CuO nanoparticles (CuO-NP) were synthesized in a hydrogen diffusion flame. Particle size and morphology were characterized using scanning mobility particle sizing, Brunauer–Emmett–Teller analysis, dynamic light scattering, and transmission electron microscopy. The solubility of CuO-NP varied with both pH and presence of other ions. CuO-NP and comparable doses of soluble Cu were applied to duckweeds, Landoltia punctata. Growth was inhibited 50% by either 0.6 mg L−1 soluble copper or by 1.0 mg L−1 CuO-NP that released only 0.16 mg L−1 soluble Cu into growth medium. A significant decrease of chlorophyll was observed in plants stressed by 1.0 mg L−1 CuO-NP, but not in the comparable 0.2 mg L−1 soluble Cu treatment. The Cu content of fronds exposed to CuO-NP is four times higher than in fronds exposed to an equivalent dose of soluble copper, and this is enough to explain the inhibitory effects on growth and chlorophyll content.
The release of nanoparticles (NPs) to the environment poses an increasing potential threat to biological systems. This study investigated the phytotoxicity and accumulation of copper oxide (CuO) NPs to Elsholtzia splendens (a Cu-tolerant plant) under hydroponic conditions. The 50% effective concentration (EC50) of CuO NPs to E. splendens was about 480 mg/L, implying the tolerance of E. splendens to CuO NPs. The Cu content in the shoots treated with 1000 mg/L CuO NPs was much higher than those exposed to the comparable 0.5 mg/L soluble Cu and CuO bulk particles. CuO NPs-like deposits were found in the root cells and leaf cells. Cu K-edge X-ray absorption near-edge structure analysis further revealed that the accumulated Cu species existed predominantly as CuO NPs in the plant tissues. All these results suggested that CuO NPs can be absorbed by the roots and translocated to the shoots in E. splendens.
Agricultural soil is gradually becoming a primary sink for metal-based nanoparticles (MNPs). The uptake and accumulation of MNPs by crops may contaminate food chain and pose unexpected risks for human health. Here, we investigated the fate and transformation of CuO nanoparticles (NPs) in the soil-rice system during the rice lifecycle. The results show that at the maturation stage, 1000 mg/kg CuO NPs significantly decreased redox potential by 202.75 mV but enhanced electrical conductivity by 497.07 mS/cm compared to controls. Moreover, the bioavailability of highest CuO NPs in the soil was reduced by 69.84% along with the plant growth but then was significantly increased by 165% after drying-wetting cycles. Meanwhile, CuO and Cu combined with humic acid were transformed to CuS and Cu associated with goethite by X-ray absorption near edge structure analysis. Additionally, CuO NPs had an acute negative effect on the plant growth than bulk particles, which dramatically reduced the fresh weight of grains to 6.51% of controls. Notably, CuO NPs were found to be translocated from soil to plant especially to the chaff and promoted the Cu accumulation in the aleurone layer of rice using micro X-ray fluorescence technique, but could not reach the polished rice.
Ultisols in China need phosphorus (P) fertilization to sustain crop production but are prone to P loss in runoff. Balancing P inputs and loss requires detailed information about soil P forms because P speciation influences P cycling. Analytical methods vary in the information they provide on P speciation; thus, we used sequential fractionation (SF), solution P nuclear magnetic resonance (P-NMR), and P K-edge X-ray absorption near-edge structure (XANES) spectroscopy to investigate organic P (P) and inorganic P (P) species in Chinese Ultisols managed for different crops and with different fertilizer inputs in the first study to combine these techniques to characterize soil P. Sequential fractionation showed that moderately labile NaOH-P was the largest P pool in these soils, P varied from 20 to 47%, and residual P ranged from 9 to 31%. Deoxyribonucleic acid (1-5%) and -inositol hexakisphosphate (-IHP, 4-10%) were the major P forms from P-NMR. Orthophosphate diesters determined by NMR were significantly correlated with labile NaHCO-P in SF ( > 0.981; < 0.001). Soil P was shown to be predominantly associated with iron and soluble calcium (Ca) by XANES. Furthermore, XANES identified hydroxyapatite in the soil receiving the highest rates of Ca-phosphate fertilizer, which had the highest HCl-P pool by SF, and also identified IHP (7%) in the soil with the highest proportion of -IHP from P-NMR. These results strongly suggest that a combined use of SF, solution P-NMR, and P K-edge XANES spectroscopy will provide the comprehensive information about soil P species needed for effective soil P management.
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