CuO and ZnO Nanoparticle Application in Synthetic Soil Modulates Morphology, Nutritional Contents, and Metal Analysis of Brassica nigra.
ABSTRACT: Black mustard (Brassica nigra) was grown in pots amended with 41 nm ZnO (200-600 mg/kg soil) and 47 nm CuO (12.5-50 mg/kg soil) nanoparticles (NPs) to analyze growth response and yield characteristics. B. nigra seed germination was not affected by CuO NPs, but significant toxicity was observed by ZnO NP treatment. Both NPs significantly increased the growth profile of B. nigra, i.e., the stem height, number of leaves, average leaf area, number of branches, and number of nodes per plant. Application of ZnO and CuO NPs brought a significant dose-dependent decrease in primary root length; however, the number of secondary roots increased in the presence of CuO NPs. The average number of flowers and pods per plant significantly increased in the presence of CuO NPs. The seed yield, average seed weight per plant, and seed diameter parameters were observed to be better in the presence of CuO NPs as compared with ZnO NPs. Total protein contents and glucosinolates increased in the seeds grown in the NP-amended soil, while total oil contents decreased. Oil analysis depicted that oleic acid and linolenic acid percentage decreased while erucic acid percentage increased in seeds in the presence of both NPs in the soil. An atomic absorption spectrophotometer showed accumulation of Cu and Zn in B. nigra in the following order: root > stem > leaves > seeds. The study concludes that CuO and ZnO NPs have detrimental effect on the B. nigra plant and yield. The release of NPs and type of metal in NPs might also have a positive effect on the plant; however, their concentration in the soil also matters.
Project description:The effect of surface or lattice modification of nanoparticles (NPs) on terrestrial plants is poorly understood. We investigated the impact of different zinc oxide (ZnO) NPs on green pea (Pisum sativum L.), one of the highest consumed legumes globally. Pea plants were grown for 65 d in soil amended with commercially available bare ZnO NPs (10 nm), 2 wt% alumina doped (Al2O3@ZnO NPs, 15 nm), or 1 wt% aminopropyltriethoxysilane coated NPs (KH550@ZnO NP, 20 nm) at 250 and 1000 mg NP/kg soil inside a greenhouse. Bulk (ZnO) and ionic Zn (zinc chloride) were included as controls. Plant fresh and dry biomass, changes in leaf pigment concentrations, elements (Zn, Al, Si), and protein and carbohydrate profile of green pees were quantified upon harvest at 65 days. With the exception of the coated 1000 mg/kg NP treatment, fresh and dry weight were unaffected by Zn exposure. Although, all treated plants showed higher tissue Zn than controls, those exposed to Al2O3@ZnO NPs at 1000 mg/kg had greater Zn concentration in roots and seeds, compared to bulk Zn and the other NP treatments, keeping Al and Si uptake largely unaffected. Higher Zn accumulation in green pea seeds were resulted in coated ZnO at 250 mg/kg treatments. In leaves, Al2O3@ZnO NP at 250 mg/kg significantly increased Chl-a and carotenoid concentrations relative to the bulk, ionic, and the other NP treatments. The protein and carbohydrate profiles remained largely unaltered across all treatments with the exception of Al2O3@ZnO NPs at 1000 mg/kg where sucrose concentration of green peas increased significantly, which is likely a biomarker of stress. Importantly, these findings demonstrate that lattice and surface modification can significantly alter the fate and phytotoxic effects of ZnO NPs in food crops and seed nutritional quality. To the authors' knowledge, this is the first report of a life cycle study on comparative toxicity of bare, coated, and doped ZnO NPs on a soil-grown food crop.
Project description:The effects of engineered nanoparticles (ENPs) on heavy metal fate and biotoxicity in farmland soil are mostly unknown. A flooding-drying simulation experiment was conducted to study the effects of three typical metal oxide nanoparticles (TiO2-NPs, ZnO-NPs and CuO-NPs) on the chemical speciation of heavy metals and micronutrient bioavailability in paddy soil. The results showed that the addition of ZnO-NPs and CuO-NPs caused significant increases in soil pH, Eh and EC after a 90-d flooding-drying process. ZnO-NPs and CuO-NPs addition caused clearly increase in the Zn and Cu concentrations in the acid-soluble fraction, Fe/Mn oxides-bound fraction and organic-bound fraction, leading to higher bioavailability in the soil. DTPA-extractable Zn and Cu increased to 184.6 mg kg-1 and 145.3 mg kg-1 in the maximum ZnO-NPs and CuO-NPs concentration treatments (500 mg kg-1). TiO2-NPs promoted the transformation of Mn from a Fe/Mn oxides-bound fraction to an acid-soluble fraction. Soil Cd bioavailability obviously decreased in the TiO2-NPs treatment but increased in the ZnO-NPs and CuO-NPs treatments.
Project description:The beneficial bacterium Pseudomonas chlororaphis O6 produces indole-3-acetic acid (IAA), a plant growth regulator. However, the pathway involved in IAA production in this bacterium has not been reported. In this paper we describe the involvement of the indole-3-acetamide (IAM) pathway in IAA production in P. chlororaphis O6 and the effects of CuO and ZnO nanoparticles (NPs). Sublethal levels of CuO and ZnO NPs differentially affected the levels of IAA secreted in medium containing tryptophan as the precursor. After 15 h of growth, CuO NP-exposed cells had metabolized more tryptophan than the control and ZnO NP-challenged cells. The CuO NP-treated cells produced higher IAA levels than control cultures lacking NPs. In contrast, ZnO NPs inhibited IAA production. Mixing of CuO and ZnO NPs resulted in an intermediate level of IAA production relative to the levels in the separate CuO and ZnO NP treatments. The effect of CuO NPs on IAA levels could be duplicated by ions at the concentrations released from the NPs. However, ion release did not account for the inhibition caused by the ZnO NPs. The mechanism underlying changes in IAA levels cannot be accounted for by effects on transcript accumulation from genes encoding a tryptophan permease or the IAM hydrolase in 15-h cultures. These findings raise the issue of whether sublethal doses of NPs would modify the beneficial effects of association between plants and bacteria.
Project description:Herein, CuO/ZnO nanocomposites at different ratios were successfully synthesized through a green biosynthesis approach. This was performed by harnessing the fungal-secreted enzymes and proteins during the sol-gel process for nanocomposites seed growth. All fabricated nanoparticles/nanocomposites were characterized using Fourier Transform Infra-Red (FT-IR) Spectroscopy, X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM-EDX) and X-ray Photoelectron Spectroscopy (XPS) analyses. The photocatalytic degradation efficacy of the synthesized nanocomposites was evaluated using a cationic methylene blue (MB) dye as a model of reaction. Results obtained from the FT-IR and EDX analyses revealed that CuO-NPs, ZnO-NPs, CuO/ZnO50/50, CuO/ZnO80/20, and CuO/ZnO20/80 were successfully prepared by harnessing the biomass filtrate of Penicillium corylophilum As-1. Furthermore, XRD and TEM revealed the variation in the particle size of the nanocomposites (10-55 nm) with the ratio of the nanoparticles. Notably, the size of the nanocomposites was proportionally increased with an increasing ratio of ZnO-NPs. XPS analysis affirmed the presence of both Cu and Zn in the nanocomposites with varying binding energies compared with individual nanoparticles. Furthermore, a high photo-degradation efficacy was achieved by increasing the ratio of ZnO-NPs in the nanocomposite formulation, and 97% of organic MB dye was removed after 85 min of irradiation using the CuO/ZnO20/80 nanocomposite.
Project description:A facile cost effective wet chemical method of synthesis is proposed for Cu-NPs, CuO-NPs and Cu-doped ZnO-NPs. The nanomaterials are opto-physically characterized for nano standard quality. Cu-doped ZnO-NPs based catalytic system is found to possess most efficient photocatalytic activity in degradation of two organic azo-dyes namely methyl red (MR) and malachite green (MG) that are released as industrial effluents in eco-environment intercollegium. Two possible photocatalytic degradation pathways are proposed to understand the mechanism of interaction prevailing during the mineralization of MR and MG dyes. Such study provides insight for waste water management. The uniqueness of the present work is 1) possible routes of MG dye degradation by Cu-doped ZnO-NPs and subsequent intermediate by-products are novel and pioneered of its kind. 2) two new intermediate byproducts are identified suggesting prevalence of multiple MR degradation pathways by Cu-doped ZnO-NPs.For assessment of residual NPs impact on environment, eco-toxicological assay is performed using plant system (Sesamum indicum L.) as model. The study encompasses seed germination, seedling morphology, quantification of endogenous H2O2 and MDA generation, estimation of DNA double strand break and analysis of cell cycle inhibition. Results highlight reduced ecotoxicity of Cu-doped ZnO-NPs compared to the other synthesized nanomaterials thereby suggesting better environmental applicability in waste water purification.
Project description:In this research, quasi-spherical-shaped zinc oxide nanoparticles (ZnO NPs) were synthesized by a simple cost-competitive aqueous precipitation method. The engineered NPs were characterized using several validation methodologies: UV–Vis spectroscopy, diffuse reflection UV–Vis, spectrofluorometry, transmission electron microscopy (TEM), nanoparticle tracking analysis (NTA), and Fourier transform infrared (FTIR) spectroscopy with attenuated total reflection (ATR). A procedure was established to coat a landrace of red maize using gelatinized maize starch. Each maize seed was treated with 0.16 mg ZnO NPs (~7.7 × 10? particles). The standard germination (SG) and accelerated aging (AA) tests indicated that ZnO NP-treated maize seeds presented better physiological quality (higher percentage of normal seedlings) and sanitary quality (lower percentage of seeds contaminated by microorganisms) as compared to controls. The application of ZnO NPs also improved seedling vigor, correlated to shoot length, shoot diameter, root length, and number of secondary roots. Furthermore, shoots and roots of the ZnO NP-treated maize seeds showed a marked increment in the main active FTIR band areas, most notably for the vibrations associated with peptide-protein, lipid, lignin, polysaccharide, hemicellulose, cellulose, and carbohydrate. From these results, it is concluded that ZnO NPs have potential for applications in peasant agriculture to improve the quality of small-scale farmers’ seeds and, as a result, preserve germplasm resources.
Project description:Metal-oxide nanoparticles (NPs) such as copper oxide (CuO) NPs offer promising perspectives for the development of novel agro-chemical formulations of pesticides and fertilizers. However, their potential impact on agro-ecosystem functioning still remains to be investigated. Here, we assessed the impact of CuO-NPs (0.1, 1, and 100 mg/kg dry soil) on soil microbial activities involved in the carbon and nitrogen cycles in five contrasting agricultural soils in a microcosm experiment over 90 days. Additionally, in a pot experiment, we evaluated the influence of plant presence on the toxicity of CuO-NPs on soil microbial activities. CuO-NPs caused significant reductions of the three microbial activities measured (denitrification, nitrification, and soil respiration) at 100 mg/kg dry soil, but the low concentrations (0.1 and 1 mg/kg) had limited effects. We observed that denitrification was the most sensitive microbial activity to CuO-NPs in most soil types, while soil respiration and nitrification were mainly impacted in coarse soils with low organic matter content. Additionally, large decreases in heterotrophic microbial activities were observed in soils planted with wheat, even at 1 mg/kg for soil substrate-induced respiration, indicating that plant presence did not mitigate or compensate CuO-NP toxicity for microorganisms. These two experiments show that CuO-NPs can have detrimental effects on microbial activities in soils with contrasting physicochemical properties and previously exposed to various agricultural practices. Moreover, we observed that the negative effects of CuO-NPs increased over time, indicating that short-term studies (hours, days) may underestimate the risks posed by these contaminants in soils.
Project description:The unregulated discharge of nanoparticles (NPs) from various nanotechnology industries into the environment is expected to alter the composition and physiological functions of soil microbiota. Considering this knowledge gap, the impact of five NPs (Ag, ZnO, CuO, Al2O3, and TiO2) differing in size and morphology on growth behavior and physiological activity of Azotobacter chroococcum, Bacillus thuringiensis, Pseudomonas mosselii, and Sinorhizobium meliloti were investigated. Various biochemical and microscopic approaches were adopted. Interestingly, all bacterial strains were found sensitive to Ag-NPs and ZnO-NPs but showed tolerance toward CuO, Al2O3, and TiO2-NPs. The loss of cellular respiration due to NPs was coupled with a reduction in population size. ZnO-NPs at 387.5 ?g mL-1 had a maximum inhibitory impact on A. chroococcum and reduced its population by 72%. Under Ag-NP stress, the reduction in IAA secretion by bacterial strains followed the order S. meliloti (74%) > P. mosselii (63%) > A. chroococcum (49%). The surface of bacterial cells had small- or large-sized aggregates of NPs. Also, numerous gaps, pits, fragmented, and disorganized cell envelopes were visible. Additionally, a treated cell surface appeared corrugated with depressions and alteration in cell length and a strong heterogeneity was noticed under atomic force microscopy (AFM). For instance, NPs induced cell roughness for P. mosselii followed the order 12.6 nm (control) > 58 nm (Ag-NPs) > 41 nm (ZnO-NPs). TEM analysis showed aberrant morphology, cracking, and disruption of the cell envelope with extracellular electron-dense materials. Increased permeability of the inner cell membrane caused cell death and lowered EPS production. Ag-NPs and ZnO-NPs also disrupted the surface adhering ability of bacteria, which varied with time and concentration of NPs. Conclusively, a plausible mechanism of NP toxicity to bacteria has been proposed to understand the mechanistic basis of ecological interaction between NPs and resourceful bacteria. These results also emphasize to develop strategies for the safe disposal of NPs.
Project description:Nanoparticles (NPs) of copper oxide (CuO), zinc oxide (ZnO) and especially nanosilver are intentionally used to fight the undesirable growth of bacteria, fungi and algae. Release of these NPs from consumer and household products into waste streams and further into the environment may, however, pose threat to the 'non-target' organisms, such as natural microbes and aquatic organisms. This review summarizes the recent research on (eco)toxicity of silver (Ag), CuO and ZnO NPs. Organism-wise it focuses on key test species used for the analysis of ecotoxicological hazard. For comparison, the toxic effects of studied NPs toward mammalian cells in vitro were addressed. Altogether 317 L(E)C50 or minimal inhibitory concentrations (MIC) values were obtained for algae, crustaceans, fish, bacteria, yeast, nematodes, protozoa and mammalian cell lines. As a rule, crustaceans, algae and fish proved most sensitive to the studied NPs. The median L(E)C50 values of Ag NPs, CuO NPs and ZnO NPs (mg/L) were 0.01, 2.1 and 2.3 for crustaceans; 0.36, 2.8 and 0.08 for algae; and 1.36, 100 and 3.0 for fish, respectively. Surprisingly, the NPs were less toxic to bacteria than to aquatic organisms: the median MIC values for bacteria were 7.1, 200 and 500 mg/L for Ag, CuO and ZnO NPs, respectively. In comparison, the respective median L(E)C50 values for mammalian cells were 11.3, 25 and 43 mg/L. Thus, the toxic range of all the three metal-containing NPs to target- and non-target organisms overlaps, indicating that the leaching of biocidal NPs from consumer products should be addressed.
Project description:Airborne ultrafine particles (UFP) mainly derive from combustion sources (e.g., diesel exhaust particles-DEP), abrasion sources (non-exhaust particles) or from the unintentional release of engineered nanoparticles (e.g., metal oxide nanoparticles-NPs), determining human exposure to UFP mixtures. The aim of the present study was to analyse the combined in vitro effects of DEP and metal oxide NPs (ZnO, CuO) on human lung A549 cells. The mixtures and the relative single NPs (DEP, ZnO, CuO) were characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS) and inductively coupled plasma-optic emission spectroscopy (ICP-OES). Cells were exposed for different times (3-72 h) to mixtures of standard DEP at a subcytotoxic concentration and ZnO and CuO at increasing concentrations. At the end of the exposure, the cytotoxicity was assessed by 3-(4,5-Dimethylthiazol-2-yl)-2,5-Diphenyltetrazolium Bromide (MTT) and clonogenic tests, the pro-inflammatory potential was evaluated by interleukin-8 (IL-8) release and the cell morphology was investigated by fluorescence and transmission electron microscopy. The obtained results suggest that the presence of DEP may introduce new physico-chemical interactions able to increase the cytotoxicity of ZnO and to reduce that of CuO NPs.