Multifunctional biomolecular corona-inspired nanoremediation of antibiotic residues.

Facing complex and variable emerging antibiotic pollutants, the traditional development of functional materials is a "trial-and-error" process based on physicochemical principles, where laborious steps and long timescales make it difficult to accelerate technical breakthroughs. Notably, natural biomolecular coronas derived from highly tolerant organisms under significant contamination scenarios can be used in conjunction with nanotechnology to tackling emerging contaminants of concern. Here, super worms (Tubifex tubifex) with high pollutant tolerance were integrated with nano-zero valent iron (nZVI) to effectively reduce the content of 17 antibiotics in wastewater within 7 d. Inspired by the synergistic remediation, nZVI-augmented worms were constructed as biological nanocomposites. Neither nZVI (0.3 to 3 g/L) nor worms (104 to 105 per liter) alone efficiently degraded florfenicol (FF, as a representative antibiotic), while their composite removed 87% of FF (3 µmol/L). Under antibiotic exposure, biomolecules secreted by worms formed a corona on and modified the nZVI particle surface, enabling the nano-bio interface greater functionality, including responsiveness, enrichment, and reduction. Mechanistically, FF exposure activated glucose-alanine cycle pathways that synthesize organic acids and amines as major metabolites, which were assembled into vesicles and secreted, thereby interacting with nZVI in a biologically response design strategy. Lactic acid and urea formed hydrogen bonds with FF, enriched analyte presence at the heterogeneous interface. Succinic and lactic acids corroded the nZVI passivation layer and promoted electron transfer through surface conjugation. This unique strategy highlights biomolecular coronas as a complex resource to augment nano-enabled technologies and will provide shortcuts for rational manipulation of nanomaterial surfaces with coordinated multifunctionalities.

Amino-modified upcycled biochar achieves selective chromium removal in complex aqueous matrices.

Chromium pollution of groundwater sources is a growing global issue, which correlates with various anthropogenic activities. Remediation of both the Cr(VI) and Cr(III), via adsorption technologies, has been championed in recent years due to ease of use, minimal energy requirements, and the potential to serve as a highly sustainable remediation technology. In the present study, a biochar sorbent sourced from pineapple skins, allowed for the upcycling of agricultural waste into water purification technology. The biochar material was chemically modified, through a green amination method, to produce an efficient and selective adsorbent for the removal of both Cr(VI) and Cr(III) from complex aqueous matrices. From FTIR analysis it was evident that the chemical modification introduced new C-N and N-H bonds observed in the modified biochar along with a depletion of N-O and C-H bonds found in the pristine biochar. The amino modified biochar was found to spontaneously adsorb both forms of chromium at room temperature, with binding capacities of 46.5 mg/g of Cr(VI) and 27.1 mg/g of Cr(III). Interference studies, conducted in complex matrices, showed no change in adsorption capacity for Cr(VI) in matrices containing up to 3,000× the concentration of interfering ions. Finally, Cr(III) removal was synergized to 100% adsorption at interfering ions concentrations up to 330× of the analyte, which were suppressed at higher interference concentrations. Considering such performance, the amino modified biochar achieved selective removal for both forms of chromium, showing great potential for utilization in complex chromium pollution sources.

Seed Priming with Reactive Oxygen Species-Generating Nanoparticles Enhanced Maize Tolerance to Multiple Abiotic Stresses.

Climate change-induced extreme weather events (heat, cold, drought, and flooding) will severely affect crop production. Increasing the resilience of crops to fluctuating environmental conditions is critically important. Here, we report that nanomaterials (NMs) with reactive oxygen species (ROS)-generating properties can be used as seed priming agents to simultaneously enhance the tolerance of maize seeds and seedlings to diverse and even multiple stresses. Maize seeds primed with 40 mg/L silver nanoparticles (AgNPs) exhibited accelerated seed germination and an increased germination rate, greater seedling vigor, and better seedling growth under drought (10% and 20% PEG), saline (50 and 100 mM NaCl), and cold (15 °C) stress conditions, indicating enhanced resilience to diverse stresses. Importantly, maize resistance to simultaneous multiple stresses (drought and cold, drought and salt, and salt and cold) was markedly enhanced. Under drought conditions, seed priming significantly boosted root hair density and length (17.3-82.7%), which enabled greater tolerance to water deficiency. RNA-seq analysis reveals that AgNPs seed priming induced a transcriptomic shift in maize seeds. Plant hormone signal transduction and MAPK signaling pathways were activated upon seed priming. Importantly, low-cost and environmentally friendly ROS-generating Fe-based NMs (Fe2O3 and Fe3O4 NPs) were also demonstrated to enhance the resistance of seeds and seedlings to drought, salt, and cold stresses. These findings demonstrate that a simple seed priming strategy can be used to significantly enhance the climate resilience of crops through modulated ROS homeostasis and that this approach could be a powerful nanoenabled tool for addressing worsening food insecurity.

Mechanistic Insight into the Internalization, Distribution, and Autophagy Process of Manganese Nanoparticles in Capsicum annuum L.: Evidence from Orthogonal Microscopic Analysis.

Orthogonal techniques were used to track manganese nanoparticles (MnNPs) in Capsicum annuum L. leaf tissue and cell compartments and subsequently to explain the mechanism of uptake, translocation, and cellular interaction. C. annuum L was cultivated and foliarly exposed to MnNPs (100 mg/L, 50 mL/per leaf) before analysis by using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS) as well as dark-field hyperspectral and two-photon microscopy. We visualized the internalization of MnNP aggregates from the leaf surface and observed particle accumulation in the leaf cuticle and epidermis as well as spongy mesophyll and guard cells. These techniques enabled a description of how MnNPs cross different plant tissues as well as selectively accumulate and translocate in specific cells. We also imaged abundant fluorescent vesicles and vacuoles containing MnNPs, indicating likely induction of autophagy processes in C. annuum L., which is the bio-response upon storing or transforming the particles. These findings highlight the importance of utilizing orthogonal techniques to characterize nanoscale material fate and distribution with complex biological matrices and demonstrate that such an approach offers a significant mechanistic understanding that can inform both risk assessment and efforts aimed at applying nanotechnology to agriculture.

Targeting Metal Impurities for the Detection and Quantification of Carbon Black Particles in Water via spICP-MS.

Carbon black (CB) is a nanomaterial with numerous industrial applications and high potential for integration into nano-enabled water treatment devices. However, few analytical techniques are capable of measuring CB in water at environmentally relevant concentrations. Therefore, we intended to establish a quantification method for CB with lower detection limits through utilization of trace metal impurities as analytical tracers. Various metal impurities were investigated in six commercial CB materials, and the Monarch 1000 CB was chosen as a model for further testing. The La impurity was chosen as a tracer for spICP-MS analysis based on measured concentration, low detection limits, and lack of polyatomic interferences. CB stability in water and adhesion to the spICP-MS introduction system presented a challenge that was mitigated by the addition of a nonionic surfactant to the matrix. Following optimization, the limit of detection (64 µg/L) and quantification (122 µg/L) for Monarch 1000 CB demonstrated the applicability of this approach to samples expected to contain trace amounts of CB. When compared against gravimetric analysis and UV-visible absorption spectroscopy, spICP-MS quantification exhibited similar sensitivity but with the ability to detect concentrations an order of magnitude lower. Method detection and sensitivity was unaffected when dissolved La was spiked into CB samples at environmentally relevant concentrations. Additionally, a more complex synthetic matrix representative of drinking water caused no appreciable impact to CB quantification. In comparison to existing quantification techniques, this method has achieved competitive sensitivity, a wide working range for quantification, and high selectivity for tracing possible release of CB materials with known metal contents.

Soil-Weathered CuO Nanoparticles Compromise Foliar Health and Pigment Production in Spinach (Spinacia oleracea).

In this study, spinach plants exposed to fresh/unweathered (UW) or weathered (W) copper compounds in soil were analyzed for growth and nutritional composition. Plants were exposed for 45 days to freshly prepared or soil-aged (35 days) nanoparticulate CuO (nCuO), bulk-scale CuO (bCuO), or CuSO4 at 0 (control), 400, 400, and 40 mg/kg of soil, respectively. Foliar health, gas exchange, pigment content (chlorophyll and carotenoid), catalase and ascorbate peroxidase enzymes, gene expression, and Cu bioaccumulation were evaluated along with SEM imagery for select samples. Foliar biomass was higher in UW control (84%) and in UW ionic treatment (87%), compared to the corresponding W treatments (p ≤ 0.1). Root catalase activity was increased by 110% in UW bCuO treatment as compared to the W counterpart; the value for the W ionic treatment was increased by 2167% compared to the UW counterpart (p ≤ 0.05). At 20 days post-transplantation, W nCuO-exposed plants had ∼56% lower carotenoid content compared to both W control and the UW counterpart (p ≤ 0.05). The findings indicate that over the full life cycle of spinach plant the weathering process significantly deteriorates leaf pigment production under CuO exposure in particular and foliar health in general.

Insights into the Biogeochemical Cycling of Cobalt: Precipitation and Transformation of Cobalt Sulfide Nanoparticles under Low-Temperature Aqueous Conditions.

Cobalt sulfide precipitates, key phases in the natural biogeochemistry of cobalt and in relevant remediation and resource recovery processes, are poorly defined under low-temperature aqueous conditions. Here, we systematically studied Co (Fe) sulfides precipitated and aged in environmentally relevant solutions, defined by different combinations of pH, initial cobalt to iron ratios ([Co]aq/[Fe]aq), with/without S0, and the presence/absence of sulfate-reducing bacteria. The initial abiogenic precipitates were composed exclusively of amorphous Co sulfide nanoparticles (CoS·xH2O) that were stable in anoxic solution for 2 months, with estimated log K* values 1-5 orders of magnitude higher than that previously reported for Co sulfides. The addition of S0, in combination with acidic pH and elevated temperature (60 °C), resulted in recrystallization of the amorphous precipitates into nanocrystalline jaipurite (hexagonal CoS) within 1 month. In the presence of Fe(II)aq, the abiogenic precipitates were composed of more crystalline Co sulfides and/or Co-rich mackinawite, the exact phase being dependent on the [Co]aq/[Fe]aq value. The biogenic precipitates displayed higher crystallinity for Co sulfides (up to the formation of nanocrystalline cobalt pentlandite, Co9S8) and lower crystallinity for Co-rich mackinawite, suggestive of mineral-specific bacterial interaction. The revealed precipitation and transformation pathways of Co (Fe) sulfides in this study allows for a better constraint of Co biogeochemistry in various natural and engineered environments.

Silver Nanoparticles Alter Soil Microbial Community Compositions and Metabolite Profiles in Unplanted and Cucumber-Planted Soils.

The rapid development of nanotechnology makes the environmental impact assessment a necessity to ensure the sustainable use of engineered nanomaterials. Here, silver nanoparticles (AgNPs) at 100 mg/kg were added to soils in the absence or presence of cucumber (Cucumis sativa) plants for 60 days. The response of the soil microbial community and associated soil metabolites was investigated by 16S rRNA gene sequencing and gas chromatography-mass spectrometry (GC-MS)-based metabolomics, respectively. The results show that AgNP exposure significantly increased the soil pH in both unplanted and cucumber-planted soils. The soil bacterial community structure was altered upon Ag exposure in both soils. Several functionally significant bacterial groups, which are associated with carbon, nitrogen, and phosphorus cycling, were compromised by AgNPs in both unplanted and cucumber-planted soils. Generally, plants played a limited role in mediating the impact of AgNPs on the bacterial community. Soil metabolomic analysis showed that AgNPs altered the metabolite profile in both unplanted and cucumber-planted soils. The significantly changed metabolites are involved in sugar and amino acid-related metabolic pathways, indicating the perturbation of C and N metabolism, which is consistent with the bacterial community structure results. In addition, several fatty acids were significantly decreased upon exposure to AgNPs in both unplanted and cucumber-planted soils, suggesting the possible oxidative stress imposed on microbial cell membranes. These results provide valuable information for understanding the biological and biochemical impact of AgNP exposure on both plant species and on soil microbial communities; such understanding is needed to understand the risk posed by these materials in the environment.

Antioxidant and defense genetic expressions in corn at early-developmental stage are differentially modulated by copper form exposure (nano, bulk, ionic): Nutrient and physiological effects.

In the present study, Zea mays seedlings grown under nano Cu(OH)2 (nCu), bulk Cu(OH)2 (bCu), and ionic CuSO4 (iCu) compound exposure were harvested after six days. The nutritional profile was determined to be significantly disrupted in the roots by 1000 ppm bCu treatment, resulting in a 58.7% reduction in potassium compared to the control. In the shoots, a significant decrease of manganese was observed for 10 and 1000 ppm iCu treatments with 55.7% and 64.2% reductions, respectively. The overall protein content and catalase (CAT) enzymatic activity, however, remained unaffected in either roots or shoots, while an absence of polyphenol oxidase (PPO) activity was observed for all samples. The genetic expression of defense-related genes, metallothionein (MT), CAT, ascorbate peroxidase (APX), and PPO was assessed. The genetic expression of MT was upregulated 50-fold in roots treated with 1000 ppm bCu. There were no significant differences in CAT transcripts among the various treatments, while APX was upregulated 28 and 19-fold in shoots treated with 10 ppm bCu and 10 ppm nCu, respectively. Meanwhile, APX mRNA levels were downregulated five-fold in shoots treated with 1000 ppm iCu. Thus, indicating that the role of APX in plant defense was reinforced in seedlings exposed to low concentration of particulate Cu compounds. Remarkably, no PPO expression was found in any of the treatments and controls, which suggests this enzyme is expressed only under specific external factors or seedlings have an "immature" cascade signaling activation of the PPO system. Taken together, these results show that bCu and nCu treatments at a low concentration do not compromise vital cell machinery but rather elicit the enhancement of defense responses as observed through the increase in APX expression. Furthermore, under optimal concentrations, these Cu treatments show promise in enhancing corn defense responses, which can ultimately lead to increases in future global crop yields.

C60 Fullerols Enhance Copper Toxicity and Alter the Leaf Metabolite and Protein Profile in Cucumber.

Abiotic and biotic stress induce the production of reactive oxygen species (ROS), which limit crop production. Little is known about ROS reduction through the application of exogenous scavengers. In this study, C60 fullerol, a free radical scavenger, was foliar applied to three-week-old cucumber plants (1 or 2 mg/plant) before exposure to copper ions (5 mg/plant). Results showed that C60 fullerols augmented Cu toxicity by increasing the influx of Cu ions into cells (170% and 511%, respectively, for 1 and 2 mg of C60 fullerols/plant). We further use metabolomics and proteomics to investigate the mechanism of plant response to C60 fullerols. Metabolomics revealed that C60 fullerols up-regulated antioxidant metabolites including 3-hydroxyflavone, 1,2,4-benzenetriol, and methyl trans-cinnamate, among others, while it down-regulated cell membrane metabolites (linolenic and palmitoleic acid). Proteomics analysis revealed that C60 fullerols up-regulated chloroplast proteins involved in water photolysis (PSII protein), light-harvesting (CAB), ATP production (ATP synthase), pigment fixation (Mg-PPIX), and electron transport ( Cyt b6f). Chlorophyll fluorescence measurement showed that C60 fullerols significantly accelerated the electron transport rate in leaves (13.3% and 9.4%, respectively, for 1 and 2 mg C60 fullerols/plant). The global view of the metabolic pathway network suggests that C60 fullerols accelerated electron transport rate, which induced ROS overproduction in chloroplast thylakoids. Plant activated antioxidant and defense pathways to protect the cell from ROS damaging. The revealed benefit (enhance electron transport) and risk (alter membrane composition) suggest a cautious use of C60 fullerols for agricultural application.

Can abiotic stresses in plants be alleviated by manganese nanoparticles or compounds?

Abiotic stress has become one of the most challenging problems for agriculture as the world population keeps increasing dramatically. Crop stress management using manganese (Mn) compounds has been recently employed to reduce the negative effects caused by drought, harsh temperature, and salinity. In response to abiotic stress, an adequate supply of Mn has shown to remediate plant manganese deficiency, induce Mn superoxide dismutase at the transcriptional level to face reactive oxygen species production, and stimulate manganese-dependent proteins to maintain cell integrity. Lately, nanoparticles (NPs) have been explored in agriculture applications. Recent studies have implied that Mn NPs may help plants to overcome abiotic stresses at higher efficiency and lower toxicity, compared to their bulk or ionic counterparts. Although studies have shown that Mn compounds promote crop growth and alleviate abiotic stress, many questions related to Mn-plant networking, their mode of signaling, and the Mn-dependent regulation processes need to be answered.

Effects of carbonaceous nanomaterials on soil-grown soybeans under combined heat and insect stresses.

Because carbonaceous nanomaterials (CNMs) are expected to enter soils, the exposure implications to crop plants and plant-microbe interactions should be understood. Most investigations have been under ideal growth conditions, yet crops commonly experience abiotic and biotic stresses. Little is known how co-exposure to these environmental stresses and CNMs would cause combined effects on plants. We investigated the effects of 1000 mg kg-1 multiwalled carbon nanotubes (CNTs), graphene nanoplatelets (GNPs) and industrial carbon black (CB) on soybeans grown to the bean production stage in soil. Following seed sowing, plants became stressed by heat and infested with an insect (thrips). Consequently, all plants had similarly stunted growth, leaf damage, reduced final biomasses and fewer root nodules compared with healthy control soybeans previously grown without heat and thrips stresses. Thus, CNMs did not significantly influence the growth and yield of stressed soybeans, and the previously reported nodulation inhibition by CNMs was not specifically observed here. However, CNMs did significantly alter two leaf health indicators: the leaf chlorophyll a/b ratio, which was higher in the GNP treatment than in either the control (by 15 %) or CB treatment (by 14 %), and leaf lipid peroxidation, which was elevated in the CNT treatment compared with either the control (by 47 %) or GNP treatment (by 66 %). Overall, these results show that, while severe environmental stresses may impair plant production, CNMs (including CNTs and GNPs) in soil could additionally affect foliar health of an agriculturally important legume.

Carbonaceous Nanomaterials Have Higher Effects on Soybean Rhizosphere Prokaryotic Communities During the Reproductive Growth Phase than During Vegetative Growth.

Carbonaceous nanomaterials (CNMs) can affect agricultural soil prokaryotic communities, but how the effects vary with the crop growth stage is unknown. To investigate this, soybean plants were cultivated in soils amended with 0, 0.1, 100, or 1000 mg kg-1 of carbon black, multiwalled carbon nanotubes (MWCNTs), or graphene. Soil prokaryotic communities were analyzed by Illumina sequencing at day 0 and at the soybean vegetative and reproductive stages. The sequencing data were functionally annotated using the functional annotation of prokaryotic taxa (FAPROTAX) database. The prokaryotic communities were unaffected at day 0 and were altered at the plant vegetative stage only by 0.1 mg kg-1 MWCNTs. However, at the reproductive stage, when pods were filling, most treatments (except 1000 mg kg-1 MWCNTs) altered the prokaryotic community composition, including functional groups associated with C, N, and S cycling. The lower doses of CNMs, which were previously shown to be less agglomerated and thus more bioavailable in soil relative to the higher doses, were more effective toward both overall communities and individual functional groups. Taken together, prokaryotic communities in the soybean rhizosphere can be significantly phylogenetically and functionally altered in response to bioavailable CNMs, especially when soybean plants are actively directing resources to seed production.

Metabolomics Reveals How Cucumber ( Cucumis sativus) Reprograms Metabolites To Cope with Silver Ions and Silver Nanoparticle-Induced Oxidative Stress.

Due to their well-known antifungal activity, the intentional use of silver nanoparticles (AgNPs) as sustainable nanofungicides is expected to increase in agriculture. However, the impacts of AgNPs on plants must be critically evaluated to guarantee their safe use in food production. In this study, 4-week-old cucumber ( Cucumis sativus) plants received a foliar application of AgNPs (4 or 40 mg/plant) or Ag+ (0.04 or 0.4 mg/plant) for 7 days. Gas chromatography-mass spectrometry (GC-MS)=based nontarget metabolomics enabled the identification and quantification of 268 metabolites in cucumber leaves. Multivariate analysis revealed that all the treatments significantly altered the metabolite profile. Exposure to AgNPs resulted in metabolic reprogramming, including activation of antioxidant defense systems (upregulation of phenolic compounds) and downregulation of photosynthesis (upregulation of phytol). Additionally, AgNPs enhanced respiration (upregulation of tricarboxylic acid cycle intermediates), inhibited photorespiration (downregulation of glycine/serine ratio), altered membrane properties (upregulation of pentadecanoic and arachidonic acids, downregulation of linoleic and linolenic acids), and reduced inorganic nitrogen fixation (downregulation of glutamine and asparagine). Although Ag ions induced some of the same metabolic changes, alterations in the levels of carbazole, lactulose, raffinose, citraconic acid, lactamide, acetanilide, and p-benzoquinone were AgNP-specific. The results of this study offer new insight into the molecular mechanisms by which cucumber responds to AgNP exposure and provide important information to support the sustainable use of AgNPs in agriculture.

Cerium Biomagnification in a Terrestrial Food Chain: Influence of Particle Size and Growth Stage.

Mass-flow modeling of engineered nanomaterials (ENMs) indicates that a major fraction of released particles partition into soils and sediments. This has aggravated the risk of contaminating agricultural fields, potentially threatening associated food webs. To assess possible ENM trophic transfer, cerium accumulation from cerium oxide nanoparticles (nano-CeO2) and their bulk equivalent (bulk-CeO2) was investigated in producers and consumers from a terrestrial food chain. Kidney bean plants (Phaseolus vulgaris var. red hawk) grown in soil contaminated with 1000-2000 mg/kg nano-CeO2 or 1000 mg/kg bulk-CeO2 were presented to Mexican bean beetles (Epilachna varivestis), which were then consumed by spined soldier bugs (Podisus maculiventris). Cerium accumulation in plant and insects was independent of particle size. After 36 days of exposure to 1000 mg/kg nano- and bulk-CeO2, roots accumulated 26 and 19 µg/g Ce, respectively, and translocated 1.02 and 1.3 µg/g Ce, respectively, to shoots. The beetle larvae feeding on nano-CeO2 exposed leaves accumulated low levels of Ce since ∼98% of Ce was excreted in contrast to bulk-CeO2. However, in nano-CeO2 exposed adults, Ce in tissues was higher than Ce excreted. Additionally, Ce content in tissues was biomagnified by a factor of 5.3 from the plants to adult beetles and further to bugs.

Considerations of Environmentally Relevant Test Conditions for Improved Evaluation of Ecological Hazards of Engineered Nanomaterials.

Engineered nanomaterials (ENMs) are increasingly entering the environment with uncertain consequences including potential ecological effects. Various research communities view differently whether ecotoxicological testing of ENMs should be conducted using environmentally relevant concentrations-where observing outcomes is difficult-versus higher ENM doses, where responses are observable. What exposure conditions are typically used in assessing ENM hazards to populations? What conditions are used to test ecosystem-scale hazards? What is known regarding actual ENMs in the environment, via measurements or modeling simulations? How should exposure conditions, ENM transformation, dose, and body burden be used in interpreting biological and computational findings for assessing risks? These questions were addressed in the context of this critical review. As a result, three main recommendations emerged. First, researchers should improve ecotoxicology of ENMs by choosing test end points, duration, and study conditions-including ENM test concentrations-that align with realistic exposure scenarios. Second, testing should proceed via tiers with iterative feedback that informs experiments at other levels of biological organization. Finally, environmental realism in ENM hazard assessments should involve greater coordination among ENM quantitative analysts, exposure modelers, and ecotoxicologists, across government, industry, and academia.

Physiological and Biochemical Changes Imposed by CeO2 Nanoparticles on Wheat: A Life Cycle Field Study.

Interactions of nCeO2 with plants have been mostly evaluated at seedling stage and under controlled conditions. In this study, the effects of nCeO2 at 0 (control), 100 (low), and 400 (high) mg/kg were monitored for the entire life cycle (about 7 months) of wheat plants grown in a field lysimeter. Results showed that at high concentration nCeO2 decreased the chlorophyll content and increased catalase and superoxide dismutase activities, compared with control. Both concentrations changed root and leaf cell microstructures by agglomerating chromatin in nuclei, delaying flowering by 1 week, and reduced the size of starch grains in endosperm. Exposed to low concentration produced embryos with larger vacuoles, while exposure to high concentration reduced number of vacuoles, compared with control. There were no effects on the final biomass and yield, Ce concentration in shoots, as well as sugar and starch contents in grains, but grain protein increased by 24.8% and 32.6% at 100 and 400 mg/kg, respectively. Results suggest that more field life cycle studies are needed in order to better understand the effects of nCeO2 in crop plants.

Monitoring the environmental effects of CeO2 and ZnO nanoparticles through the life cycle of corn (Zea mays) plants and in situ µ-XRF mapping of nutrients in kernels.

Information about changes in physiological and agronomic parameters through the life cycle of plants exposed to engineered nanoparticles (NPs) is scarce. In this study, corn (Zea mays) plants were cultivated to full maturity in soil amended with either nCeO2 or nZnO at 0, 400, and 800 mg/kg. Gas exchange was monitored every 10 days, and at harvest, bioaccumulation of Ce and Zn in tissues was determined by ICP-OES/MS. The effects of NPs exposure on nutrient concentration and distribution in ears were also evaluated by ICP-OES and µ-XRF. Results showed that nCeO2 at both concentrations did not impact gas exchange in leaves at any growth stage, while nZnO at 800 mg/kg reduced net photosynthesis by 12%, stomatal conductance by 15%, and relative chlorophyll content by 10% at day 20. Yield was reduced by 38% with nCeO2 and by 49% with nZnO. Importantly, µ-XRF mapping showed that nCeO2 changed the allocation of calcium in kernels, compared to controls. In nCeO2 treated plants, Cu, K, Mn, and Zn were mainly localized at the insertion of kernels into cobs, but Ca and Fe were distributed in other parts of the kernels. Results showed that nCeO2 and nZnO reduced corn yield and altered quality of corn.

Environmental Effects of Nanoceria on Seed Production of Common Bean (Phaseolus vulgaris): A Proteomic Analysis.

The rapidly growing literature on the response of edible plants to nanoceria has provided evidence of its uptake and bioaccumulation, which delineates a possible route of entry into the food chain. However, little is known about how the residing organic matter in soil may affect the bioavailability and resulting impacts of nanoceria on plants. Here, we examined the effect of nanoceria exposure (62.5-500 mg/kg) on kidney bean (Phaseolus vulgaris) productivity and seed quality as a function of soil organic matter content. Cerium accumulation in the seeds produced from plants in organic matter enriched soil showed a dose-dependent increase, unlike in low organic matter soil treatments. Seeds obtained upon nanoceria exposure in soils with higher organic matter were more susceptible to changes in nutrient quality. A quantitative proteomic analysis of the seeds produced upon nanoceria exposure provided evidence for upregulation of stress-related proteins at 62.5 and 125 mg/kg nanoceria treatments. Although the plants did not exhibit overt toxicity, the major seed proteins primarily associated with nutrient storage (phaseolin) and carbohydrate metabolism (lectins) were significantly down-regulated in a dose dependent manner upon nanoceria exposure. This study thus suggests that nanoceria exposures may negatively affect the nutritional quality of kidney beans at the cellular and molecular level. More confirmatory studies with nanoceria along different species using alternative and orthogonal "omic" tools are currently under active investigation, which will enable the identification of biomarkers of exposure and susceptibility.