Quantifying the Chemical Composition and Real-Time Mass Loading of Nanoplastic Particles in the Atmosphere Using Aerosol Mass Spectrometry.

Plastic debris, including nanoplastic particles (NPPs), has emerged as an important global environmental issue due to its detrimental effects on human health, ecosystems, and climate. Atmospheric processes play an important role in the transportation and fate of plastic particles in the environment. In this study, a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was employed to establish the first online approach for identification and quantification of airborne submicrometer polystyrene (PS) NPPs from laboratory-generated and ambient aerosols. The fragmentation ion C8H8+ is identified as the major tracer ion for PS nanoplastic particles, achieving an 1-h detection limit of 4.96 ng/m3. Ambient PS NPPs measured at an urban location in Texas are quantified to be 30 ± 20 ng/m3 by applying the AMS data with a constrained positive matrix factorization (PMF) method using the multilinear engine (ME-2). Careful analysis of ambient data reveals that atmospheric PS NPPs were enhanced as air mass passed through a waste incinerator plant, suggesting that incineration of waste may serve as a source of ambient NPPs. The online quantification of NPPs achieved through this study can significantly improve our understanding of the source, transport, fate, and climate effects of atmospheric NPPs to mitigate this emerging global environmental issue.

Single atom catalyst-mediated generation of reactive species in water treatment.

Water is one of the most essential components in the sustainable development goals (SDGs) of the United Nations. With worsening global water scarcity, especially in some developing countries, water reuse is gaining increasing acceptance. A key challenge in water treatment by conventional treatment processes is the difficulty of treating low concentrations of pollutants (micromolar to nanomolar) in the presence of much higher levels of inorganic ions and natural organic matter (NOM) in water (or real water matrices). Advanced oxidation processes (AOPs) have emerged as an attractive treatment technology that generates reactive species with high redox potentials (E0) (e.g., hydroxyl radical (HO˙), singlet oxygen (1O2), sulfate radical (SO4˙-), and high-valent metals like iron(IV) (Fe(IV)), copper(III) (Cu(III)), and cobalt(IV) (Co(IV))). The use of single atom catalysts (SACs) in AOPs and water treatment technologies has appeared only recently. This review introduces the application of SACs in the activation of hydrogen peroxide and persulfate to produce reactive species in treatment processes. A significant part of the review is devoted to the mechanistic aspects of traditional AOPs and their comparison with those triggered by SACs. The radical species, SO4˙- and HO˙, which are produced in both traditional and SACs-activated AOPs, have higher redox potentials than non-radical species, 1O2 and high-valent metal species. However, SO4˙- and HO˙ radicals are non-selective and easily affected by components of water while non-radicals resist the impact of such constituents in water. Significantly, SACs with varying coordination environments and structures can be tuned to exclusively generate non-radical species to treat water with a complex matrix. Almost no influence of chloride, carbonate, phosphate, and NOM was observed on the performance of SACs in treating pollutants in water when nonradical species dominate. Therefore, the appropriately designed SACs represent game-changers in purifying water vs. AOPs with high efficiency and minimal interference from constituents of polluted water to meet the goals of water sustainability.

Enhanced Oxidation of Antibiotics by Ferrate Mediated with Natural Organic Matter: Role of Phenolic Moieties.

The increasing presence of antibiotics in water sources threatens public health and ecosystems. Various treatments have been previously applied to degrade antibiotics, yet their efficiency is commonly hindered by the presence of natural organic matter (NOM) in water. On the contrary, we show here that nine types of NOM and NOM model compounds improved the removal of trimethoprim and sulfamethoxazole by ferrate(VI) (FeVIO42-, Fe(VI)) under mild alkaline conditions. This is probably associated with the presence of phenolic moieties in NOMs, as suggested by first-order kinetics using NOM, phenol, and hydroquinone. Electron paramagnetic resonance reveals that NOM radicals are generated within milliseconds in the Fe(VI)-NOM system via single-electron transfer from NOM to Fe(VI) with the formation of Fe(V). The dominance of the Fe(V) reaction with antibiotics resulted in their enhanced removal despite concurrent reactions between Fe(V) and NOM moieties, the radicals, and water. Kinetic modeling considering Fe(V) explains the enhanced kinetics of antibiotics abatement at low phenol concentrations. Experiments with humic and fulvic acids of lake and river waters show similar results, thus supporting the enhanced abatement of antibiotics in real water situations.

Reaction of FeaqII with Peroxymonosulfate and Peroxydisulfate in the Presence of Bicarbonate: Formation of FeaqIV and Carbonate Radical Anions.

Many advanced oxidation processes (AOPs) use Fenton-like reactions to degrade organic pollutants by activating peroxymonosulfate (HSO5-, PMS) or peroxydisulfate (S2O82-, PDS) with Fe(H2O)62+ (FeaqII). This paper presents results on the kinetics and mechanisms of reactions between FeaqII and PMS or PDS in the absence and presence of bicarbonate (HCO3-) at different pH. In the absence of HCO3-, FeaqIV, rather than the commonly assumed SO4•-, is the dominant oxidizing species. Multianalytical methods verified the selective conversion of dimethyl sulfoxide (DMSO) and phenyl methyl sulfoxide (PMSO) to dimethyl sulfone (DMSO2) and phenyl methyl sulfone (PMSO2), respectively, confirming the generation of FeaqIV by the FeaqII-PMS/PDS systems without HCO3-. Significantly, in the presence of environmentally relevant concentrations of HCO3-, a carbonate radical anion (CO3•-) becomes the dominant reactive species as confirmed by the electron paramagnetic resonance (EPR) analysis. The new findings suggest that the mechanisms of the persulfate-based Fenton-like reactions in natural environments might differ remarkably from those obtained in ideal conditions. Using sulfonamide antibiotics (sulfamethoxazole (SMX) and sulfadimethoxine (SDM)) as model contaminants, our study further demonstrated the different reactivities of FeaqIV and CO3•- in the FeaqII-PMS/PDS systems. The results shed significant light on advancing the persulfate-based AOPs to oxidize pollutants in natural water.

Mobilization of Colloid- and Nanoparticle-Bound Arsenic in Contaminated Paddy Soils during Reduction and Reoxidation.

The association of arsenic (As) with colloidal particles could facilitate its transport to adjacent water systems or alter its availability in soil-rice systems. However, little is known about the size distribution and composition of particle-bound As in paddy soils, particularly under changing redox conditions. Here, we incubated four As-contaminated paddy soils with distinctive geochemical properties to study the mobilization of particle-bound As during soil reduction and subsequent reoxidation. Using transmission electron microscopy-energy dispersive spectroscopy and asymmetric flow field-flow fractionation, we identified organic matter (OM)-stabilized colloidal Fe, most likely in the form of (oxy)hydroxide-clay composite, as the main arsenic carriers. Specifically, colloidal As was mainly associated with two size fractions of 0.3-40 and >130 kDa. Soil reduction facilitated the release of As from both fractions, whereas reoxidation caused their rapid sedimentation, coinciding with solution Fe variations. Further quantitative analysis demonstrated that As concentrations positively correlated with both Fe and OM concentrations at nanometric scales (0.3-40 kDa) in all studied soils during reduction and reoxidation, yet the correlations are pH-dependent. This study provides a quantitative and size-resolved understanding of particle-bound As in paddy soils, highlighting the importance of nanometric Fe-OM-As interactions in paddy As geochemical cycling.

Integrated Photocatalytic Reduction and Oxidation of Perfluorooctanoic Acid by Metal-Organic Frameworks: Key Insights into the Degradation Mechanisms.

The high porosity and tunability of metal-organic frameworks (MOFs) have made them an appealing group of materials for environmental applications. However, their potential in the photocatalytic degradation of per- and polyfluoroalkyl substances (PFAS) has been rarely investigated. Hereby, we demonstrate that over 98.9% of perfluorooctanoic acid (PFOA) was degraded by MIL-125-NH2, a titanium-based MOF, in 24 h under Hg-lamp irradiation. The MOF maintained its structural integrity and porosity after three cycles, as indicated by its crystal structure, surface area, and pore size distribution. Based on the experimental results and density functional theory (DFT) calculations, a detailed reaction mechanism of the chain-shortening and H/F exchange pathways in hydrated electron (eaq-)-induced PFOA degradation were revealed. Significantly, we proposed that the coordinated contribution of eaq- and hydroxyl radical (•OH) is vital for chain-shortening, highlighting the importance of an integrated system capable of both reduction and oxidation for efficient PFAS degradation in water. Our results shed light on the development of effective and sustainable technologies for PFAS breakdown in the environment.

Zinc Fertilizers Modified the Formation and Properties of Iron Plaque and Arsenic Accumulation in Rice (Oryza sativa L.) in a Life Cycle Study.

This study examined the effect of three forms of zinc fertilizers on arsenic (As) accumulation and speciation in rice tissues over the life cycle of this cereal crop in a paddy soil. The formation and properties of iron plaque on rice roots at the maximum tillering stage and the mature stage were also determined. Elevated As at 5 mg/kg markedly lowered the rice yield by 86%; however, 100 mg/kg Zn fertilizers significantly increased the rice yield by 354-686%, regardless of the Zn form. Interestingly, only Zn2+ significantly lowered the total As in rice grains by 17% to 3.5 mg/kg and As(III) by 64% to around 0.5 mg/kg. Zinc amendments substantially hindered and, in the case of zinc oxide bulk particles (ZnOBPs), fully prevented the crystallization of iron oxides (Fe3O4 and Fe2O3) and silicon oxide (SiO2) and altered the composition of iron plaques on rice roots. SiO2 was first reported to be a significant component of iron plaque. Overall, ZnOBPs, ZnO nanoparticles, and Zn2+ displayed significant yet distinctive effects on the properties of iron plaque and As accumulation in rice grains, providing a fresh perspective on the potentially unintended consequences of different Zn fertilizers on food safety.

Visible Light-Induced Catalyst-Free Activation of Peroxydisulfate: Pollutant-Dependent Production of Reactive Species.

Activation of peroxydisulfate (PDS, S2O82-) via various catalysts to degrade pollutants in water has been extensively investigated. However, catalyst-free activation of PDS by visible light has been largely ignored. This paper reports effective visible light activation of PDS without any additional catalyst, leading to the degradation of a wide range of organic compounds of high environmental and human health concerns. Importantly, the formation of reactive species is distinctively different in the PDS visible light system with and without pollutants [e.g., atrazine (ATZ)]. In addition to SO4•- generated via S2O82- dissociation under visible light irradiation, O2•- and 1O2 are also produced in both systems. However, in the absence of ATZ, H2O2 and O2•- are key intermediates and precursors for 1O2, whereas in the presence of ATZ, a different pathway was followed to produce O2•- and 1O2. Both radical and nonradical processes contribute to the degradation of ATZ in the PDS visible light system. The active role of 1O2 in the degradation of ATZ besides SO4•- is manifested by the enhanced degradation of contaminants and electron paramagnetic resonance spectroscopy measurements in D2O.

Reactive High-Valent Iron Intermediates in Enhancing Treatment of Water by Ferrate.

Efforts are being made to tune the reactivity of the tetraoxy anion of iron in the +6 oxidation state (FeVIO42-), commonly called ferrate, to further enhance its applications in various environmental fields. This review critically examines the strategies to generate highly reactive high-valent iron intermediates, FeVO43- (FeV) and FeIVO44- or FeIVO32- (FeIV) species, from FeVIO42-, for the treatment of polluted water with greater efficiency. Approaches to produce FeV and FeIV species from FeVIO42- include additions of acid (e.g., HCl), metal ions (e.g., Fe(III)), and reductants (R). Details on applying various inorganic reductants (R) to generate FeV and FeIV from FeVIO42- via initial single electron-transfer (SET) and oxygen-atom transfer (OAT) to oxidize recalcitrant pollutants are presented. The common constituents of urine (e.g., carbonate, ammonia, and creatinine) and different solids (e.g., silica and hydrochar) were found to accelerate the oxidation of pharmaceuticals by FeVIO42-, with potential mechanisms provided. The challenges of providing direct evidence of the formation of FeV/FeIV species are discussed. Kinetic modeling and density functional theory (DFT) calculations provide opportunities to distinguish between the two intermediates (i.e., FeIV and FeV) in order to enhance oxidation reactions utilizing FeVIO42-. Further mechanistic elucidation of activated ferrate systems is vital to achieve high efficiency in oxidizing emerging pollutants in various aqueous streams.

An Alternative Strategy for Screening and Confirmation of 330 Pesticides in Ground- and Surface Water Using Liquid Chromatography Tandem Mass Spectrometry.

The presence of pesticide residues in water is a huge worldwide concern. In this paper we described the development and validation of a new liquid chromatography tandem mass spectrometric (LC-MS/MS) method for both screening and quantification of pesticides in water samples. In the sample preparation stage, the samples were buffered to pH 7.0 and pre-concentrated on polymeric-based cartridges via solid-phase extraction (SPE). Highly sensitive detection was carried out with mobile phases containing only 5 mM ammonium formate (pH of 6.8) as an eluent additive and using only positive ionization mode in MS/MS instrument. Hence, only 200-fold sample enrichment was required to set a screening detection limit (SDL) and reporting limit (RL) of 10 ng/L. The confirmatory method was validated at 10 and 100 ng/L spiking levels. The apparent recoveries obtained from the matrix-matched calibration (5-500 ng/L) were within the acceptable range (60-120%), also the precision (relative standard deviation, RSD) was not higher than 20%. During the development, 480 pesticides were tested and 330 compounds fulfilled the requirements of validation. The method was successfully applied to proficiency test samples to evaluate its accuracy. Moreover, the method robustness test was carried out using higher sample volume (500 mL) followed by automated SPE enrichment. Finally, the method was used to analyze 20 real samples, in which some compounds were detected around 10 ng/L, but never exceeded the assay maximum level.

Prediction of Plant Uptake and Translocation of Engineered Metallic Nanoparticles by Machine Learning.

Machine learning was applied to predict the plant uptake and transport of engineered nanoparticles (ENPs). A back propagation neural network (BPNN) was used to predict the root concentration factor (RCF) and translocation factor (TF) of ENPs from their essential physicochemical properties (e.g., composition and size) and key external factors (e.g., exposure time and plant species). The relative importance of input variables was determined by sensitivity analysis, and gene-expression programming (GEP) was used to generate predictive equations. The BPNN model satisfactorily predicted the RCF and TF in both hydroponic and soil systems, with an R2 higher than 0.8 for all simulations. Inclusion of the initial ENP concentration as an input variable further improved the accuracy of the BPNN for soil systems. Sensitivity analysis indicated that the composition of ENPs (e.g., metals vs metal oxides) is a major factor affecting RCF and TF values in a hydroponic system. However, the soil organic matter and clay contents are more dominant in a soil system. The GEP model (R2 = 0.8088 and 0.8959 for RCF and TF values) generated more accurate predictive equations than the conventional regression model (R2 = 0.5549 and 0.6664 for RCF and TF values) in a hydroponic system, which could guide the sustainable design of ENPs for agricultural applications.

Machine Learning: New Ideas and Tools in Environmental Science and Engineering.

The rapid increase in both the quantity and complexity of data that are being generated daily in the field of environmental science and engineering (ESE) demands accompanied advancement in data analytics. Advanced data analysis approaches, such as machine learning (ML), have become indispensable tools for revealing hidden patterns or deducing correlations for which conventional analytical methods face limitations or challenges. However, ML concepts and practices have not been widely utilized by researchers in ESE. This feature explores the potential of ML to revolutionize data analysis and modeling in the ESE field, and covers the essential knowledge needed for such applications. First, we use five examples to illustrate how ML addresses complex ESE problems. We then summarize four major types of applications of ML in ESE: making predictions; extracting feature importance; detecting anomalies; and discovering new materials or chemicals. Next, we introduce the essential knowledge required and current shortcomings in ML applications in ESE, with a focus on three important but often overlooked components when applying ML: correct model development, proper model interpretation, and sound applicability analysis. Finally, we discuss challenges and future opportunities in the application of ML tools in ESE to highlight the potential of ML in this field.

Recent insights into the impact, fate and transport of cerium oxide nanoparticles in the plant-soil continuum.

The advent of the nanotechnology era offers a unique opportunity for sustainable agriculture provided that the exposure and toxicity are adequately assessed and properly controlled. The global production and application of cerium oxide nanoparticles (CeO2-NPs) in various industrial sectors have tremendously increased. Most of the nanoparticles end up in water and soil where they interact with soil microorganisms and plants. Investigating the uptake, translocation and accumulation of CeO2-NPs is critical for its safe application in agriculture. Plant uptake of CeO2-NPs may lead to their accumulation in different plant tissues and interference with key metabolic processes of plants. Soil microbes can also be affected by increasing CeO2-NPs in soil, leading to changes in the physiology and enzymatic activity of soil microorganisms. The interactions between CeO2-NPs, microbes and plants in the agricultural system need systemic research in ecologically relevant conditions. In the present review, The uptake pathways and in-planta translocation of CeO2-NPs,and their impact on plant morphology, nutritional values, antioxidant enzymes and molecular determinants are presented. The role of CeO2-NPs in modifying soil microbial community in plant rhizosphere is also discussed. Overall, the review aims to provide a comprehensive account on the behaviour of CeO2-NPs in soil-plant systems and their potential impacts on the soil microbial community and plant health.

Zinc oxide (ZnO) nanoparticles elevated iron and copper contents and mitigated the bioavailability of lead and cadmium in different leafy greens.

Advances in large hydroponic production of leafy greens, easy adoption in urban agriculture, and large leaf surface area of many leafy greens, greatly increase their exposure to heavy metals and nanoparticles. Cadmium (Cd) and lead (Pb) are two highly toxic heavy metals, which threaten the health of humans and livestock even at trace levels. These heavy metals may be taken up by plant roots through the protein transporters used for essential minerals such as iron (Fe2+) and copper (Cu2+). Previous studies have shown that some metallic nanoparticles affect the performance of protein transporters and modify the plant uptake of co-existing heavy metal ions. This study aims to understand the role of zinc oxide nanoparticles (ZnONPs) in the uptake pattern of Cd and Pb and two key micronutrients of iron and copper in edible tissues of three leafy green species including spinach (Spinaciae oleracea), parsley (Petroselinum sativum) and cilantro (Coriandrum sativum). Pre-grown plant seedlings in soil (containing Cu and Fe) were transplanted to a hydroponic system (1/4th Hoagland solution) for 7 days as a transition, and then were exposed to four treatments in deionized water (1.0 mg L-1 Cd2++100.0 mg L-1 Pb2+, 1.0 mg L-1 Cd2++100.0 mg L-1 Pb2+ + 100 mg L-1 ZnONPs, 100 mg L-1 ZnO-ENPs and a control with no chemical exposure) for additional two weeks. At termination, shoots were gently separated from the roots, and the concentrations of Pb, Cd, Fe, Zn, and Cu in all plant tissues were quantified by inductively coupled plasma-mass spectrometry (ICP-MS). The results revealed that ZnONPs mitigated the uptake of both heavy metals in roots. The translocation of heavy metals was similar in the edible tissues of three species. The response of three leafy greens to the co-exposure of heavy metals and ZnONPs was different in Cu and Fe accumulation in edible tissues. Fe concentration in edible tissues in the co-exposed plants was increased in spinach (+10%) and cilantro (+9%) but decreased in parsley (-8%) compared to controls, while the Cu level in edible tissues increased in all three species following the order of cilantro (+8%)> spinach (+4%)> parsley (+1.5%).

Elucidating the physiological mechanisms underlying enhanced arsenic hyperaccumulation by glutathione modified superparamagnetic iron oxide nanoparticles in Isatis cappadocica.

Widespread arsenic (As) contamination is a severe environmental and public health concern. Isatis cappadocica, an arsenic hyperaccumulator, holds great potential to clean up As-contaminated soil and groundwater. Iron oxide is one of the most common metal oxides in the natural environment and its nanoparticulate form has been previously utilized for the removal of heavy metals/metalloids from wastewater. However, there is a paucity of information on the impact of iron oxide nanoparticles on the growth and physiological properties of I. cappadocica and its effectiveness on As removal. Current study reports for the first time the impact of superparamagnetic iron oxide nanoparticles and glutathione (GSH) modified superparamagnetic iron oxide nanoparticles (nFe3O4 and nFe3O4@GSH) on the physiological characteristic of I. cappadocica and its accumulation of As under hydroponic condition. nFe3O4@GSH alleviated the harmful impact of As and significantly increased the shoot biomass of I. cappadocica by enhancing the plant defense mechanisms. The application of GSH, nFe3O4 and nFe3O4@GSH all lowered the As concentration in plant shoots as a protective mechanism. However, the substantial shoot biomass increase due to nFe3O4@GSH resulted in a 56% higher As accumulation in plant shoots than in plants exposed to As alone, indicating the strong effectiveness of nFe3O4@GSH as a novel enhancer of the As phytoremediation by I. cappadocica. Our data further showed that the beneficial effect of nFe3O4@GSH on As phytoremediation is due to the enhancement of activities of several enzymatic and nonenzymatic antioxidants.

Impact of nanoparticle surface charge and phosphate on the uptake of coexisting cerium oxide nanoparticles and cadmium by soybean (Glycine max. (L.) merr.).

Engineered nanoparticles (ENPs) often interact closely with coexisting environmental pollutants; however, the effect of their surface properties on such interactions in a plant system has not been examined. This study investigated the roles of ENP surface charge and growth media chemistry on the mutual effects of cerium oxide nanoparticles (CeO2NPs) and cadmium (Cd) on their plant uptake and accumulation in a hydroponic system. Soybean seedlings were exposed to five nanoparticle/Cd treatments including: 100 mg L-1 CeO2NPs(+); 100 mg L-1 CeO2NPs(-); 100 mg L-1 CeO2NPs(+) + 1 mg L-1 Cd; 100 mg L-1 CeO2NPs(-) + 1 mg L-1 Cd; and 1 mg L-1 Cd only, in the presence or absence of 15 mg L-1 phosphorous in the form of phosphate. After 4 days of exposure, concentrations of Cd and Ce in plant tissues were quantified by inductively coupled plasma-mass spectrometry. Roots exposed to CeO2NPs(+) contained 87% higher Ce than plants exposed to CeO2NPs(-). Phosphate significantly increased the root concentration of Ce by 61% and 66% exposed to CeO2NPs(+) and CeO2NPs(-), respectively. The mutual effect of CeO2NPs and Cd was also affected by phosphate, and the net effect of phosphate depended upon the surface charge of CeO2NPs.

Attachment of cerium oxide nanoparticles of different surface charges to kaolinite: Molecular and atomic mechanisms.

Sustainable applications of nanotechnology in agriculture require insights into the interactions between engineered nanoparticles (ENPs) and clay minerals, a key component in soil that governs the soil properties and functions. This study investigated the charge-dependent interactions of cerium oxide nanoparticles (CeO2NPs) with kaolinite at atomic level with several complementary surface characterization techniques. High resolution transmission electron microscope (HRTEM) and atomic force microscope (AFM) images showed strong attachment of positively charged and neutral CeO2NPs to the surface of kaolinite while the negatively charged CeO2NPs demonstrated low affinity to the surface of kaolinite, indicating strong electrostatic interactions between CeO2NPs and kaolinite surface. Attached CeO2NPs on kaolinite surface displayed charge-dependent aggregation, with neutral CeO2NPs showing the most substantial aggregation on kaolinite surface. The variation in hydrodynamic size and surface charge of kaolinite with the charge on CeO2NPs was observed. The attachment of CeO2NPs also changed the surface charge density distribution on the surface of kaolinite, converting a relatively homogenously charged basal plane into a heterogeneously charged plate. The change on kaolinite surface charge density may markedly affect the interactions of clay minerals with surrounding macro- and micro-nutrients in soil pore water and affect their bioavailability to plants.

Elucidating the Effects of Cerium Oxide Nanoparticles and Zinc Oxide Nanoparticles on Arsenic Uptake and Speciation in Rice ( Oryza sativa) in a Hydroponic System.

The accumulation of arsenic (As) in rice grains depends greatly on the redox chemistry in rice rhizosphere. Intentional or accidental introduction of strong oxidizing or reducing agents, such as metallic engineered nanoparticles (ENPs) into the plant-soil ecosystem, can change As speciation and plant uptake. However, investigation on the effects of ENPs on plant uptake of co-occurring redox sensitive heavy metals and their speciation in plant tissues is scarce. We investigated the mutual effects of two commonly encountered ENPs, cerium oxide nanoparticles (CeO2 NPs) and zinc oxide nanoparticles (ZnO NPs), and two inorganic species of As on their uptake and accumulation in rice seedlings in a hydroponic system. Rice seedlings were exposed to different combinations of 1 mg/L of As(III) or As(V) and 100 mg/L of CeO2 NPs and ZnO NPs for 6 days about 40 days after germination. ZnO NPs significantly reduced the accumulation of As(III) in rice roots by 88.1 and 96.7% and in rice shoots by 71.4 and 77.4% when the initial As was supplied as As(III) and As(V), respectively. ZnO NPs also reduced As(V) in rice roots by 68.3 and 52.3% when the As was provided as As(III) and As(V), respectively. However, the As(V) in rice shoots was unaffected by ZnO NPs regardless of the initial oxidation state of As. Neither the total As nor the individual species of As in rice tissues was significantly changed by CeO2 NPs. The co-presence of As(III) and As(V) increased Ce in rice shoots by 6.5 and 2.3 times but did not affect plant uptake of Zn. The results confirmed the active interactions between ENPs and coexisting inorganic As species, and the extent of their interactions depends on the properties of ENPs as well as the initial oxidation state of As.

Impact of Nanoparticle Surface Properties on the Attachment of Cerium Oxide Nanoparticles to Sand and Kaolin.

Soil texture has been found to be a critical factor in regulating the fate and transport of cerium oxide nanoparticles (CeONPs) in the terrestrial environment. However, the underlying mechanisms for the interactions between CeONPs and different components of soil are still poorly understood. The attachment of CeONPs onto two typical components of soil (sand and kaolin) in batch experiments were investigated to provide insights into the retention and bioavailability of CeONPs in soil. Surface properties of CeONPs, including surface charge and surface coating condition, had strong impacts on the interactions between CeONPs and soil particles. Positively charged CeONPs [CeONPs(+)] displayed the greatest attachment onto kaolin, whereas the negatively charged CeONPs [CeONPs(-)] showed poorest attachment onto sand. The attachment of CeONPs onto kaolin was significantly greater than onto sand, irrespective of surface charge. Homoaggregation of CeONPs increased the size of CeONPs on the surface of sand and kaolin. Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) calculations agreed with the experimental observations that surface charge and coating condition of CeONPs played a vital role in the homoaggregation and adsorption of CeONPs. For CeONPs(-) coated with polyvinylpyrrolidone (PVP), the steric repulsion between soil particles and CeONPs increases rapidly with the increase of maximum surface concentration of PVP. Adsorption isothermal fittings indicated that the adsorption of CeONPs onto sand and kaolin can be properly described by the Dubinin-Radushkevich isotherm. The results obtained in this study are crucial for the understanding of the fate and transport of engineered nanomaterials in the environment.

Uptake, Accumulation, and in Planta Distribution of Coexisting Cerium Oxide Nanoparticles and Cadmium in Glycine max (L.) Merr. .

Agricultural soils are likely to be polluted by both conventional and emerging contaminants at the same time. Understanding the interactions of coexisting engineered nanoparticles (ENPs) and trace elements (a common source of abiotic stress) is critical to gaining insights into the accumulation of these two groups of chemicals by plants. The objectives of this study were to determine the uptake and accumulation of coexisting ENPs and trace elements by soybeans and to gain insights into the physiological mechanisms resulting in different plant accumulation of these materials. The combinations of three cadmium levels (0 [control] and 0.25 and 1 milligrams per kilogram of dry soil) and two CeO2 NPs concentrations (0 [control] and 500 milligrams per kilogram of dry soil) were investigated. Measurements of the plant biomass and physiological parameters indicated that CeO2 NPs led to higher variable fluorescence to maximum fluorescence ratio, suggesting that CeO2 NPs enhanced the plant light energy use efficiency by photosystem II. In addition, the presence of CeO2 NPs did not affect Cd accumulation in soybean, but Cd significantly increased the accumulation of Ce in plant tissues, especially in roots and older leaves. The altered Ce in planta distribution was partially associated with the formation of root apoplastic barriers in the co-presence of Cd and CeO2 NPs.