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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.

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Many studies have shown the effect of solution chemistry on the environmental behavior of metal-based nanoparticles (NPs), except CuO NPs. Here, we investigated the agglomeration, sedimentation, dissolution, and speciation of CuO NPs by varying pH, ionic strength, ionic valence, and natural organic matter (NOM). The results showed that as the pH moved away from 6, the size of CuO agglomerates decreased, along with the enhanced NP suspension stabilization, due to the increase of electrostatic repulsive force. Increasing ionic strength and valence intensified the agglomeration and sedimentation of CuO NPs because of the compression of electrical double layers. The presence of humic acid and citric acid enhanced the dispersion and stabilization of CuO NP suspension, but l-cysteine showed a different impact. Decreasing pH, increasing ionic strength and all NOM improved the dissolution of CuO NPs, but the divalent electrolyte (CaCl2) inhibited the Cu2+ release from CuO NPs compared to the monovalent electrolyte (NaCl). In addition, X-ray absorption near edge structure (XANES) analysis demonstrated that the presence of l-cysteine transformed more than 30% of CuO NPs to Cu(I)-cysteine by coordinating with thiol group. This study can give us an in-depth understanding on the environmental behavior and fate of CuO NPs in the aquatic environment.

The specific properties of metal-based nanoparticles (NPs) have not only led to rapidly increasing applications in various industrial and commercial products, but also caused environmental concerns due to the inevitable release of NPs and their unpredictable biological/ecological impacts. This review discusses the environmental behavior of metal-based NPs with an in-depth analysis of the mechanisms and kinetics. The focus is on knowledge gaps in the interaction of NPs with aquatic organisms, which can influence the fate, transport and toxicity of NPs in the aquatic environment. Aggregation transforms NPs into micrometer-sized clusters in the aqueous environment, whereas dissolution also alters the size distribution and surface reactivity of metal-based NPs. A unique toxicity mechanism of metal-based NPs is related to the generation of reactive oxygen species (ROS) and the subsequent ROS-induced oxidative stress. Furthermore, aggregation, dissolution and ROS generation could influence each other and also be influenced by many factors, including the sizes, shapes and surface charge of NPs, as well as the pH, ionic strength, natural organic matter and experimental conditions. Bioaccumulation of NPs in single organism species, such as aquatic plants, zooplankton, fish and benthos, is summarized and compared. Moreover, the trophic transfer and/or biomagnification of metal-based NPs in an aquatic ecosystem are discussed. In addition, genetic effects could result from direct or indirect interactions between DNA and NPs. Finally, several challenges facing us are put forward in the review.

The waterlogging environment generally results in the deposition of iron plaque on plant roots, which may impact the fate of metal-based nanoparticles. Here, we investigated the influence of iron plaque on the uptake, translocation, and transformation of copper oxide nanoparticles (CuO NPs) in rice plants. The results show that the presence of iron plaque dramatically reduced the Cu contents in roots and shoots by 89% and 78% of those without iron plaque under 100 mg/L CuO NP treatment. Meanwhile, the Cu accumulation in plants was negatively related to the amount of iron plaque. X-ray absorption near edge structure (XANES) analysis demonstrated lower percentage of CuO but higher proportion of Cu(I) in shoots exposed to CuO NPs with the formation of iron plaque. Furthermore, micro X-ray fluorescence (μ-XRF) combined with μ-XANES revealed that the iron plaque in the root epidermis and exodermis consisted of goethite and ferrihydrite, which hindered the uptake of CuO NPs by roots. However, a few CuO NPs were still absorbed by roots via root hairs or lateral roots, and further translocated to shoots. But eventually, more than 90% of total Cu(II) was reduced to Cu(I)-cysteine and Cu 2 O in leaf veins of rice plants with iron plaque.

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