Alia D. Servin

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.

Terrestrial Trophic Transfer of Bulk and Nanoparticle La2O3 Does Not Depend on Particle Size

The bioaccumulation and trophic transfer of bulk and nanoparticle (NP) La2O3 from soil through a terrestrial food chain was determined. To investigate the impact of growth conditions, lettuce (Lactuca sativa) was grown in 350 or 1200 g of bulk/NP amended soil. Leaf tissues were fed to crickets (Acheta domesticus) or darkling beetles (Tenebrionoidea); select crickets were fed to mantises. In the small pot (350 g), La2O3 exposure reduced plant biomass by 23-30% and La tissue content did not differ with particle size. In the large pot (1200 g), biomass was unaffected by exposure and La content in the tissues were significantly greater with bulk particle treatment. Darkling beetles exposed to bulk and NP La2O3-contaminated lettuce contained La at 0.18 and 0.08 mg/kg; respectively (significantly different, P < 0.05). Crickets fed bulk or NP La2O3-exposed lettuce contained 0.53 and 0.33 mg/kg, respectively (significantly different, P < 0.05) with 48 h of depuration. After 7 d of depuration, La content did not differ with particle size, indicating that 48 h may be insufficient to void the digestive system. Mantises that consumed crickets from bulk and NP-exposed treatments contained La at 0.05-0.060 mg/kg (statistically equivalent). These results demonstrate that although La does trophically transfer, biomagnification does not occur and NP levels are equivalent or less than the bulk metal.

Molecular Response of Crop Plants to Engineered Nanomaterials

Functional toxicology has enabled the identification of genes involved in conferring tolerance and sensitivity to engineered nanomaterial (ENM) exposure in the model plant Arabidopsis thaliana (L.) Heynh. Several genes were found to be involved in metabolic functions, stress response, transport, protein synthesis, and DNA repair. Consequently, analysis of physiological parameters, metal content (through ICP-MS quantification), and gene expression (by RT-qPCR) of A. thaliana orthologue genes were performed across different plant species of agronomic interest to highlight putative biomarkers of exposure and effect related to ENMs. This approach led to the identification of molecular markers in Solanum lycopersicum L. and Cucurbita pepo L. (tomato and zucchini) that might not only indicate exposure to ENMs (CuO, CeO2, and La2O3) but also provide mechanistic insight into response to these materials. Through Gene Ontology (GO) analysis, the target genes were mapped in complex interatomic networks representing molecular pathways, cellular components, and biological processes involved in ENM response. The transcriptional response of 38 (out of 204) candidate genes studied varied according to particle type, size, and plant species. Importantly, some of the genes studied showed potential as biomarkers of ENM exposure and effect and may be useful for risk assessment in foods and in the environment.

Arsenic Localization and Speciation in the Root-Soil Interface of the Desert Plant Prosopis juliflora-velutina

The bioavailability and mobility of arsenic (As) in soils depends on several factors such as pH, organic matter content, speciation, and the concentration of oxides and clay minerals, among others. Plants modify As bioavailability in the rhizosphere; thus, the biogeochemical processes of As in vegetated and non-vegetated soils are different. Changes in As speciation induced by the rhizosphere can be monitored using micro-focused synchrotron-based X-ray fluorescence (μXRF) combined with μX-ray absorption near-edge spectroscopy (μXANES). This research investigated As speciation in the rhizosphere of mesquite (Prosopis juliflora-velutina) plants grown in a sandy clay loam treated with As(III) and As(V) at 40 mg kg−1. Rhizosphere soil and freeze-dried root tissues of one-month-old plants were analyzed by bulk XAS. Bulk XAS results showed that As(V) was the predominant species in the soil (rhizosphere and non-vegetated), whereas As(III) was dominant in the root tissues from both As(V) and As(III) treated plants. μXAS and μXRF studies of thin sections from resin embedded soil cores revealed the As(III)–S interactions in root tissues and a predominant As–Fe interaction in the soil. This research demonstrated that the combination of bulk XAS and μXAS techniques is a powerful analytical technique for the study of As speciation in soil and plant samples

Bioaccumulation of CeO2 Nanoparticles by Earthworms in Biochar-Amended Soil: A Synchrotron Microspectroscopy Study

The interactions of nanoparticles (NPs) with biochar and soil components may substantially influence NP availability and toxicity to biota. In the present study, earthworms ( Eisenia fetida) were exposed for 28 days to a residential or agricultural soil amended with 0-2000 mg of CeO2 NP/kg and with biochar (produced by the pyrolysis of pecan shells at 350 and 600 °C) at various application rates [0-5% (w/w)]. After 28 days, earthworms were depurated and analyzed for Ce content, moisture content, and lipid peroxidation. The results showed minimal toxicity to the worms; however, biochar (350 or 600 °C) was the dominant factor, accounting for 94 and 84% of the variance for the moisture content and lipid peroxidation, respectively, in the exposed earthworms. For both soils with 1000 mg of CeO2/kg at 600 °C, biochar significantly decreased the accumulation of Ce in the worm tissues. Amendment with 350 °C biochar had mixed responses on Ce uptake. Analysis by micro X-ray fluorescence (μ-XRF) and micro X-ray absorption near edge structure (μ-XANES) was used to evaluate Ce localization, speciation, and persistence in CeO2- and biochar-exposed earthworms after depuration for 12, 48, and 72 h. Earthworms from the 500 mg of CeO2/kg and 0% biochar treatments eliminated most Ce after a 48 h depuration period. However, in the same treatment and with 5% BC-600 (biochar pyrolysis temperature of 600 °C), ingested biochar fragments (∼50 μm) with Ce adsorbed to the surfaces were retained in the gut after 72 h. Additionally, Ce remained in earthworms from the 2000 mg of CeO2/kg and 5% biochar treatments after depuration for 48 h. Analysis by μ-XANES showed that, within the earthworm tissues, Ce remained predominantly as Ce4+O2, with only few regions (2-3 μm2) where it was found in the reduced form (Ce3+). The present findings highlight that soil and biochar properties have a significant influence in the internalization of CeO2 NPs in earthworms; such interactions need to be considered when estimating NP fate and effects in the environment.