Jose A. Hernandez-Viezcas

In Situ Synchrotron X-ray Fluorescence Mapping and Speciation of CeO2 and ZnO Nanoparticles in Soil Cultivated Soybean (Glycine max)

With the increased use of engineered nanomaterials such as ZnO and CeO₂ nanoparticles (NPs), these materials will inevitably be released into the environment, with unknown consequences. In addition, the potential storage of these NPs or their biotransformed products in edible/reproductive organs of crop plants can cause them to enter into the food chain and the next plant generation. Few reports thus far have addressed the entire life cycle of plants grown in NP-contaminated soil. Soybean ( Glycine max ) seeds were germinated and grown to full maturity in organic farm soil amended with either ZnO NPs at 500 mg/kg or CeO₂ NPs at 1000 mg/kg. At harvest, synchrotron μ-XRF and μ-XANES analyses were performed on soybean tissues, including pods, to determine the forms of Ce and Zn in NP-treated plants. The X-ray absorption spectroscopy studies showed no presence of ZnO NPs within tissues. However, μ-XANES data showed O-bound Zn, in a form resembling Zn-citrate, which could be an important Zn complex in the soybean grains. On the other hand, the synchrotron μ-XANES results showed that Ce remained mostly as CeO₂ NPs within the plant. The data also showed that a small percentage of Ce(IV), the oxidation state of Ce in CeO₂ NPs, was biotransformed to Ce(III). To our knowledge, this is the first report on the presence of CeO₂ and Zn compounds in the reproductive/edible portion of the soybean plant grown in farm soil with CeO₂ and ZnO NPs.

Synchrotron Verification of TiO2 Accumulation in Cucumber Fruit: A Possible Pathway of TiO2 Nanoparticle Transfer from Soil into the Food Chain

The transfer of nanoparticles (NPs) into the food chain through edible plants is of great concern. Cucumis sativus L. is a freshly consumed garden vegetable that could be in contact with NPs through biosolids and direct agrichemical application. In this research, cucumber plants were cultivated for 150 days in sandy loam soil treated with 0 to 750 mg TiO2 NPs kg(-1). Fruits were analyzed using synchrotron μ-XRF and μ-XANES, ICP-OES, and biochemical assays. Results showed that catalase in leaves increased (U mg(-1) protein) from 58.8 in control to 78.8 in 750 mg kg(-1) treatment; while ascorbate peroxidase decreased from 21.9 to 14.1 in 500 mg kg(-1) treatment. Moreover, total chlorophyll content in leaves increased in the 750 mg kg(-1) treatment. Compared to control, FTIR spectra of fruit from TiO2 NP treated plants showed significant differences (p ≤ 0.05) in band areas of amide, lignin, and carbohydrates, suggesting macromolecule modification of cucumber fruit. In addition, compared with control, plants treated with 500 mg kg(-1) had 35% more potassium and 34% more phosphorus. For the first time, μ-XRF and μ-XANES showed root-to-fruit translocation of TiO2 in cucumber without biotransformation. This suggests TiO2 could be introduced into the food chain with unknown consequences.

Synchrotron micro-XRF and micro-XANES confirmation of the uptake and translocation of TiO2 nanoparticles in cucumber (Cucumis sativus) plants

Advances in nanotechnology have raised concerns about possible effects of engineered nanomaterials (ENMs) in the environment, especially in terrestrial plants. In this research, the impacts of TiO(2) nanoparticles (NPs) were evaluated in hydroponically grown cucumber (Cucumis sativus) plants. Seven day old seedlings were treated with TiO(2) NPs at concentrations varying from 0 to 4000 mg L(-1). At harvest, the size of roots and shoots were measured. In addition, micro X- ray fluorescence (micro-XRF) and micro X-ray absorption spectroscopy (micro-XAS), respectively, were used to track the presence and chemical speciation of Ti within plant tissues. Results showed that at all concentrations, TiO(2) significantly increased root length (average >300%). By using micro-XRF it was found that Ti was transported from the roots to the leaf trichomes, suggesting that trichomes are possible sink or excretory system for the Ti. The micro-XANES spectra showed that the absorbed Ti was present as TiO(2) within the cucumber tissues, demonstrating that the TiO(2) NPs were not biotransformed.

Stress response and tolerance of Zea mays to CeO2 nanoparticles: Cross talk among H2O2, heat shock protein, and lipid peroxidation

The rapid development of nanotechnology will inevitably release nanoparticles (NPs) into the environment with unidentified consequences. In addition, the potential toxicity of CeO(2) NPs to plants and the possible transfer into the food chain are still unknown. Corn plants (Zea mays) were germinated and grown in soil treated with CeO(2) NPs at 400 or 800 mg/kg. Stress-related parameters, such as H(2)O(2), catalase (CAT), and ascorbate peroxidase (APX) activity, heat shock protein 70 (HSP70), lipid peroxidation, cell death, and leaf gas exchange were analyzed at 10, 15, and 20 days post-germination. Confocal laser scanning microscopy was used to image H(2)O(2) distribution in corn leaves. Results showed that the CeO(2) NP treatments increased accumulation of H(2)O(2), up to day 15, in phloem, xylem, bundle sheath cells and epidermal cells of shoots. The CAT and APX activities were also increased in the corn shoot, concomitant with the H(2)O(2) levels. Both 400 and 800 mg/kg CeO(2) NPs triggered the up-regulation of the HSP70 in roots, indicating a systemic stress response. None of the CeO(2) NPs increased the level of thiobarbituric acid reacting substances, indicating that no lipid peroxidation occurred. CeO(2) NPs, at both concentrations, did not induce ion leakage in either roots or shoots, suggesting that membrane integrity was not compromised. Leaf net photosynthetic rate, transpiration, and stomatal conductance were not affected by CeO(2) NPs. Our results suggest that the CAT, APX, and HSP70 might help the plants defend against CeO(2) NP-induced oxidative injury and survive NP exposure.

Toxicity assessment of cerium oxide nanoparticles in cilantro (Coriandrum sativum L.) plants grown in organic soil

Studies have shown that CeO₂ nanoparticles (NPs) can be accumulated in plants without modification, which could pose a threat for human health. In this research, cilantro (Coriandrum sativum L.) plants were germinated and grown for 30 days in soil amended with 0 to 500 mg kg⁻¹ CeO₂ NPs and analyzed by spectroscopic techniques and biochemical assays. At 125 mg kg⁻¹, plants produced longer roots (p ≤ 0.05), and at 500 mg kg⁻¹, there was higher Ce accumulation in tissues (p ≤ 0.05). At 125 mg, catalase activity significantly increased in shoots and ascorbate peroxidase in roots (p ≤ 0.05). The FTIR analyses revealed that at 125 mg kg⁻¹ the CeO₂ NPs changed the chemical environment of carbohydrates in cilantro shoots, for which changes in the area of the stretching frequencies were observed. This suggests that the CeO₂ NPs could change the nutritional properties of cilantro.

Exposure of engineered nanomaterials to plants: Insights into the physiological and biochemical responses-A review.

Recent investigations show that carbon-based and metal-based engineered nanomaterials (ENMs), components of consumer goods and agricultural products, have the potential to build up in sediments and biosolid-amended agricultural soils. In addition, reports indicate that both carbon-based and metal-based ENMs affect plants differently at the physiological, biochemical, nutritional, and genetic levels. The toxicity threshold is species-dependent and responses to ENMs are driven by a series of factors including the nanomaterial characteristics and environmental conditions. Effects on the growth, physiological and biochemical traits, production and food quality, among others, have been reported. However, a complete understanding of the dynamics of interactions between plants and ENMs is not clear enough yet. This review presents recent publications on the physiological and biochemical effects that commercial carbon-based and metal-based ENMs have in terrestrial plants. This document focuses on crop plants because of their relevance in human nutrition and health. We have summarized the mechanisms of interaction between plants and ENMs as well as identified gaps in knowledge for future investigations.

Exposure of cerium oxide nanoparticles to kidney bean shows disturbance in the plant defense mechanisms

Overwhelming use of engineered nanoparticles demands rapid assessment of their environmental impacts. The transport of cerium oxide nanoparticles (nCeO2) in plants and their impact on cellular homeostasis as a function of exposure duration is not well understood. In this study, kidney bean plants were exposed to suspensions of ∼ 8 ± 1 nm nCeO2 (62.5 to 500 mg/L) for 15 days in hydroponic conditions. Plant parts were analyzed for cerium accumulation after one, seven, and 15 days of nCeO2 exposure. The primary indicators of stress like lipid peroxidation, antioxidant enzyme activities, total soluble protein and chlorophyll contents were studied. Cerium in tissues was localized using scanning electron microscopy and synchrotron μ-XRF mapping, and the chemical forms were identified using μ-XANES. In the root epidermis, cerium was primarily shown to exist as nCeO2, although a small fraction (12%) was biotransformed to Ce(III) compound. Cerium was found to reach the root vascular tissues and translocate to aerial parts with time. Upon prolonged exposure to 500 mg nCeO2/L, the root antioxidant enzyme activities were significantly reduced, simultaneously increasing the root soluble protein by 204%. In addition, leafs guaiacol peroxidase activity was enhanced with nCeO2 exposure in order to maintain cellular homeostasis.

Cerium dioxide and zinc oxide nanoparticles alter the nutritional value of soil cultivated soybean plants

The aim of this study was to determine nutrient elements in soybean (Glycine max) plants cultivated in farm soil amended with nCeO2 at 0-1000 mg kg(-1) and nZnO at 0-500 mg kg(-1). Digested samples were analyzed by ICP-OES/MS. Compared to control, pods from nCeO2 at 1000 mg kg(-1) had significantly less Ca but more P and Cu, while pods from 100 mg kg(-1)nZnO had more Zn, Mn, and Cu. Plants treated with nZnO showed significant correlations among Zn, P, and S in pods with Zn in roots. Correlations among pod Zn/root Zn was r = 0.808 (p ≤ 0.01) and pod P/root P was r = 0.541 (p ≤ 0.05). The correlation among pod S/root S was r = -0.65 (p ≤ 0.01). While nCeO2 treatments exhibited significant correlations between pod Ca/root Ca (r = 0.645, p ≤ 0.05). The data suggest that nCeO2 and nZnO alter the nutritional value of soybean, which could affect the health of plants, humans, and animals.

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.

ZnO nanoparticle fate in soil and zinc bioaccumulation in corn plants (Zea mays) influenced by alginate

Nanoparticles (NPs) can interact with naturally occurring inorganic and organic substances in soils, which may change their transport behavior in soil and plants. This study was performed in two steps. In the first step, corn (Zea mays) plants were cultivated for one month in soil amended with 10 nm commercial spheroid ZnO NPs at 0–800 mg kg−1 and sodium alginate at 10 mg kg−1. In the second step, the plants were grown with ZnO NPs at 400 mg kg−1 and alginate at 0, 10, 50, and 100 mg kg−1. The dynamics of Zn concentrations in soil solution and Zn accumulation in plant tissues were determined by ICP-OES. Biomass accumulation, chlorophyll concentration, and the activity of antioxidant enzymes in leaves were also quantified. Results indicate that ZnO NPs coexisting with Zn dissolved species were continuously released to the soil solution to replenish the Zn ions or ZnO NPs scavenged by roots. At 400 and 800 mg kg−1, without alginate, ZnO NPs significantly reduced the root and shoot biomass production; however, plants treated with these NP concentrations, plus alginate, had significantly more Zn in tissues with no reduction in biomass production. Alginate significantly reduced the activity of stress enzymes catalase and peroxidase, which could indicate damage in the defense system. The effects of ZnO NPs in a food crop grown in alginate enriched soil, showing an excess of Zn in the aerial parts, are yet to be reported.