW scenario, indicating that a steady-state condition was not achieved after a single irrigation season (FW→TWW). For example, the concentrations of 1H-benzotriazole in Nir Oz soil solutions were 638, 310, and 1577 ng/L for the three irrigation scenarios (FW→TWW, TWW→FW, and TWW→TWW), respectively. Moreover, CECs concentrations in soil solutions were slightly lower in the TWW→FW irrigation scenario compared to the TWW→TWW scenario. This suggests that rain-fed crops are also exposed to TWW-derived CECs released from the adsorbed phase into the soil solution. The readily available CEC concentration in soil solutions depends on the soil irrigation history and the CEC concentration in the irrigation water, the soil characteristics, and the physicochemical properties of the CEC.

Irrigation with reclaimed wastewater is a growing practice aimed at conserving freshwater sources, especially in arid and semiarid regions. Despite the apparent advantages to water management, the practice of irrigation with reclaimed wastewater exposes the agroenvironment to contaminants of emerging concern (CECs). In this report, we estimated the unintentional dietary exposure of the Israeli population (2808 participants) to CECs from consumption of produce irrigated with reclaimed wastewater using detailed dietary data obtained from a National Health and Nutrition Survey (Rav Mabat adults; 2014–2016). Human health risk analyses were conducted based on acceptable daily intake (ADI) and threshold of toxicological concern (TTC) approaches. The highest unintentional exposure to wastewater-borne CECs was found to occur through the consumption of leafy vegetables. All analyzed CECs exhibited hazard quotients <1 for the mean- and high-exposure scenarios, indicating no human health concerns. However, for the extreme exposure scenario, the anticonvulsant agents lamotrigine and carbamazepine, and the carbamazepine metabolite epoxide-carbamazepine exhibited the highest exposure levels of 29,100, 27,200, and 19,500 ng/person (70 kg) per day, respectively. These exposure levels exceeded the TTC of lamotrigine and the metabolite epoxide-carbamazepine, and the ADI of carbamazepine, resulting in hazard quotients of 2.8, 1.1, and 1.9, respectively. According to the extreme estimated scenario, consumption of produce irrigated with reclaimed wastewater (leafy vegetables in particular) may pose a threat to human health. Minimizing irrigation of leafy vegetables using reclaimed wastewater and/or improving the quality of the reclaimed wastewater using an advanced treatment would significantly reduce human dietary exposure to CECs.

The exposure of plants to pharmaceuticals via treated wastewater irrigation and biosolid application presents an important route of chronic exposure of crops to a wide variety of bioactive pollutants. This paper presents a novel approach which aims to improve our understanding of the interactions of bioactive pollutants with plants through the concept of plant pharmacology and two main sub-divisions: (i) plant pharmacokinetics which describes the fate of exogenous xenobiotics in the plant based on the processes of absorption, distribution, metabolism and accumulation (ADMA), processes that are analogous to pharmacokinetics in animals; and (ii) plant pharmacodynamics that proposes that exogenous xenobiotics interact with plant enzymes and biochemical pathways, establishing a relationship with pharmacological concepts and emphasizing the importance of exposure-response interactions. The concept of plant pharmacology and its two subdivisions provide a foundation for the development of in-depth knowledge regarding the fate of xenobiotics in plants and establishing plant pharmacokinetic-pharmacodynamic models that include both the ADMA processes and time-dependent response of the plant to these compounds. This concept provides a new perspective on pharmacovigilance, focusing on plant-xenobiotic compound interactions, and a conceptual framework for understanding the fate and interactions of these bioactive molecules in agricultural systems, to enable more accurate risks assessments of environmental and human health.

Bisphenol-A (BPA), 17 alpha-ethinylestradiol (EE2), and 4-nonylphenol (4NP) are endocrine-disrupting chemicals (EDCs) that are useful models for studying the potential fate and transport of EDCs in soil and water environments. Two alluvial soils with contrasting physicochemical properties were used as adsorbents for this study. The Zook soil material had more organic matter and clay than the sandy loam Hanlon soil material. Batch equilibrium experiments were performed to generate adsorption isotherms, to determine the adsorption parameters, and to assess desorption hysteresis. Adsorption of BPA to both soils followed an L-type isotherm, and 4NP adsorbed to both Hanlon and Zook soils exhibited S-shape isotherms. EE2 adsorbed to the Zook soil also followed an S-shaped isotherm, but EE2 adsorbed to the Hanlon soil showed an H-type isotherm. Overall, the Sips model fit the data well, with standard errors of prediction generally <= 6%. The adsorption affinity (K-LF) values were highest for 4NP, and BPA had the lowest hysteresis indices. The data suggest that BPA was most likely adsorbed by soil organic matter via hydrogen bonding involving its two phenolic groups. In contrast, isotherm shape, model affinity indices, lack of desorption, and molecular-scale characteristics led us to infer that 4NP was adsorbed largely by the retention of molecular clusters, perhaps in clay nanopores. Finally, the adsorption of EE2 exhibited different isotherm shapes for the two soils as well as intermediate affinity and desorption indices, suggesting that EE2 molecules could be retained both by soil organic matter and by clay.

Pharmaceuticals and other contaminants of emerging concern (CECs) are continuously introduced into the agroecosystem via reclaimed wastewater irrigation, a common agricultural practice in water-scarce regions. Although reclaimed wastewater irrigated crops are sold and consumed, only limited information is available on the occurrence of pharmaceuticals and other CECs in edible produce. Here, we report data on CECs in irrigation water, soils, and crops collected from 445 commercial fields irrigated with reclaimed wastewater in Israel. The following produce were analyzed: leafy greens, carrot, potato, tomato, orange, tangerine, avocado, and banana. Pharmaceuticals and CECs were found in quantifiable levels in all irrigation water, soils, and plants (>99.6%). Leafy greens exhibited the largest number and the highest concentration of pharmaceuticals. Within the same crop, contamination levels varied due to wastewater source and quality of treatment, and soil characteristics. Anticonvulsants (carbamazepine, lamotrigine, and gabapentin) were the most dominant therapeutic group found in the reclaimed wastewater-soil-plant continuum. Antimicrobials were detected in similar to 85% of the water and soil samples, however they exhibited low detection frequencies and concentrations in produce. Irrigation with reclaimed wastewater should be limited to crops where the risk for pharmaceutical transfer to the food chain is minimal.

Reclaimed wastewater is increasingly used to irrigate agriculture crops. We have previously shown that carbamazepine (CBZ), an anticonvulsant human medication, not entirely discarded during wastewater purification, induces a stress response in tomatoes grown with roots bathing in CBZ-containing water. Induction of stress-related osmoprotectants (sugars, amino acids, proteins) was conspicuous in CBZ-treated seedlings. Here, tomato seedlings were grown in pots watered with increasing concentrations of CBZ. Soluble sugars effectively reacted to CBZ in both leaves and roots. However, the induction of stress-related amino acids and proteins was relevant in roots, but insignificant in leaves. Therefore, roots may be the site where CBZ stress is exerted. Moreover, roots may protect the whole plant from the pharmaceutical. Tomato crops endure biotic stresses, caused by whitefly (Bemisia tabaci) infestation and by the tomato yellow leaf curl begomovirus (TYLCV) they vector. The interplay between CBZ, TYLCV infection and B. tabaci was studied in tomato. Whiteflies preferred CBZ-treated plantlets than control plants, which may be due to increased amount of sugars in leaves. The increased amount of viruliferous whiteflies on CBZ-treated plants is expected to be accompanied by a rise in virus amounts. In fact, CBZ caused a reduction of TYLCV amounts. CBZ-dependent activation of autophagy degradation may explain this decrease in virus amounts. TYLCV infection mitigates the activation of stress markers associated with CBZ treatment. Altogether, CBZ in the water used to irrigate tomatoes grown in pots causes a relatively weak plant stress response, but is definitively sensed by insect and by virus.

The anticonvulsant drug lamotrigine is a recalcitrant environmental pollutant. It was detected in drinking water, surface water, reclaimed wastewater, arable soils, and even in edible crops. In this work, we studied the mechanisms of lamotrigine transformation by a common redox soil mineral, birnessite, in a single-solute system and in bisolute systems with vanillic acid or o-methoxyphenol. In the single-solute system, 28% of lamotrigine was transformed and 14 transformation products (TPs) were identified. Based on a detailed analysis of the TPs, we suggested that lamotrigine is transformed mainly by oxidation, addition, and dechlorination reactions. In the bisolute systems, the redox-active phenolic compounds enhanced the elimination and transformation of lamotrigine. Vanillic acid was more efficient, generating 92% transformation of lamotrigine (58 TPs were identified), whereas o-methoxyphenol induced 48% transformation (35 TPs were identified). In the bisolute system with phenolic compounds, lamotrigine has possibly been transformed mainly via addition reactions with phenolic compounds and their oxidation products (protocatechuic acid, quinone, and oligomers). Thus, masses of the formed TPs were elevated as compared to the parent compound. The current study demonstrates the important role of redox-active minerals and naturally occurring phenolic compounds in abiotic removal and transformation of a recalcitrant environmental pollutant.

The exposure of plants to pharmaceuticals via treated wastewater irrigation and biosolid application presents an important route of chronic exposure of crops to a wide variety of bioactive pollutants. This paper presents a novel approach which aims to improve our understanding of the interactions of bioactive pollutants with plants through the concept of plant pharmacology and two main sub-divisions: (i) plant pharmacokinetics which describes the fate of exogenous xenobiotics in the plant based on the processes of absorption, distribution, metabolism and accumulation (ADMA), processes that are analogous to pharmacokinetics in animals; and (ii) plant pharmacodynamics that proposes that exogenous xenobiotics interact with plant enzymes and biochemical pathways, establishing a relationship with pharmacological concepts and emphasizing the importance of exposure-response interactions. The concept of plant pharmacology and its two subdivisions provide a foundation for the development of in-depth knowledge regarding the fate of xenobiotics in plants and establishing plant pharmacokinetic-pharmacodynamic models that include both the ADMA processes and time-dependent response of the plant to these compounds. This concept provides a new perspective on pharmacovigilance, focusing on plant-xenobiotic compound interactions, and a conceptual framework for understanding the fate and interactions of these bioactive molecules in agricultural systems, to enable more accurate risks assessments of environmental and human health.

Dissolved organic matter (DOM) is ubiquitous in aquatic environments where it interacts with a variety of particles including carbonaceous materials (CMs). The complexity of both DOM and the CMs makes DOM-CM interactions difficult to predict. In this study we have identified the preferential sorption of specific DOM fractions as being dependent on their aromaticity and molecular weight, as well as on the surface properties of the CMs. This was achieved by conducting sorption batch experiments with three types of DOM (humic acid, Suwannee River natural organic matter, and a compost extract) and three types of CMs (graphite, carbon nanotubes, and biochar) with different geometries and surface complexities. The non-adsorbed DOM fraction was analyzed by size exclusion chromatography and preferentially sorbed molecular weight fractions were analyzed by UV/vis and fluorescence spectroscopy. All three sorbent types were found to preferentially sorb aromatic DOM fractions, but DOM fractionation depended on the particular combination of sorbent and sorbate characteristics. Single-walled carbon nanotubes only sorbed the smaller molecular weight fractions (<1 kDa). The sorption of smaller DOM fractions was not accompanied by a preference for less aromatic compounds, contrary to what was suggested in previous studies. While graphite preferentially sorbed the most aromatic DOM fraction (1-3 kDa), the structural heterogeneity of biochar resulted in reduced selectivity, sorbing all DOM > 1 kDa. The results explain the lack of correlation found in previous studies between the amount of aromatic carbon in a bulk DOM and its sorption coefficient. DOM sorption by CMs was generally controlled by DOM aromaticity but complex sorbent surfaces with high porosity, curvatures and functional groups strongly reduced the importance of aromaticity.

Pesticides are potentially toxic to aquatic systems, even at low concentration, depending on their individual ecotoxicological properties and their mixture composition. Thus, to evaluate possible ecological stress due to pesticide load, a thorough assessment of the potential toxicity of pesticide mixtures is required. Here we report water discharge and quality data of an eastern Mediterranean micro-estuary (Alexander stream), targeting the temporal distribution of a pesticide mixture. Over 150 water samples were collected during 2 hydrological years representing base-flow and flood conditions. On average, each water sample contained 34 and 45 different pesticides with peak concentrations of 1.4 mu g L-1 of Imidacloprid and 55 mu g L-1 of Diuron during base-flow and flood events, respectively. Pesticide mixtures were potentially toxic to benthic invertebrates and algae during flood events, surpassing the toxicity benchmark with medians of 110% and 155%, respectively. The herbicide Diuron and the insecticide Imidacloprid were the main pesticides responsible for the high potential toxicity during flood events. The falling limb of the flood hydrographs was found to inflict the highest stress on the estuarine environment due to elevated toxicity combined with prolonged residence time of the water. Examination of the potential chronic toxicity of single compounds showed continuous stress for plants, algae, amphibians, crustaceans, insects and fish from nine pesticides. Our data show that the ecosystem of the Alexander micro-estuary is under a continuous chronic stress with acute peaks in potential toxicity during flood events and the period that follows them. We propose that analyzing a small set of flood-tail samples is needed for the evaluation of small estuarine ecosystems risk during the rainy season. From a management perspective, we suggest better control of application practices for Diuron in the watershed to minimize the stress to the estuarine ecosystem. (C) 2020 Elsevier Ltd. All rights reserved.

Treated wastewater (TWW) is increasingly used for agricultural irrigation, especially in arid and semi-arid regions. Carbamazepine is among the most frequently detected pharmaceuticals in TWW. Moreover, its uptake and accumulation have been demonstrated in crops irrigated with TWW. A previous controlled trial found that urine concentrations of carbamazepine were higher in healthy volunteers consuming TWW-irrigated produce as compared to freshwater-irrigated produce. The aim of the current study was to assess whether carbamazepine is quantifiable in urine of Israelis consuming their usual diets and whether concentrations vary according to age, personal characteristics and diet. In this cross-sectional study, we recruited 245 volunteers, including a reference group of omnivorous healthy adults aged 18-66; pregnant women; children aged 3-6 years; adults aged > 75 years; and vegetarians/vegans. Participants provided spot urine samples and reported 24-hour and ``usual'' dietary consumption. Urinary carbamazepine levels were compared according to group, personal characteristics, health behaviors, and reported diet. Carbamazepine was detectable (>= 1.66 ng/L) in urine of 84%, 76%, 75.5%, 66%, and 19.6% of the reference group, vegetarians, older adults, pregnant women, and children, respectively. Quantifiable concentrations (>= 5.0 ng/L) of carbamazepine were found in 58%, 46%, 36.7%, 14%, and 0% of these groups, respectively (p = 0.001 for comparison of proportions across groups). In adults, higher carbamazepine concentrations were significantly associated (p < 0.05) with self-defined vegetarianism, usual consumption of dairy products and at least five vegetables/day, and no meat or fish consumption in the past 24 hours. This study demonstrates that people living in a water-scarce region with widespread TWW irrigation, are unknowingly exposed to carbamazepine. Individuals adhering to recommended guidelines for daily fresh produce consumption may be at higher risk of exposure to TWW-derived contaminants of emerging concern.

The use of nanotechnology to suppress crop diseases is gaining increasing interest in agriculture. Copper sulfide nanoparticles (CuS NPs) were synthesized at 1 : 1 and 1 : 4 ratios of Cu and S and their respective antifungal efficacy was evaluated against the pathogenic activity ofGibberella fujikuroi(bakanae disease) in rice (Oryza sativaL.). In a 2 din vitrostudy, CuS (1 : 1) and CuS (1 : 4) NPs at 50 mg L(-1)decreasedG. fujikuroicolony-forming units (CFU) by 35.7 and 33%, respectively, compared to controls; commercial CuO NPs caused an 18.7% inhibition. In a greenhouse study, treating with both types of CuS NPs at 50 mg L(-1)at the seed stage significantly decreased disease incidence on rice by 35.1 and 45.9%, respectively. Comparatively, CuO NPs achieved only 8.1% disease reduction, and the commercial Cu-based pesticide Kocide 3000 had no impact on disease. Foliar-applied CuO NPs and CuS (1 : 1) NPs decreased disease incidence by 30.0 and 32.5%, respectively, which outperformed CuS (1 : 4) NPs (15%) and Kocide 3000 (12.5%). Notably, CuS (1 : 4) NPs also modulated the shoot salicylic acid (SA) and jasmonic acid (JA) production to enhance the plant defense mechanisms againstG. fujikuroiinfection. These findings provide useful information for improving the delivery efficiency of agrichemicalsvianano-enabled strategies while minimizing their environmental impact, and advance our understanding of the defense mechanisms triggered by the NPs presence in plants.

Pharmaceuticals remain in treated wastewater used to irrigate agricultural crops. Their effect on terrestrial plants is practically unknown. Here we tested whether these compounds can be considered as plant stress inducers. Several features characterize the general stress response in plants: production of reactive oxygen species acting as stress-response signals, MAPKs signaling cascade inducing expression of defense genes, heat shock proteins preventing protein denaturation and degradation, and amino acids playing signaling roles and involved in osmoregulation. Tomato seedlings bathing in a cocktail of pharmaceuticals (Carbamazepine, Valporic acid, Phenytoin, Diazepam, Lamotrigine) or in Carbamazepine alone, at different concentrations and during different time-periods, were used to study the patterns of stress-related markers. The accumulation of the stress-related biomarkers in leaf and root tissues pointed to a cumulative stress response, mobilizing the cell protection machinery to avoid metabolic modifications and to restore homeostasis. The described approach is suitable for the investigation of stress response of different crop plants to various contaminants present in treated wastewater.

Micro-estuarine ecosystems have a surface area <1 km2 and are abundant in Mediterranean regions. As a result of their small size, these systems are particularly vulnerable to the effects of chemical pollution. Due to the fluctuating flow conditions of base flow dominated by treated wastewater effluents and flood events transporting rural and urban non-point-source pollution, micro-estuaries are under a dynamic risk regime, consequently struggling to provide ecological services. This 2 year study explored the occurrence and risks of pharmaceutical contamination in the Alexander micro-estuary in Israel. Pharmaceuticals were detected in all samples (n = 280) at as high as 18 μg L–1 in flood events and 14 μg L–1 in base flow. The pharmaceutical mixture composition was affected by flow conditions with carbamazepine dominating the base flow and caffeine dominating flood events. The median annual risk quotients for fish, crustaceans, and algae were 19.6, 5.2, and 4.5, respectively, indicating that pharmaceuticals pose a high risk to the ecosystem. Ibuprofen, carbamazepine, and caffeine contributed most to the risk quotients. The current work highlights that micro-estuary ecosystems, like the Alexander estuary, are continuously exposed to pharmaceuticals and most likely to other pollutants, placing these ecologically important systems under an elevated risk in comparison to the more frequently studied large estuarine systems.Micro-estuarine ecosystems have a surface area <1 km2 and are abundant in Mediterranean regions. As a result of their small size, these systems are particularly vulnerable to the effects of chemical pollution. Due to the fluctuating flow conditions of base flow dominated by treated wastewater effluents and flood events transporting rural and urban non-point-source pollution, micro-estuaries are under a dynamic risk regime, consequently struggling to provide ecological services. This 2 year study explored the occurrence and risks of pharmaceutical contamination in the Alexander micro-estuary in Israel. Pharmaceuticals were detected in all samples (n = 280) at as high as 18 μg L–1 in flood events and 14 μg L–1 in base flow. The pharmaceutical mixture composition was affected by flow conditions with carbamazepine dominating the base flow and caffeine dominating flood events. The median annual risk quotients for fish, crustaceans, and algae were 19.6, 5.2, and 4.5, respectively, indicating that pharmaceuticals pose a high risk to the ecosystem. Ibuprofen, carbamazepine, and caffeine contributed most to the risk quotients. The current work highlights that micro-estuary ecosystems, like the Alexander estuary, are continuously exposed to pharmaceuticals and most likely to other pollutants, placing these ecologically important systems under an elevated risk in comparison to the more frequently studied large estuarine systems.

Pharmaceuticals remain in treated wastewater used to irrigate agricultural crops. Their effect on terrestrial plants is practically unknown. Here we tested whether these compounds can be considered as plant stress inducers. Several features characterize the general stress response in plants: production of reactive oxygen species acting as stress-response signals, MAPKs signaling cascade inducing expression of defense genes, heat shock proteins preventing protein denaturation and degradation, and amino acids playing signaling roles and involved in osmoregulation. Tomato seedlings bathing in a cocktail of pharmaceuticals (Carbamazepine, Valporic acid, Phenytoin, Diazepam, Lamotrigine) or in Carbamazepine alone, at different concentrations and during different time-periods, were used to study the patterns of stress-related markers. The accumulation of the stress-related biomarkers in leaf and root tissues pointed to a cumulative stress response, mobilizing the cell protection machinery to avoid metabolic modifications and to restore homeostasis. The described approach is suitable for the investigation of stress response of different crop plants to various contaminants present in treated wastewater.

Ternary interactions between carbon nanotubes (CNTs), dissolved organic matter (DOM) and small organic molecules (namely low molecular mass organic pollutants) are of great importance since they can affect the reactivity and fate of all involved compartments in the environment. This review thoroughly assesses existing knowledge on the adsorption of DOM and small organic molecules by CNTs, while giving special attention to (i) the complex nature of DOM, (ii) the ternary rather than binary interactions between CNTs, DOM and the small organic molecules and (iii) the DOM-organic molecule interactions. We discuss in detail the main factors influencing DOM adsorption by CNTs and attempt to differentiate between the role of DOM composition and conformation. We then outline how the presence of DOM influences the adsorption of small organic molecules by CNTs, considering the introduction stage of DOM and the impact of the organic molecule's properties. DOM adsorption by CNTs is highly dependent on its composition and is governed by the size, hydrophobicity and aromaticity of DOM. DOM adsorption was found to alter the assembly of the CNTs, resulting in changes in the distribution of adsorption sites. Small organic molecules may adsorb to residual surface area on the CNTs, to DOM-coating the CNTs or remain in solution, possibly complexed with DOM. This results in their suppressed or enhanced adsorption in comparison to DOM-free media. The physicochemical properties of the organic molecules (hydrophobicity, size, structure and charge) also play a major role in this process. We present knowledge gaps that need clarification such as the extent of DOM desorption from CNTs, the amount of co-adsorbed DOM during competition with small organic molecules for adsorption sites on the CNTs and the behavior of CNTs under realistic conditions. More data generated from experiments using natural DOM rather than dissolved humic substances are required to improve our understanding of the interactions between CNTs and small organic molecules in realistic environmental scenarios. This review provides conclusions and research directions needed to evaluate the nature of interactions between CNTs, DOM and organic pollutants in aquatic systems affected by anthropogenic activities. © 2019 Elsevier B.V.

Heteroaggregation with clay mineral particles (CMPs) is significant to the environmental application and fate of increasingly produced nanoparticulate zero-valent iron (nZVI). Co-settling, kinetic aggregation, calculation of the classical Derjaguin-Landau-Verwey-Overbeek interaction energy, and electron microscopic observation were carried out to investigate the interaction between nZVIs (three naked nZVIs of different sizes and one carboxymethyl cellulose (CMC) coated nZVI) and CMPs (kaolinite and montmorillonite). Under pH 6.5 and 9.5 conditions, Lewis acid-base interaction contributed to the attachment between nZVIs and CMPs, while electrostatic attraction was involved in nZVI-CMP attachment under pH 3.5. Compared with the heteroaggregates formed by nZVIs attaching to CMP edges and faces under pH 6.5 and 3.5 conditions, the heteroaggregates were smaller with nZVIs mainly connecting to CMP edges under pH 9.5. Small nZVI homoaggregates were bound to CMP edges at low nZVI concentrations (nZVI/CMP mass ratio at 0.015) with CMP concentrations of 330 mg L-1 and large nZVI-CMP heteroaggregates formed by nZVI bridging with increasing nZVI concentrations. The smallest nZVI exhibited the strongest heteroaggregation with CMPs; the CMC coating inhibited the interfacial interaction and heteroaggregation between nZVIs and CMPs; kaolinite had higher potential to interact with nZVIs under neutral conditions. These findings are helpful for understanding the interaction between nZVIs and minerals and of significance to environmental remediation using nZVIs. © 2019 The Royal Society of Chemistry.

Irrigation with treated wastewater (TWW) and application of biosolids introduce numerous pharmaceutical and personal care products (PPCPs) into agro-food systems. While the use of TWW and biosolids has many societal benefits, introduction of PPCPs in production agriculture poses potential food safety and human health risks. A comprehensive risk assessment and management scheme of PPCPs in agro-food systems is limited by multiple factors, not least the sheer number of investigated compounds and their diverse structures. Here we follow the fate of PPCPs in the water-soil-produce continuum by considering processes and variables that influence PPCP transfer and accumulation. By analyzing the steps in the soil-plant-human diet nexus, we propose a tiered framework as a path forward to prioritize PPCPs that could have a high potential for plant accumulation and thus pose greatest risk. This article examines research progress to date and current research challenges, highlighting the potential value of leveraging existing knowledge from decades of research on other chemicals such as pesticides. A process-driven scheme is outlined to derive a short list that may be used to refocus our future research efforts on PPCPs and other analogous emerging contaminants in agro-food systems. © 2019 American Chemical Society.

Carbamazepine (CBZ)is an anticonvulsant drug used for epilepsy and other disorders. Prescription of CBZ during pregnancy increases the risk for congenital malformations. CBZ is ubiquitous in effluents and persistent during wastewater treatment. Thus, it is re-introduced into agricultural ecosystems upon irrigation with reclaimed wastewater. People consuming produce irrigated with reclaimed wastewater were found to be exposed to CBZ. However, environmental concentrations of CBZ (μg L−1)are magnitudes lower than its therapeutic levels (μg ml−1), raising the question of whether and how environmental levels of CBZ affect embryonic development. The chick embryo is a powerful and highly sensitive amniotic model system that enables to assess environmental contaminants in the living organism. Since the chick embryonic development is highly similar to mammalians, yet, it develops in an egg, toxic effects can be directly analyzed in a well-controlled system without maternal influences. This research utilized the chick embryo to test whether CBZ is embryo-toxic by using morphological, cellular, molecular and imaging strategies. Three key embryonic stages were monitored: after blastulation (st.1HH), gastrulation/neurulation (st.8HH)and organogenesis (st.15HH). Here we demonstrate that environmental relevant concentrations of CBZ impair morphogenesis in a dose- and stage- dependent manner. Effects on gastrulation, neural tube closure, differentiation and proliferation were exhibited in early stages by exposing embryos to CBZ dose as low as 0.1 μg L−1. Quantification of developmental progression revealed a significant difference in the total score obtained by CBZ-treated embryos compared to controls (up to 5-fold difference, p < 0.05). Yet, defects were unnoticed as embryos passed gastrulation/neurulation. This study provides the first evidence for teratogenic effect of environmental-relevant concentrations of CBZ in amniotic embryos that impair early but not late stages of development. These findings call for in-depth risk analysis to ensure that the environmental presence of CBZ and other drugs is not causing irreversible ecological and public-health damages. © 2019