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Publications

2022
Ben Mordechay, E. ; Sinai, T. ; Berman, T. ; Dichtiar, R. ; Keinan-Boker, L. ; Tarchitzky, J. ; Maor, Y. ; Mordehay, V. ; Manor, O. ; Chefetz, B. Wastewater-derived organic contaminants in fresh produce: Dietary exposure and human health concerns. 2022, 223, 118986. Publisher's VersionAbstract
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.
Malchi, T. ; Eyal, S. ; Czosnek, H. ; Shenker, M. ; Chefetz, B. Plant pharmacology: Insights into in-planta kinetic and dynamic processes of xenobiotics. Critical Reviews in Environmental Science and Technology 2022, 52, 3525 - 3546. Publisher's VersionAbstract
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.
2021
Rivas Chen, F. ; Chefetz, B. ; Thompson, M. L. Comparison of adsorption behaviors of selected endocrine-disrupting compounds in soil. JOURNAL OF ENVIRONMENTAL QUALITY 2021, 50, 756-767.Abstract
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.
Ben Mordechay, E. ; Mordehay, V. ; Tarchitzky, J. ; Chefetz, B. Pharmaceuticals in edible crops irrigated with reclaimed wastewater: Evidence from a large survey in Israel. JOURNAL OF HAZARDOUS MATERIALS 2021, 416.Abstract
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.
Gorovits, R. ; Shteinberg, M. ; Mishra, R. ; Ben Ari, J. ; Malchi, T. ; Chefetz, B. ; Anfoka, G. ; Czosnek, H. Interplay of stress responses to carbamazepine treatment, whitefly infestation and virus infection in tomato plants. PLANT STRESS 2021, 1.Abstract
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.
Karpov, M. ; Seiwert, B. ; Mordehay, V. ; Reemtsma, T. ; Polubesova, T. ; Chefetz, B. Abiotic Transformation of Lamotrigine by Redox-Active Mineral and Phenolic Compounds. ENVIRONMENTAL SCIENCE & TECHNOLOGY 2021, 55, 1535-1544.Abstract
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.
Malchi, T. ; Eyal, S. ; Czosnek, H. ; Shenker, M. ; Chefetz, B. Plant pharmacology: Insights into in-planta kinetic and dynamic processes of xenobiotics. CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 2021.Abstract
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.
2020
Castan, S. ; Sigmund, G. ; Hueffer, T. ; Tepe, N. ; von der Kammer, F. ; Chefetz, B. ; Hofmann, T. The importance of aromaticity to describe the interactions of organic matter with carbonaceous materials depends on molecular weight and sorbent geometry. ENVIRONMENTAL SCIENCE-PROCESSES & IMPACTS 2020, 22, 1888-1897.Abstract
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.
Topaz, T. ; Egozi, R. ; Suari, Y. ; Ben-Ari, J. ; Sade, T. ; Chefetz, B. ; Yahel, G. Environmental risk dynamics of pesticides toxicity in a Mediterranean micro-estuary. ENVIRONMENTAL POLLUTION 2020, 265.Abstract
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.
Schapira, M. ; Manor, O. ; Golan, N. ; Kalo, D. ; Mordehay, V. ; Kirshenbaum, N. ; Goldsmith, R. ; Chefetz, B. ; Paltiel, O. Involuntary human exposure to carbamazepine: A cross-sectional study of correlates across the lifespan and dietary spectrum. ENVIRONMENT INTERNATIONAL 2020, 143.Abstract
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.
Shang, H. ; Ma, C. ; Li, C. ; White, J. C. ; Polubesova, T. ; Chefetz, B. ; Xing, B. Copper sulfide nanoparticles suppressGibberella fujikuroiinfection in rice (Oryza sativaL.) by multiple mechanisms: contact-mortality, nutritional modulation and phytohormone regulation. ENVIRONMENTAL SCIENCE-NANO 2020, 7 2632-2643.Abstract
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.
Gorovits, R. ; Sobol, I. ; Akama, K. ; Chefetz, B. ; Czosnek, H. Pharmaceuticals in treated wastewater induce a stress response in tomato plants. SCIENTIFIC REPORTS 2020, 10.Abstract
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.
Topaz, T. ; Boxall, A. ; Suari, Y. ; Egozi, R. ; Sade, T. ; Chefetz, B. Ecological Risk Dynamics of Pharmaceuticals in Micro-Estuary Environments. Environmental Science & TechnologyEnvironmental Science & Technology 2020. Publisher's VersionAbstract
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.
Gorovits, R. ; Sobol, I. ; Akama, K. ; Chefetz, B. ; Czosnek, H. Pharmaceuticals in treated wastewater induce a stress response in tomato plants. Sci Rep 2020, 10, 1856.Abstract
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.
2019
Engel, M. ; Chefetz, B. The missing link between carbon nanotubes, dissolved organic matter and organic pollutants. Advances in Colloid and Interface Science 2019, 271. Publisher's VersionAbstract
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.
Wang, Y. ; Yang, K. ; Chefetz, B. ; Xing, B. ; Lin, D. The pH and concentration dependent interfacial interaction and heteroaggregation between nanoparticulate zero-valent iron and clay mineral particles. Environmental Science: Nano 2019, 6 2129-2140. Publisher's VersionAbstract
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.
Fu, Q. ; Malchi, T. ; Carter, L. J. ; Li, H. ; Gan, J. ; Chefetz, B. Pharmaceutical and Personal Care Products: From Wastewater Treatment into Agro-Food Systems. Environmental Science and Technology 2019. Publisher's VersionAbstract
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.
Kohl, A. ; Golan, N. ; Cinnamon, Y. ; Genin, O. ; Chefetz, B. ; Sela-Donenfeld, D. A proof of concept study demonstrating that environmental levels of carbamazepine impair early stages of chick embryonic development. Environment International 2019, 129, 583-594. Publisher's VersionAbstract
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
Guo, H. ; Ma, C. ; Thistle, L. ; Huynh, M. ; Yu, C. ; Clasby, D. ; Chefetz, B. ; Polubesova, T. ; White, J. C. ; He, L. ; et al. Transformation of Ag ions into Ag nanoparticle-loaded AgCl microcubes in the plant root zone. Environmental Science: Nano 2019, 6 1099-1110. Publisher's VersionAbstract
Natural formation of metal nanoparticles is an important pathway that will modify the fate, behavior, and biological availability of heavy metal ions in the environment. Most work has focused on the ability of natural organic matter (NOM) and extracellular polymeric substances (EPS) to convert metal ions into nanoparticles. However, plant roots, ubiquitous in soil and aquatic environments, may have a significant role in the formation of naturally occurring metal nanoparticles. This work demonstrates the importance of plant roots and associated exudates in mediating the transformation of Ag+ in the presence of sunlight. Using Ag+ as the starting material, transformation took place in three steps: 1) formation of AgCl microcubes (μAgCl) through complexation of Ag+ by plant-released chloride ions in root exudates; 2) stabilization of μAgCl by biomolecules in root exudates; 3) partial photoreduction of μAgCl to Ag(0) nanoparticles (nAg) facilitated by exudate biomolecules. Morphological and compositional changes were observed by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) on the particles from 0-24 h: Cubic AgCl microcrystals were converted into cauliflower-shaped core-shell structures with nAg clusters as the shell and μAgCl as the core. The quantification of Ag+, μAgCl and nAg species over time demonstrates that the transformation kinetics fit (R2 = 0.99) a second-order reaction (k = 1.11 mM-1 h-1). The discovery of plant root exudate-mediated phototransformation of Ag+ adds new knowledge to our understanding of Ag transformation in the plant root zone and will guide the assessment of both exposure and risk in the environment. © 2019 The Royal Society of Chemistry.
Chefetz, B. ; Marom, R. ; Salton, O. ; Oliferovsky, M. ; Mordehay, V. ; Ben-Ari, J. ; Hadar, Y. Transformation of lamotrigine by white-rot fungus Pleurotus ostreatus. Environmental Pollution 2019, 250, 546-553. Publisher's VersionAbstract
One of the most persistent pharmaceutical compounds commonly found in treated wastewater is lamotrigine (LTG). It has also been detected in soils and crops irrigated with treated wastewater. Here we focused on the ability of the white-rot edible mushroom Pleurotus ostreatus to remove and transform LTG in liquid cultures. At concentrations of environmental relevance (1 and 10 μg L−1) LTG was almost completely removed from the culture medium within 20 days. To elucidate the mechanism of LTG removal and transformation, we applied a physiological-based approach using inhibitors and a competing agent. These experiments were conducted at a higher concentration for metabolites detection. Based on identification of sulfur-containing metabolites and LTG N2-oxide and the effect of specific inhibitors, cytochrome P450 oxidation is suggested as one of the reaction mechanisms leading to LTG transformation. The variety and number of transformation products (i.e., conjugates) found in the current study were larger than reported in mammals. Moreover, known conjugates with glucuronide, glutathione, or cysteine/glycine, were not found in our system. Since the majority of the identified transformation products were conjugates of LTG, this study highlights the persistence of LTG as an organic pollutant in ecosystems exposed to wastewater. © 2019 Elsevier Ltd