Toxicity mechanisms of graphene oxide and cadmium in Microcystis aeruginosa: evaluation of photosynthetic and oxidative responses.

The potential ecotoxicological hazard of gaphene oxide (GO) is not fully clarified for photoautotrophic organisms, especially when the interactions of GO with other environmental toxicants are considered. The objective of the current study was to better understand the mechanisms of toxicity of GO in the cyanobacteria Microcystis aeruginosa, and to identify its interactions with cadmium (Cd). The individual and combined contribution of both pollutants in cyanobacteria were evaluated after 96 hours of exposure to GO and/or Cd, using photosynthetic pigments, photosynthetic parameters, cellular indicators of peroxidative damage, viability, and intracellular ROS formation as indicators of toxicity. Interactions between GO and Cd were evaluated using Toxic Units based on the EC50 of each parameter evaluated. The results of this study indicate that single concentrations ≥ 5 µg mL-1 of GO and ≥ 0.1 µg mL-1 of Cd induced a decrease in cell biomass and a change in the photosynthetic parameters associated with primary productivity in M. aeruginosa. In the combined experiments, higher GO ratios (≥ 9.1 µg mL-1) in terms of Toxic Units decreased photochemical processes and cellular metabolism, increased oxidative stress, and ultimately affected the size of M. aeruginosa. Finally, the relationship between GO concentration, Cd concentration, and the adsorption capacity of GO with respect to the co-pollutant must be taken into account when assessing the environmental risk of GO in aquatic environments.

Increasing bromide removal by graphene-silver nanocomposites: Nanoparticulate silver enhances bromide selectivity through direct surface interactions.

Bromide forms toxic brominated disinfection by-products during disinfection. Current bromide removal technologies are often non-specific and costly due to naturally occurring competing anions. A silver-impregnated graphene oxide (GO) nanocomposite is reported here that reduced the amount of Ag needed for Br- removal by increasing its selectivity towards Br-. GO was impregnated with ionic (GO-Ag+) or nanoparticulate Ag (GO-nAg) and compared against Ag+ or unsupported nAg to identify molecular level interactions. In nanopure water, Ag+ and nAg had the highest Br- removal (∼0.89 mol Br-/mol Ag+) followed by GO-nAg at 0.77 mol Br-/mol Ag+. However, under anionic competition, the Ag+ removal was reduced to 0.10 mol Br-/mol Ag+ while all nAg forms retained good Br- removal. To understand the removal mechanism, anoxic experiments were performed to prevent nAg dissolution, which resulted in higher Br- removal for all nAg forms compared to oxic conditions. This suggests that reaction of Br- with the nAg surface is more selective than with Ag+. Finally, jar tests showed that anchoring nAg on GO enhances Ag removal during coagulation/flocculation/sedimentation compared to unsupported nAg or Ag+. Thus, our results identify strategies that can be used to design selective and silver-efficient adsorbents for Br- removal in water treatment.

Evaluation of bioaccumulation of nanoplastics, carbon nanotubes, fullerenes, and graphene family materials.

Bioaccumulation is a key factor in understanding the potential ecotoxicity of substances. While there are well-developed models and methods to evaluate bioaccumulation of dissolved organic and inorganic substances, it is substantially more challenging to assess bioaccumulation of particulate contaminants such as engineered carbon nanomaterials (CNMs; carbon nanotubes (CNTs), graphene family nanomaterials (GFNs), and fullerenes) and nanoplastics. In this study, the methods used to evaluate bioaccumulation of different CNMs and nanoplastics are critically reviewed. In plant studies, uptake of CNMs and nanoplastics into the roots and stems was observed. For multicellular organisms other than plants, absorbance across epithelial surfaces was typically limited. Biomagnification was not observed for CNTs and GFNs but were observed for nanoplastics in some studies. However, the reported absorption in many nanoplastic studies may be a consequence of an experimental artifact, namely release of the fluorescent probe from the plastic particles and subsequent uptake. We identify that additional work is needed to develop analytical methods to provide robust, orthogonal methods that can measure unlabeled (e.g., without isotopic or fluorescent labels) CNMs and nanoplastics.

Potential Artifacts and Control Experiments in Toxicity Tests of Nanoplastic and Microplastic Particles.

To fully understand the potential ecological and human health risks from nanoplastics and microplastics (NMPs) in the environment, it is critical to make accurate measurements. Similar to past research on the toxicology of engineered nanomaterials, a broad range of measurement artifacts and biases are possible when testing their potential toxicity. For example, antimicrobials and surfactants may be present in commercially available NMP dispersions, and these compounds may account for toxicity observed instead of being caused by exposure to the NMP particles. Therefore, control measurements are needed to assess potential artifacts, and revisions to the protocol may be needed to eliminate or reduce the artifacts. In this paper, we comprehensively review and suggest a next generation of control experiments to identify measurement artifacts and biases that can occur while performing NMP toxicity experiments. This review covers the broad range of potential NMP toxicological experiments, such as in vitro studies with a single cell type or complex 3-D tissue constructs, in vivo mammalian studies, and ecotoxicity experiments testing pelagic, sediment, and soil organisms. Incorporation of these control experiments can reduce the likelihood of false positive and false negative results and more accurately elucidate the potential ecological and human health risks of NMPs.

Controlling silver release from antibacterial surface coatings on stainless steel for biofouling control.

This study focuses on the in-situ nucleation of silver nanoparticles (AgNPs) on stainless steel (SS) to provide a localized antibacterial action for biofouling control during space missions. Since AgNPs rapidly dissolve in water, partial passivation of AgNPs was provided to slow down silver release and extend the lifetime of the antibacterial coating. Two different passivation approaches, based on the formation of low solubility silver sulfide (Ag2S) or silver bromide (AgBr) shells, were compared to identify the optimal passivation for biofouling control. Highest bacterial inactivation (up to 75%) occurred with sulfidized AgNPs as opposed to bromidized (up to 50%) NPs. The optimal passivation treatment for biofouling control was found at 10-5 M Na2S (for Ag2S) and 10-3 M NaBr (for AgBr) concentrations. Scanning Electron Microscopy (SEM) analyses confirmed the presence of AgNPs on AgBr and Ag2S-coated samples. Further investigation revealed that compared to pristine AgNPs, Ag release from both sulfidized and bromidized NPs was significantly lower (16% vs 6% or less). Overall, both sulfidized and bromidized AgNPs were effective at controlling biofilm formation; however, sulfidized NPs exhibited the maximum antibacterial activity, making it the preferable passivation strategy for AgNPs on SS surfaces.

Aging of microplastics increases their adsorption affinity towards organic contaminants.

When released in the environment, microplastics undergo surface weathering due to mechanical abrasion and ultraviolet exposure. In this study, the adsorption of two model contaminants, phenanthrene and methylene blue, by weathered high density polyethylene (HDPE) and polypropylene (PPE) was evaluated to understand how the microplastics' aging influences contaminant adsorption. Microplastics were aged through an accelerated weathering process using ultraviolet exposure with or without hydrogen peroxide. Adsorption isotherms were conducted for both contaminants on pristine and aged microplastics. The adsorption of organic contaminants was higher on aged microplastics than on pristine ones, with methylene blue having the highest affinity increase with aging at 4.7-fold and phenanthrene having a 1.9-fold increase compared to the pristine particles. To understand the mechanisms involved with higher adsorption of contaminants by aged microplastics, changes in the specific surface area and surface chemistry of aged microplastics were characterized by Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy, zeta potential, X-ray tomography, and Brunauer-Emmett-Teller krypton adsorption analyses. The results of this study show that oxidation of microplastics can enhance the adsorption of organic contaminants, which may increase their role as vectors of contaminants in the aquatic food chain.

Similar toxicity mechanisms between graphene oxide and oxidized multi-walled carbon nanotubes in Microcystis aeruginosa.

In photosynthetic microorganisms, the toxicity of carbon nanomaterials (CNMs) is typically characterized by a decrease in growth, viability, photosynthesis, as well as the induction of oxidative stress. However, it is currently unclear how the shape of the carbon structure in CNMs, such as in the 1-dimensional carbon nanotubes (CNTs) compared to the two-dimensional graphene oxide (GO), affects the way they interact with cells. In this study, the effects of GO and oxidized multi-walled CNTs were compared in the cyanobacterium Microcystis aeruginosa to determine the similarities or differences in how the two CNMs interact with and induce toxicity to cyanobacteria. Using change in Chlorophyll a concentrations, the effective concentrations inducing 50% inhibition (EC50) at 96 h are found to be 11.1 µg/mL and 7.38 µg/mL for GO and CNTs, respectively. The EC50 of the two CNMs were not found to be statistically different. Changes in fluorescein diacetate and 2',7'-dichlorodihydrofluorescein diacetate fluorescence, measured at the EC50 concentrations, suggest a decrease in esterase enzyme activity but no oxidative stress. Scanning and transmission electron microscopy imaging did not show extensive membrane damage in cells exposed to GO or CNTs. Altogether, the decrease in metabolic activity and photosynthetic activity without oxidative stress or membrane damage support the hypothesis that both GO and CNTs induced indirect toxicity through physical mechanisms associated with light shading and cell aggregation. This indirect toxicity explains why the intrinsic differences in shape, size, and surface properties between CNTs and GO did not result in differences in how they induce toxicity to cyanobacteria.

Portable point-of-use photoelectrocatalytic device provides rapid water disinfection.

Portable water purification devices are needed to provide safe drinking water in rural communities, developing communities with low quality centralized water distribution, and military or recreational applications. Filtration, ultraviolet light, or chemical additives provide a spectrum of alternatives to remove pathogens from water. For the first time, we design, fabricate and demonstrate the performance of a small portable photoelectric point-of-use device, and document its performance on pathogen inactivation. The device utilizes a commercial teacup from which TiO2 nanotube photoanodes were produced in-situ and, with a small rechargeable battery powered 365 nm light emitting diode, was able to achieve 5-log inactivation of Escherichia coli in 10 s and 2.6-log of Legionella in 60 s of treatment in model water samples. Treatment of natural water achieved a 1-log bacteria inactivation after 30 s due to matrix effects. The electro-photocatalytic disinfection reactor in a kup (e-DRINK) can provide a feasible and affordable solution to ensure access to clean water. More broadly, this work demonstrates the potential for illumination to improve the efficiency of electrocatalytic surfaces.

Pore wetting in membrane distillation treatment of municipal wastewater desalination brine and its mitigation by foam fractionation.

Reverse Osmosis (RO) desalination is an important step of wastewater reuse as it can remove salts and trace contaminants. However, RO also generates high salinity brines that need to be dealt with. Membrane distillation (MD), a process largely unaffected by salinity, provides a way to treat desalination brines up to high water recovery and has been proposed as a solution for RO brine management. However, pore wetting of membranes in MD is one of the major hurdles that prevents its implementation in wastewater treatment systems, as amphiphilic organic compounds present in wastewater can lead to pore wetting and loss of selectivity over time. The objective of this study was to identify a pre-treatment strategy to prevent wetting in MD treatment of municipal wastewater RO brines. We compared three pre-treatments with different separation or removal mechanisms: foam fractionation, advanced oxidation, and ultrafiltration. We evaluated membrane wetting by measuring the change in conductivity in the distillate and identified the most effective pre-treatment to prevent wetting in MD. The results show that wetting is prevented by pre-treating the brine with foam fractionation. The effectiveness of foam fractionation as a wetting control strategy was confirmed for a high wetting propensity synthetic water using sodium dodecyl sulfate as a model wetting compound. Finally, the effect of the pre-treatments on the desalination brine was evaluated to understand the nature of the compounds removed by each treatment. The results of this study will help implement MD as a treatment process for desalination brines in municipal wastewater reuse systems.

Scaling Resistance in Nanophotonics-Enabled Solar Membrane Distillation.

This study compares the scaling behavior of membrane distillation (MD) with that of nanophotonics-enabled solar membrane distillation (NESMD). Previous research has shown that NESMD, due to its localized surface heating driven by photothermal membrane coatings, is an energy-efficient system for off-grid desalination; however, concerns remained regarding the scaling behavior of self-heating surfaces. In this work, bench-scale experiments were performed, using model brackish water, to compare the scaling propensity of NESMD with MD. The results showed NESMD to be highly resistant to scaling; a three times higher salt concentration factor (c/c0) was achieved in NESMD compared to MD without any decline in flux. Analyses of the scaling layer on NESMD membranes revealed that salt deposition was 1/4 of that observed for MD. Scaling resistance in NESMD is attributed to its lower operating temperature, which increases the solubility of common scalants and decreases salt precipitation rates. Precipitation kinetics measurements revealed an order of magnitude faster precipitation under heated conditions (62 °C, k = 8.7 × 10-2 s-1) compared to ambient temperature (22 °C, k = 7.1 × 10-3 s-1). These results demonstrate a distinct advantage of NESMD over MD for the treatment of high scaling potential water, where scaling is a barrier to high water recovery.

Graphene/polymer nanocomposite degradation by ultraviolet light: The effects of graphene nanofillers and their potential for release.

The ultraviolet (UV)-induced degradation of graphene/polymer nanocomposites was investigated in this study. Specifically, the effect of few-layer graphene nanofillers on the degradation of a thermoplastic polyurethane (TPU) and the release potential of graphene from the degraded nanocomposite surfaces were assessed. Graphene/TPU (G/TPU) nanocomposites and neat TPU were UV-exposed under both dry and humid conditions in the NIST SPHERE, a precisely controlled, high intensity UV-weathering device. Neat TPU and G/TPU were characterized over the time course of UV exposure using color measurements and infrared spectroscopy, for appearance and chemical changes, respectively. Changes in thickness and surface morphology were obtained with scanning electron microscopy. A new fluorescence quenching measurement approach was developed to identify graphene sheets at the nanocomposite surface, which was supported by contact angle measurements. The potential for graphene release from the nanocomposite surface was evaluated using a tape-lift method followed by microscopy of any particles present on the tape. The findings suggest that graphene improves the service life of TPU with respect to UV exposure, but that graphene becomes exposed at the nanocomposite surface over time, which may potentially lead to its release when exposed to small mechanical forces or upon contact with other materials.

Structure-Property-Toxicity Relationships of Graphene Oxide: Role of Surface Chemistry on the Mechanisms of Interaction with Bacteria.

Graphene oxide (GO) is an antimicrobial agent with tunable surface chemistry. To identify the physicochemical determinants of GO's antimicrobial activity, we generated different modified Hummer's GO materials thermally annealed at 200, 500, or 800 °C (TGO200, TGO500, and TGO800, respectively) to modify the surface oxygen groups on the material. Plating assays show that as-received GO (ARGO) and TGO200, TGO500, and TGO800 reduce Escherichia coli viability by 50% (EC50) at 183, 143, 127, and 86 µg/mL, respectively, indicating higher bacterial toxicity as ARGO is reduced. To uncover the toxicity mechanism of GO, fluorescent dye-based assays were used to measure oxidative stress at the EC50. ARGO showed an increase in intracellular reactive oxygen species, measured as an increase in 2',7'-dichlorodihydrofluorescein diacetate fluorescence, whereas TGO500 and TGO800 induced an increase in the fluorescence of fluorescein diacetate (FDA) by 30 and 42%, suggesting a decrease in cell permeability. Because of a possible wrapping mechanism, plating assays after post-exposure sonication were performed to explain TGO's low oxidative response and high FDA levels. Results show no difference in colony-forming units, indicating that inhibition of cell growth is a result of the adsorption of bacterial cells on the GO material. By comparing different GO samples at their EC50, this study reveals that reduction of GO alters both the mechanisms of cellular interaction and the degree of toxicity to bacteria.

Development of anti-biofouling feed spacers to improve performance of reverse osmosis modules.

This study investigates the biofouling resistance of modified reverse osmosis (RO) feed spacers. Control spacers (made of polypropylene) were functionalized with a biocidal coating (silver), hydrophilic (SiO2 nanoparticles) or superhydrophobic (TMPSi-TiO2 nanoparticles) anti-adhesive coatings, or a hybrid hydrophilic-biocidal coating (graphene oxide). Performance was measured by adhesion assays, viability tests, and permeate flow decline in a bench scale RO system. The control spacers proved to be one of the better performing materials based on bacterial deposition and dynamic RO fouling experiments. The good anti-adhesive properties of the control can be explained by its near ideal surface free energy (SFE). The only surface modification that significantly reduced biofouling compared to the control was the biocidal silver coating, which outperformed the other spacers by all measured indicators. Therefore, future efforts to improve spacer materials for biofouling control should focus on engineering biocidal coatings, rather than anti-adhesive ones.

Finding the conditions for the beneficial use of ZnO nanoparticles towards plants-A review.

Zinc oxide nanoparticles (ZnO NPs) have a wide range of applications in cosmetics, electrical, and optical industries. The wide range of applications of ZnO NPs, especially in personal care products, suggest they can reach major environmental matrices causing unforeseen effects. Recent literature has shown conflicting findings regarding the beneficial or detrimental effects of ZnO NPs towards terrestrial biota. In this review we carried out a comprehensive survey about beneficial, as well as detrimental aspects, of the ZnO NPs exposure toward various terrestrial plants. A careful scrutiny of the literature indicates that at low concentrations (about 50 mg/kg), ZnO NPs have beneficial effects on plants. Conversely, at concentrations above 500 mg/kg they may have detrimental effects, unless there is a deficiency of Zn in the growing medium. This review also remarks the critical role of the biotic and abiotic factors that may elevate or ameliorate the impact of ZnO NPs in terrestrial plants.

Modulation of CuO nanoparticles toxicity to green pea (Pisum sativum Fabaceae) by the phytohormone indole-3-acetic acid.

The response of plants to copper oxide nanoparticles (nano-CuO) in presence of exogenous phytohormones is unknown. In this study, green pea (Pisum sativum) plants were cultivated to full maturity in soil amended with nano-CuO (10-100nm, 74.3% Cu), bulk-CuO (bCuO, 100-10,000nm, 79.7% Cu), and CuCl2 at 50 and 100mg/kg and indole-3-acetic acid (IAA) at 10 and 100µM. Results showed that IAA at 10 and 100µM, averaged over all Cu treatments, reduced the number of plants by ~23% and ~34%, respectively. IAA at 10µM, nano-CuO at 50mg/kg, b-CuO at 50mg/kg, and CuCl2 at 100mg/kg reduced pod biomass by about 50%. Although some combinations of IAA, mainly at 100µM, with the Cu compounds altered nutrient accumulation in tissues, none of them affected pod elements. Conversely, without IAA, nano-CuO at 50mg/kg, increased pod Fe and Ni by 258% and 325%, respectively, while bCuO at 100mg/kg increased pod Ni by 275%, compared with control. With IAA at 10µM, nano-CuO (100mg/kg) and bCuO (50mg/kg) increased stem Cu by ~84% and ~78%. When IAA increased to 100µM, nano-CuO and bCuO reduced stem Ca by 32% and 37%, and Mg by ~35%. Results suggest that both the nano-CuO and bCuO could improve the nutritional quality of pea pods, while exogenous IAA combined with Cu-based compounds could impact green pea production since these treatments reduced the number of plants and pod biomass.

Comparison of the effects of commercial coated and uncoated ZnO nanomaterials and Zn compounds in kidney bean (Phaseolus vulgaris) plants.

Bean (Phaseolus vulgaris) plants were grown for 45 days in soil amended with either uncoated (Z-COTE®) and coated (Z-COTE HP1®) ZnO nanomaterials (NMs), bulk ZnO and ZnCl2, at 0-500mg/kg. At harvest, growth parameters, chlorophyll, and essential elements were determined. None of the treatments affected germination and pod production, and only ZnCl2 at 250 and 500mg/kg reduced relative chlorophyll content by 34% and 46%, respectively. While Z-COTE® did not produce phenotypic changes, Z-COTE HP1®, at all concentrations, increased root length (∼44%) and leaf length (∼13%) compared with control. Bulk ZnO reduced root length (53%) at 62.5mg/kg and ZnCl2 reduced leaf length (16%) at 125mg/kg. Z-COTE®, at 125mg/kg, increased Zn by 203%, 139%, and 76% in nodules, stems, and leaves, respectively; while at the same concentration, Z-COTE HP1® increased Zn by 89%, 97%, and 103% in roots, stems, and leaves, respectively. At 125mg/kg, Z-COTE HP1® increased root S (65%) and Mg (65%), while Z-COTE® increased stem B (122%) and Mn (73%). Bulk ZnO and ZnCl2 imposed more toxicity to kidney bean than the NMs, since they reduced root and leaf elongation, respectively, and the concentration of several essential elements in tissues.

Surface coating changes the physiological and biochemical impacts of nano-TiO2 in basil (Ocimum basilicum) plants.

Little is known about the effects of surface coating on the interaction of engineered nanoparticles (ENPs) with plants. In this study, basil (Ocimum basilicum) was cultivated for 65 days in soil amended with unmodified, hydrophobic (coated with aluminum oxide and dimethicone), and hydrophilic (coated with aluminum oxide and glycerol) titanium dioxide nanoparticles (nano-TiO2) at 125, 250, 500, and 750 mg nano-TiO2 kg-1 soil. ICP-OES/MS, SPAD meter, and UV/Vis spectrometry were used to determine Ti and essential elements in tissues, relative chlorophyll content, carbohydrates, and antioxidant response, respectively. Compared with control, hydrophobic and hydrophilic nano-TiO2 significantly reduced seed germination by 41% and 59%, respectively, while unmodified and hydrophobic nano-TiO2 significantly decreased shoot biomass by 31% and 37%, respectively (p ≤ 0.05). Roots exposed to hydrophobic particles at 750 mg kg-1 had 87% and 40% more Ti than the pristine and hydrophilic nano-TiO2; however, no differences were found in shoots. The three types of particles affected the homeostasis of essential elements: at 500 mg kg-1, unmodified particles increased Cu (104%) and Fe (90%); hydrophilic increased Fe (90%); while hydrophobic increased Mn (339%) but reduced Ca (71%), Cu (58%), and P (40%). However, only hydrophobic particles significantly reduced root elongation by 53%. Unmodified, hydrophobic, and hydrophilic particles significantly reduced total sugar by 39%, 38%, and 66%, respectively, compared with control. Moreover, unmodified particles significantly decreased reducing sugar (34%), while hydrophobic particles significantly reduced starch (35%). Although the three particles affected basil plants, coated particles impacted the most its nutritional quality, since they altered more essential elements, starch, and reducing sugars.

Soil organic matter influences cerium translocation and physiological processes in kidney bean plants exposed to cerium oxide nanoparticles.

Soil organic matter plays a major role in determining the fate of the engineered nanomaterials (ENMs) in the soil matrix and effects on the residing plants. In this study, kidney bean plants were grown in soils varying in organic matter content and amended with 0-500mg/kg cerium oxide nanoparticles (nano-CeO2) under greenhouse condition. After 52days of exposure, cerium accumulation in tissues, plant growth and physiological parameters including photosynthetic pigments (chlorophylls and carotenoids), net photosynthesis rate, transpiration rate, and stomatal conductance were recorded. Additionally, catalase and ascorbate peroxidase activities were measured to evaluate oxidative stress in the tissues. The translocation factor of cerium in the nano-CeO2 exposed plants grown in organic matter enriched soil (OMES) was twice as the plants grown in low organic matter soil (LOMS). Although the leaf cover area increased by 65-111% with increasing nano-CeO2 concentration in LOMS, the effect on the physiological processes were inconsequential. In OMES leaves, exposure to 62.5-250mg/kg nano-CeO2 led to an enhancement in the transpiration rate and stomatal conductance, but to a simultaneous decrease in carotenoid contents by 25-28%. Chlorophyll a in the OMES leaves also decreased by 27 and 18% on exposure to 125 and 250mg/kg nano-CeO2. In addition, catalase activity increased in LOMS stems, and ascorbate peroxidase increased in OMES leaves of nano-CeO2 exposed plants, with respect to control. Thus, this study provides clear evidence that the properties of the complex soil matrix play decisive roles in determining the fate, bioavailability, and biological transport of ENMs in the environment.

Copper nanoparticles/compounds impact agronomic and physiological parameters in cilantro (Coriandrum sativum).

The environmental impacts of Cu-based nanoparticles (NPs) are not well understood. In this study, cilantro (Coriandrum sativum) was germinated and grown in commercial potting mix soil amended with Cu(OH)2 (Kocide and CuPRO), nano-copper (nCu), micro-copper (µCu), nano-copper oxide (nCuO), micro-copper oxide (µCuO) and ionic Cu (CuCl2) at either 20 or 80 mg Cu per kg. In addition to seed germination and plant elongation, relative chlorophyll content and micro and macroelement concentrations were determined. At both concentrations, only nCuO, µCuO, and ionic Cu, showed statistically significant reductions in germination. Although compared with control, the relative germination was reduced by ∼50% with nCuO at both concentrations, and by ∼40% with µCuO, also at both concentrations, the difference among compounds was not statistically significant. Exposure to µCuO at both concentrations and nCu at 80 mg kg(-1) significantly reduced (p≤ 0.05) shoot elongation by 11% and 12.4%, respectively, compared with control. Only µCuO at 20 mg kg(-1) significantly reduced (26%) the relative chlorophyll content, compared with control. None of the treatments increased root Cu, but all of them, except µCuO at 20 mg kg(-1), significantly increased shoot Cu (p≤ 0.05). Micro and macro elements B, Zn, Mn, Ca, Mg, P, and S were significantly reduced in shoots (p≤ 0.05). Similar results were observed in roots. These results showed that Cu-based NPs/compounds depress nutrient element accumulation in cilantro, which could impact human nutrition.

Physiological and biochemical response of soil-grown barley (Hordeum vulgare L.) to cerium oxide nanoparticles.

A soil microcosm study was performed to examine the impacts of cerium oxide nanoparticles (nCeO2) on the physiology, productivity, and macromolecular composition of barley (Hordeum vulgare L.). The plants were cultivated in soil treated with nCeO2 at 0, 125, 250, and 500 mg kg(-1) (control, nCeO2-L, nCeO2-M, and nCeO2-H, respectively). Accumulation of Ce in leaves/grains and its effects on plant stress and nutrient loading were analyzed. The data revealed that nCeO2-H promoted plant development resulting in 331 % increase in shoot biomass compared with the control. nCeO2 treatment modified the stress levels in leaves without apparent signs of toxicity. However, plants exposed to nCeO2-H treatment did not form grains. Compared with control, nCeO2-M enhanced grain Ce accumulation by as much as 294 % which was accompanied by remarkable increases in P, K, Ca, Mg, S, Fe, Zn, Cu, and Al. Likewise, nCeO2-M enhanced the methionine, aspartic acid, threonine, tyrosine, arginine, and linolenic acid contents in the grains by up to 617, 31, 58, 141, 378, and 2.47 % respectively, compared with the rest of the treatments. The findings illustrate the beneficial and harmful effects of nanoceria in barley.