Efficient Catalytic Oxidation of Ethylene at 0 °C on an in Situ Carbon Modified Pt Catalyst Supported on SBA-15.

The design of efficient catalysts for catalytic ethylene (C2H4) oxidation is of crucial importance for extending the shelf life of fruits and vegetables. Herein, a carbon modified SBA-15 supported Pt catalyst (Pt/CSBA-15) was prepared in situ by a facile solid phase grinding-infiltration-inert atmosphere calcination method. Characterization results reveal that in the Pt/CSBA-15 catalysts thin carbon layers are successfully formed in the hexagonal pores of SBA-15. Additionally, Pt particles are well dispersed in the channels of SBA-15, and Pt/CSBA-15 has a smaller Pt particle size than the catalyst without carbon modification (i.e., Pt/SBA-15). O2 is more feasibly adsorbed and activated on small-sized Pt particles, and in situ formed carbon species enhance the hydrophobicity of catalysts. As a result, both 3Pt/CSBA-15 and 5Pt/CSBA-15 are able to maintain 100% conversion of 50 ppm of C2H4 for more than 7 h at 0 °C. 3Pt/CSBA-15 even achieves 81.5% C2H4 conversion and 71.6% CO2 yield after 20 h, exhibiting much more prominent catalytic performances than 3Pt/SBA-15. DFT calculations and in situ FTIR measurements confirm that small-sized Pt particles possess strong O2 affinity to promote O2 adsorption, and in situ formed hydrophobic carbon layers efficiently suppress competitive H2O adsorption. Such a unique one-step catalyst preparation method for regulating the size of metal particles and the hydrophobicity of catalysts can be perfectly utilized to develop simple and efficient hydrophobic catalysts applied in low-temperature oxidation of C2H4.

Mitigating risks and maximizing sustainability of treated wastewater reuse for irrigation.

Scarcity of freshwater for agriculture has led to increased utilization of treated wastewater (TWW), establishing it as a significant and reliable source of irrigation water. However, years of research indicate that if not managed adequately, TWW may deleteriously affect soil functioning and plant productivity, and pose a hazard to human and environmental health. This review leverages the experience of researchers, stakeholders, and policymakers from Israel, the United-States, and Europe to present a holistic, multidisciplinary perspective on maximizing the benefits from municipal TWW use for irrigation. We specifically draw on the extensive knowledge gained in Israel, a world leader in agricultural TWW implementation. The first two sections of the work set the foundation for understanding current challenges involved with the use of TWW, detailing known and emerging agronomic and environmental issues (such as salinity and phytotoxicity) and public health risks (such as contaminants of emerging concern and pathogens). The work then presents solutions to address these challenges, including technological and agronomic management-based solutions as well as source control policies. The concluding section presents suggestions for the path forward, emphasizing the importance of improving links between research and policy, and better outreach to the public and agricultural practitioners. We use this platform as a call for action, to form a global harmonized data system that will centralize scientific findings on agronomic, environmental and public health effects of TWW irrigation. Insights from such global collaboration will help to mitigate risks, and facilitate more sustainable use of TWW for food production in the future.

Pharmacokinetics of the Recalcitrant Drug Lamotrigine: Identification and Distribution of Metabolites in Cucumber Plants.

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.

Pesticides and pharmaceuticals data collected during two consecutive years in a Mediterranean micro-estuary.

The Alexander micro-estuary, located at the eastern edge of the Mediterranean Sea, is a typical example of small water bodies that suffer from a combination of urban and agricultural pollution, and overuse of its natural water sources. It is∼6.5 km long, with maximum depth of 3 m and maximum width of 45 m. To evaluate the anthropogenic stress on the system and its ability to mitigate pollution, water samples were collected within the framework of Ruppin's Estuarine and Coastal Observatory [1]. Water samples were collected from the estuary head, which drains about 510 km2, and at a point 300 m upstream from the estuary mouth before water flows into the Mediterranean Sea. A total of 236 stormwater and 44 base-flow water samples between December 2016 and December 2018. Stormwater samples were collected every 0.25 - 4 h along the entire course of the flow events using an automated samplers (Sigma 900, Hach Company, Loveland CO, USA; and ISCO 3700 Full-Size Portable Sampler, Teledyne, Lincoln, NE, USA). Base-flow samples were taken once a month using a horizontal grab sampler (5 L, model 110B, OceanTest Equipment, Fort Lauderdale, FL, USA). All samples were filtered using 90mmGF/F filters (nominal pore size of 0.7 µm, MGF, Sartorius, Göttingen, Germany) and immediately frozen (-20°C) before chemical analysis. Chemical analysis was performed using liquid chromatography with high-resolution mass spectrometry (LC-HRMS) analysis using a QExactive Plus hybrid FT mass spectrometer coupled with a Dionex Ultimate 3000 RS UPLC (Thermo Fisher Scientific, Waltham, MA, USA). The targeted analysis, which included 15 fungicides, 25 herbicides, 18 Insecticides, and 19 pharmaceuticals, concluded with a total of 21,142 entries. All entries are organized in a worksheet, along with location, date, flood section duration, discharge rate, and the total water volume discharged during the relevant period. The provided data offers an opportunity to explore the sources, transport, and impact of a large mixture of organic pollutants in a confined aquatic system located in an urbanized coastal environment.

Wastewater-derived organic contaminants in fresh produce: Dietary exposure and human health concerns.

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.

Sorption and Mobility of Charged Organic Compounds: How to Confront and Overcome Limitations in Their Assessment.

Permanently charged and ionizable organic compounds (IOC) are a large and diverse group of compounds belonging to many contaminant classes, including pharmaceuticals, pesticides, industrial chemicals, and natural toxins. Sorption and mobility of IOCs are distinctively different from those of neutral compounds. Due to electrostatic interactions with natural sorbents, existing concepts for describing neutral organic contaminant sorption, and by extension mobility, are inadequate for IOC. Predictive models developed for neutral compounds are based on octanol-water partitioning of compounds (Kow) and organic-carbon content of soil/sediment, which is used to normalize sorption measurements (KOC). We revisit those concepts and their translation to IOC (Dow and DOC) and discuss compound and soil properties determining sorption of IOC under water saturated conditions. Highlighting possible complementary and/or alternative approaches to better assess IOC mobility, we discuss implications on their regulation and risk assessment. The development of better models for IOC mobility needs consistent and reliable sorption measurements at well-defined chemical conditions in natural porewater, better IOC-, as well as sorbent characterization. Such models should be complemented by monitoring data from the natural environment. The state of knowledge presented here may guide urgently needed future investigations in this field for researchers, engineers, and regulators.

Fate of contaminants of emerging concern in the reclaimed wastewater-soil-plant continuum.

Reclaimed wastewater irrigation, a common agricultural practice in water-scarce regions, chronically exposes the agricultural environment to a wide range of contaminants of emerging concern (CECs) including pharmaceuticals and personal care products. Here we provide new data and insights into the processes governing the translocation of CECs in the irrigation water-soil-plant continuum based on a comprehensive dataset from 445 commercial fields irrigated with reclaimed wastewater. We report on CEC exposures in irrigation water, soils, and edible produce (leafy greens, carrots, potatoes, bananas, tomatoes, avocados, and citrus fruits). Our data show that CEC concentrations in irrigation water and their physiochemical properties (mainly charge and lipophilicity) are the main factors governing their translocation and accumulation in the soil-plant continuum. CECs exhibiting the highest detection frequency in plants (lamotrigine, venlafaxine, and carbamazepine) showed a reduction in their leaf accumulation factor with increasing soil organic matter content. The higher soil organic matter likely reduced the available CEC concentration in the soil solution due to soil-CEC interactions, leading to reduced uptake. Interestingly, the concentration of carbamazepine in the leaves showed a saturation-like trend when plotted against its concentration in the soils. This probably resulted from steady-state conditions when uptake equals in-planta decomposition. Our data indicate that due to continuous reclaimed wastewater irrigation, the soil acts as a sink for CECs. CECs in the soil reservoir can be desorbed into the soil solution during the rainy season and be taken up by rain-fed crops.

Pharmaceuticals in edible crops irrigated with reclaimed wastewater: Evidence from a large survey in Israel.

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 ~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.

Comparison of adsorption behaviors of selected endocrine-disrupting compounds in soil.

Bisphenol-A (BPA), 17α-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 (KLF ) 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.

Abiotic Transformation of Lamotrigine by Redox-Active Mineral and Phenolic Compounds.

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.

ECORISK2050: An Innovative Training Network for predicting the effects of global change on the emission, fate, effects, and risks of chemicals in aquatic ecosystems.

By 2050, the global population is predicted to reach nine billion, with almost three quarters living in cities. The road to 2050 will be marked by changes in land use, climate, and the management of water and food across the world. These global changes (GCs) will likely affect the emissions, transport, and fate of chemicals, and thus the exposure of the natural environment to chemicals. ECORISK2050 is a Marie Sklodowska-Curie Innovative Training Network that brings together an interdisciplinary consortium of academic, industry and governmental partners to deliver a new generation of scientists, with the skills required to study and manage the effects of GCs on chemical risks to the aquatic environment. The research and training goals are to: (1) assess how inputs and behaviour of chemicals from agriculture and urban environments are affected by different environmental conditions, and how different GC scenarios will drive changes in chemical risks to human and ecosystem health; (2) identify short-to-medium term adaptation and mitigation strategies, to abate unacceptable increases to risks, and (3) develop tools for use by industry and policymakers for the assessment and management of the impacts of GC-related drivers on chemical risks. This project will deliver the next generation of scientists, consultants, and industry and governmental decision-makers who have the knowledge and skillsets required to address the changing pressures associated with chemicals emitted by agricultural and urban activities, on aquatic systems on the path to 2050 and beyond.

Ecological Risk Dynamics of Pharmaceuticals in Micro-Estuary Environments.

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.

Environmental risk dynamics of pesticides toxicity in a Mediterranean micro-estuary.

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 µg L-1 of Imidacloprid and 55 µg 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.

The importance of aromaticity to describe the interactions of organic matter with carbonaceous materials depends on molecular weight and sorbent geometry.

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.

Involuntary human exposure to carbamazepine: A cross-sectional study of correlates across the lifespan and dietary spectrum.

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.

Pharmaceuticals in treated wastewater induce a stress response in tomato 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.

Pharmaceutical and Personal Care Products: From Wastewater Treatment into Agro-Food Systems.

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.

Maize (Zea mays L.) root exudates modify the surface chemistry of CuO nanoparticles: Altered aggregation, dissolution and toxicity.

Copper oxide nanoparticles (CuO NPs), as an antimicrobial nanomaterial, have found many applications in agriculture. Ubiquitous and complex root exudates (RE) in the plant root zone motivates the determination of how specific components of RE interact with CuO NPs. This work aims to reveal the role of maize (Zea mays L.)-derived RE and their components on the aggregation and dissolution of CuO NPs in the rhizosphere. We observed that RE significantly inhibited the aggregation of CuO NPs regardless of ionic strength and electrolyte type. In the presence of RE, the CCC of CuO NPs in NaCl shifted from 30 to 125 mM and the value in CaCl2 shifted from 4 to 20 mM. Furthermore, this inhibition was correlated with molecular weight (MW) of RE fractions. Higher MW fraction (>10 kDa) reduced the aggregation most. We also discovered that RE significantly promoted the dissolution of CuO NPs and lower MW fraction (<3 kDa) RE mainly contributed to this process. Additionally, phytotoxicity of CuO NPs in the presence of RE and different fractions of RE was evaluated. The addition of 20 mg/L RE reduced the seedlings growth rate to 1.89% after 7 days exposure to 25 mg/L CuO NPs, which were significantly lower than the control group (4.82%). Notably, Cu accumulation in plant root tissues was significantly enhanced by 20 mg/L RE. This study provides useful insights into the interactions between RE and CuO NPs, which is of significance for the safe use of CuO NPs-based antimicrobial products in agricultural production.

The missing link between carbon nanotubes, dissolved organic matter and organic pollutants.

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.