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Heterogeneous catalysis holds great promise for oxidizing or reducing a range of pollutants in water. A well-recognized, but understudied, barrier to implementing catalytic treatment centers around fouling or aging over time of the catalyst surfaces. To better understand how to study catalyst fouling or aging, we selected a representative bimetallic catalyst (Pd-In supported on Al(2)O(3)), which holds promise to reduce nitrate to innocuous nitrogen gas by-products upon hydrogen addition, and six model solutions (deionized water, tap water, sodium hypochlorite, sodium borohydride, acetic acid, and sodium sulfide). Our novel aging experimental apparatus permitted single-passage of each model solution, separately, though a small packed bed reactor containing replicate bimetallic catalyst “beds” that could be sacrificed weekly for off-line characterization to quantify impacts of fouling or aging. The composition of the model solutions led to the following gradual changes in surface composition, morphology, or catalytic reactivity: (i) formation of passivating species, (ii) decreased catalytic sites due to metal leaching under acid conditions or sulfide poisoning, (iii) dissolution and/or transformation of indium, (iv) formation of new catalytic sites by the introduction of an additional metallic element, and (v) oxidative etching. The model solution water chemistry (solutes, Eh, pH) captured a wide range of conditions likely to be encountered in potable or industrial water treatment. Aging-induced changes altered catalytic activity and provided insights into potential strategies to improve long-term catalyst operations for water treatment.

Nanobiotechnology approaches to engineering crops with enhanced stress tolerance may be a safe and sustainable strategy to increase crop yield. Under stress conditions, cellular redox homeostasis is disturbed, resulting in the over-accumulation of reactive oxygen species (ROS) that damage biomolecules (lipids, proteins and DNA) and inhibit crop growth and yield. Delivering ROS-scavenging nanomaterials to plants has been shown to alleviate abiotic stress. Here we review the current state of knowledge of using ROS-scavenging nanomaterials to enhance plant stress tolerance. When present below a threshold level, ROS can mediate redox signalling and defence pathways that foster plant acclimatization against stress. We find that ROS-triggering nanomaterials, such as nanoparticulate silver and copper oxide, have the potential to be judiciously applied to crop species to stimulate the defence system, prime stress responses and subsequently increase the stress resistance of crops.

Verticillium wilt, caused by Verticillium dahliae, is one of the major diseases of eggplants. Nanoparticles (NPs) of CuO, Mn2O3, and ZnO were sprayed alone onto leaves of young eggplants and in different combinations and rates, and then seedlings were transplanted into soil infested with V. dahliae in the greenhouse and field between 2015 and 2018. All combinations of NPs were consistently less effective than CuO NPs applied alone at 500 µg/ml at increasing disease suppression, biomass, and fruit yield. CuO NPs were associated with an increase in fruit yield (17 and 33% increase) and disease suppression (28 and 22% reduction) in 2016 and 2017, respectively, when compared with untreated controls. However, this effect was negated in the greenhouse and field experiments when CuO NPs were combined with Mn2O3. Combining NPs of CuO with ZnO resulted in variable effects; amendments increased growth and suppressed disease in greenhouse experiments, but results were mixed in the field. Leaf tissue analyses from the greenhouse experiments showed that Cu concentration in leaves was reduced when CuO NPs were combined with other NPs, even when application rates were the same amount. A simple competition for entry sites may explain why combinations of CuO NPs and Mn2O3 NPs reduced efficacy but does not explain the lack of inhibition between Cu and Zn. NPs of CuO performed better than their larger bulk equivalent, and studies on application rate found 500 µg/ml was optimal. No phytotoxicity, as determined, by leaf burning, necrotic spots, or dead apical buds was noted even at the highest combined rates of 1,500 µg/ml.

Plant response to microelements exposure can be modulated based on particle size. However, studies are lacking on the roles of particle size and specific microelements in mixed exposure systems designed for plant nutrition, rather than toxicology. Here, an addition-omission strategy was used to address particle-size and element-specific effects in soybean exposed to a mixture of nano and bulk scale oxide particles of Zn (2 mg Zn/kg), Cu (1 mg Cu/kg) and B (1 mg B/kg) in soil. Compared to the control, mixtures of oxide particles of both sizes significantly (p

Bulk Cu compounds such as Cu(OH)2 are extensively used as pesticides in agriculture. Recent investigations suggest that Cu-based nanomaterials can replace bulk materials reducing the environmental impacts of Cu. In this study, stress responses of alfalfa (Medicago sativa L.) seedlings to Cu(OH)2 nanoparticle or compounds were evaluated. Seeds were immersed in suspension/solutions of a Cu(OH)2 nanoform, bulk Cu(OH)2, CuSO4, and Cu(NO3)2 at 25 and 75 mg/L. Six days later, the germination, seedling growth, and the physiological and biochemical responses of sprouts were evaluated. All Cu treatments significantly reduced root elongation (average = 63%). The ionic compounds at 25 and 75 mg/L caused a reduction in all elements analyzed (Ca, K, Mg, P, Zn, and Mn), excepting for S, Fe and Mo. The bulk-Cu(OH)2 treatment reduced K (48%) and P (52%) at 75 mg/L, but increased Zn at 25 (18%) and 75 (21%) mg/L. The nano-Cu(OH)2 reduced K (46%) and P (48%) at 75 mg/L, and also P (37%) at 25 mg/L, compared with control. Confocal microscopy images showed that all Cu compounds, at 75 mg/L, significantly reduced nitric oxide, concurring with the reduction in root growth. Nano Cu(OH)2 at 25 mg/L upregulated the expression of the Cu/Zn superoxide dismutase gene (1.92-fold), while ionic treatments at 75 mg/L upregulated (∼10-fold) metallothionein (MT) transcripts. Results demonstrated that nano and bulk Cu(OH)2 compounds caused less physiological impairments in comparison to the ionic ones in alfalfa seedlings.

Given the known presence of SARS-Cov-2 in wastewater, stemming disease spread in global regions where untreated effluent in the environment is common will experience additional pressure. Though development and preliminary trials of a vaccine against SARS-CoV-2 have been launched in several countries, rapid and effective alternative tools for the timely detection and remediation of SARS-CoV-2 in wastewater, especially in the developing countries, is of paramount importance. Here, we propose a promising, non-invasive technique for early prediction and targeted detection of SARS-CoV-2 to prevent current and future outbreaks. Thus, a combination of nanotechnology with wastewater-based epidemiology and artificial intelligence could be deployed for community-level wastewater virus detection and remediation.

This work presents the most extensive proteomic description of Arabidopsis thaliana in the knowledge of its responses to BPA and TiO2-NPs. Previous studies have reported that nanoparticles (NPs) and Bisphenol A (BPA) are toxic to the environment. However, the jointed toxicity is not yet well understood. This study was aimed to investigate the combined toxicity of BPA and TiO2-NPs to plants. Model plant Arabidopsis thaliana was selected as the target plant. The seedlings were randomly separated into 5 groups and treated with BPA (1000, 100, 10 and 0 µg/kg) and TiO2-NPs (100, 10, 1 and 0 mg/kg). The plant height, biomass and root length indicated no significant toxicity of low concentration of BPA and TiO2-NPs to the growth. In the results of comparative proteomics, both positive and negative effects were observed in root growth, plant development and energy metabolism, et.al, according to GO and KEGG analysis.

Rutile titanium dioxide nanoparticles (nTiO2) were weathered in field soil at 0, 100, 200, and 400 mg Ti/kg soil for four months. Two types of nTiO2 with different surface coatings (hydrophilic and hydrophobic), uncoated nTiO2 (pristine), and the untreated control were included. Thereafter, carrot seeds (Daucus carota L.) were sown in those soils and grown in a growth chamber for 115 days until full maturity. A comparison was made between this and our previous unaged study, where carrots were treated in the same way in soil with freshly amended nTiO2. The responses of plants depended on the nTiO2 surface coating and concentration. The aged hydrophobic and hydrophilic-coated nTiO2 induced more positive effects on plant development at 400 and 100 mg Ti/kg soil, respectively, compared with control and pristine treatments. Taproot and leaf fresh biomass and plant height were improved by up to 64%, 40%, and 40% compared with control, respectively. Meanwhile, nutrient elements such as Fe in leaves, Mg in taproots, and Ca, Zn, and K in roots were enhanced by up to 66%, 64%, 41, 143% and 46%, respectively. However, the contents of sugar, starch, and some other metal elements in taproots were negatively affected, which may compromise their nutritional quality. Taken together, the overall growth of carrots was benefited by the aged nTiO2 depending on coating and concentration. The aging process served as a potential sustainable strategy to alleviate the phytotoxicity of unweathered nanoparticles.

The recent application of nano copper (Cu) compounds in the agrosystem has shown potential to improve the physiological performance and agronomical parameters of crops. We grew alfalfa (Medicago sativa) in potting mix amended with bulk, nano, and ionic Cu compounds at 80 and 280 mg Cu/kg; then, we evaluated plant performance at physiological and molecular levels. Plants treated with bulk/nano Cu presented better agronomical responses. The P and S content was reduced in bulk and ionic Cu-exposed plants, compared to controls (p ≤ .05). All Cu forms increased the content of Fe and Zn in roots and Fe in leaves, compared to controls (p ≤ .05). Leaf-superoxide dismutase expression was augmented ~27-fold and rubisco mRNA was unaffected in bulk/nano Cu-treated plants, compared to controls (p ≤ .05). Bulk/nano Cu incremented the relative abundance of microorganisms involved in the elemental uptake. These results indicate that nano Cu improved the physiology of alfalfa and can be considered as potential nanofertilizers.

Little information is available on the interaction of CuO nanoparticles (nCuO) with tuberous roots. In this study, Beauregard-14 (B-14, low lignin) and Covington (COV, high lignin) sweetpotato varieties were cultivated until maturity in soil amended with nCuO, bulk copper oxide (bCuO) and CuCl2 at 25–125 mg/kg. The Cu treatments had no significant influence on chlorophyll content. Gas exchange parameters were not affected in B-14. In COV, however, at 125 mg/kg treatments, bCuO reduced the intercellular CO2 (11%), while CuCl2 increased it by 7%, compared with control (p ≤ 0.035). At 25 mg/kg nCuO increased the length of COV roots (20.7 ± 2.0 cm vs. 14.6 ± 0.8 cm, p ≤ 0.05). In periderm of B-14, nCuO, at 125 mg/kg, increased Mg by 232%, while the equivalent concentration of CuCl2 reduced P by 410%, compared with control (p ≤ 0.05). The data suggest the potential application of nCuO as nanofertilizer for sweetpotato storage root production.

In this study, we report a facile method for the preparation of sulfonic acid functionalized carbonaceous adsorbent (TW-SO3H) from tea leaves. The adsorbent was characterized using Fourier-transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy-dispersive X-ray Spectroscopy (EDS), Thermogravimetric analysis (TGA), Raman Spectroscopy and Zeta potential measurements. The adsorbent was utilized for the adsorptive removal of antibiotics such as sulfamethoxazole (SMX) and endocrine disrupting chemicals such as bisphenol A (BPA) from water. The calculated adsorption capacities of TW-SO3H were 258.87 mg/g and 236.80 mg/g towards the removal of SMX and BPA, respectively at 25 °C. The new adsorbent has the ability to form electrostatic interaction and π–π stacking that allow the efficient adsorption of SMX and BPA. The Langmuir and Temkin isotherm models best fit the experimental data for the BPA and SMX adsorption processes, respectively. The results of the kinetic studies showed that the removal of SMX and BPA by TW-SO3H followed pseudo-second order kinetic model. A thermodynamic study indicated that the adsorption process was spontaneous as well as exothermic. The adsorbent was facilely regenerated and recycled for three cycles with a nominal loss of adsorption capacity. Our results indicated that TW-SO3H could be utilized as a promising adsorbent for the rapid removal of SMX and BPA from the contaminated water.

This study explored the use of foliar sprays with nanoparticles (NP) of B, CuO, MnO, SiO, TiO, and ZnO to protect watermelon against Fusarium wilt. Leaves of young watermelon plants were sprayed (1 to 2 ml per plant) with NP suspensions (500 to 1,000 µg/ml) and were planted in potting mix infested with Fusarium oxysporum f. sp. niveum. In five of eight greenhouse experiments, CuO NP suppressed disease and, in six of eight experiments, CuO NP increased biomass or yield more than in untreated controls or other tested NP. More root Cu was detected in CuO NP-treated plants than other treatments (P = 0.015). In Griswold, CT, plants treated with CuO NP yielded 39% more fruit than untreated controls. In Hamden, CT, treatment with CuO NP produced 53% more fruit when compared with controls (P = 0.02) and was superior to other Cu fungicides. Gene expression in watermelon roots revealed strong upregulation of polyphenol oxidase (PPO) and PR1 genes when CuO NP and F. oxysporum f. sp. niveum were both present. Enzymatic assays for PPO supported the gene expression results. CuO NP may serve as a highly effective delivery agent for this micronutrient to suppress disease.

Titanium dioxide nanoparticles (NPs) have become widely used and studied in industry, cosmetics, and water treatment; however, due to their surface charge and composition, uncoated nanoparticles often aggregate and settle in a solution. This leads to loss of function and suspension, abandoning the NPs' properties that make them ideal for many applications. Loss of NP suspension can also complicate analysis of solutions containing nanoparticles. Therefore, titanium dioxide nanoparticles are good candidates for surface coatings that enable hydrophilic interactions and improved suspension. Many coating processes require complex synthesis methods and begin with titanium dioxide precursors rather than with already synthesized nanoparticles. The method presented herein examines additive processes that may increase suspension capabilities and inhibit loss of function through aggregation of large nanoparticles (50 ± 25 nm). Nineteen chelating organic compounds were tested via a 1, 2, or 3 equivalent additions to pristine, unmodified TiO2 nanoparticles in solution. Furthermore, ligands that showed the best chelating behavior were diluted and the pH was modified to understand pH dependent behavior. Dynamic light scattering and electrophoretic light scattering were used in the study of the chemical behavior of the modified TiO2 nanoparticles. Results show that nanoparticles interacting with dimethylethanolamine, dimercaptosuccinic acid, sodium citrate, dimethylglyoxime, and oxalic acid showed improved ζ-potential at a pH of 5. Physico-chemical processes are discussed in the understanding of these results.

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.

A series of novel zeolitic imidazolate framework (ZIF) decorated superparamagnetic graphene oxide hybrid nanoadsorbents were synthesized, characterized, and tested for their As(III) adsorbed amount in simulated drinking water. The three composite nanomaterials are based each on three isostructural and water stable ZIFs, (C-1 based on ZIF-8, C-2 based on ZIF-67, and C-3 based on ZIF-Zn/Co). The composite nanomaterials and there parent materials were characterized through pXRD, TEM, FTIR, BET and magnetometry methods (SQUID), and were tested as adsorbents in a representative drinking water matrix containing arsenite (As(III)) at an initial trace concentration (realistic in some natural drinking water sources) of 35 µg/L. The nanoadsorbents were magnetically captured and removed after adsorption in batch conditions. Out of the three composites, C-2 shows the highest As(III) adsorbed amount at an initial concentration of 35 µg/L (q0) of 202 µg/g, followed by C-3 with 102 µg/g and C-1 with 82 µg/g.

Given increasing use of copper-based nanomaterials, particularly in applications with direct release, it is imperative to understand their human and ecological risks. A comprehensive and systematic approach was used to determine toxicity and fate of several Cu nanoparticles (Cu NPs). When used as pesticides in agriculture, Cu NPs effectively control pests. However, even at low (5–20 mg Cu/plant) doses, there are metabolic effects due to the accumulation of Cu and generation of reactive oxygen species (ROS). Embedded in antifouling paints, Cu NPs are released as dissolved Cu + 2 and in nano- and micron-scale particles. Once released, Cu NPs can rapidly (hours to weeks) oxidize, dissolve, and form CuS and other insoluble Cu compounds, depending on water chemistry (e.g. salinity, alkalinity, organic matter content, presence of sulfide and other complexing ions). More than 95% of Cu released into the environment will enter soil and aquatic sediments, where it may accumulate to potentially toxic levels (> 50–500 μg/L). Toxicity of Cu compounds was generally ranked by high throughput assays as: Cu + 2 > nano Cu(0) > nano Cu(OH) 2 > nano CuO > micron-scale Cu compounds. In addition to ROS generation, Cu NPs can damage DNA plasmids and affect embryo hatching enzymes. Toxic effects are observed at much lower concentrations for aquatic organisms, particularly freshwater daphnids and marine amphipods, than for terrestrial organisms. This knowledge will serve to predict environmental risks, assess impacts, and develop approaches to mitigate harm while promoting beneficial uses of Cu NPs.

Concerns about the environmental safety of metal-based nanoparticles (MNPs) in aquatic ecosystems are increasing. Simultaneously, elevated atmospheric CO 2 levels are a serious problem worldwide, making it possible for the combined exposure of MNPs and elevated CO 2 to the ecosystem. Here we studied the toxicity of n ZnO to goldfish in a water-sediment ecosystem using open-top chambers flushed with ambient (400 ± 10 μL/L) or elevated (600 ± 10 μL/L) CO 2 for 30 days. We measured the content of Zn in suspension and fish, and analyzed physiological and biochemical changes in fish tissues. Results showed that elevated CO 2 increased the Zn content in suspension by reducing the pH value of water and consequently enhanced the bioavailability and toxicity of n ZnO. Elevated CO 2 led to higher accumulation of Zn in fish tissues (increased by 43.3%, 86.4% and 22.5% in liver, brain and muscle, respectively) when compared to ambient. Elevated CO 2 also intensified the oxidative damage to fish induced by n ZnO, resulting in higher ROS intensity, greater contents of MDA and MT and lower GSH content in liver and brain. Our results suggest that more studies in natural ecosystems are needed to better understand the fate and toxicity of nanoparticles in future CO 2 levels.

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.

With increasing use, manufactured nanomaterials (MNMs) may enter soils and impact agriculture. Herein, soybean (Glycine max) was grown in soil amended with either nano-CeO2 (0.1, 0.5, or 1.0gkg-1 soil) or nano-ZnO (0.05, 0.1, or 0.5gkg-1 soil). Leaf chlorosis, necrosis, and photosystem II (PSII) quantum efficiency were monitored during plant growth. Seed protein and protein carbonyl, plus leaf chlorophyll, reactive oxygen species (ROS), lipid peroxidation, and genotoxicity were measured for plants at harvest. Neither PSII quantum efficiency, seed protein, nor protein carbonyl indicated negative MNM effects. However, increased ROS, lipid peroxidation, and visible damage, along with decreased total chlorophyll concentrations, were observed for soybean leaves in the nano-CeO2 treatments. These effects correlated to aboveground leaf, pod, and stem production, and to root nodule N2 fixation potential. Soybeans grown in soil amended with nano-ZnO maintained growth, yield, and N2 fixation potential similarly to the controls, without increased leaf ROS or lipid peroxidation. Leaf damage was observed for the nano-ZnO treatments, and genotoxicity appeared for the highest nano-ZnO treatment, but only for one plant. Total chlorophyll concentrations decreased with increasing leaf Zn concentration, which was attributable to zinc complexes-not nano-ZnO-in the leaves. Overall, nano-ZnO and nano-CeO2 amended to soils differentially triggered aboveground soybean leaf stress and damage. However, the consequences of leaf stress and damage to N2 fixation, plant growth, and yield were only observed for nano-CeO2.

Evidence suggests that CO2 modifies the behavior of nanomaterials. Thus, in a few decades, plants might be exposed to additional stress if atmospheric levels of CO2 and the environmental burden of nanomaterials increase at the current pace. Here, we used a full-size free-air CO2 enrichment (FACE) system in farm fields to investigate the effect of elevated CO2 levels on phytotoxicity and microbial toxicity of nTiO2 (0, 50, and 200 mg kg− 1) in a paddy soil system. Results show that nTiO2 did not induce visible signs of toxicity in rice plants cultivated at the ambient CO2 level (370 μmol mol− 1), but under the high CO2 concentration (570 μmol mol− 1) nTiO2 significantly reduced rice biomass by 17.9% and 22.1% at 50 mg kg− 1 and 200 mg kg− 1, respectively, and grain yield by 20.8% and 44.1% at 50 mg kg− 1 and 200 mg kg− 1, respectively. In addition, at the high CO2 concentration, nTiO2 at 200 mg kg− 1 increased accumulation of Ca, Mg, Mn, P, Zn, and Ti by 22.5%, 16.8%, 29.1%, 7.4%, 15.7% and 8.6%, respectively, but reduced fat and total sugar by 11.2% and 25.5%, respectively, in grains. Such conditions also changed the functional composition of soil microbial communities, alerting specific phyla of bacteria and the diversity and richness of protista. Overall, this study suggests that increases in CO2 levels would modify the effects of nTiO2 on the nutritional quality of crops and function of soil microbial communities, with unknown implications for future economics and human health.

Little is known about the effects of surface modification on the interaction of nanoparticles (NPs) with plants. Tomato (Solanum lycopersicum L.) plants were cultivated in potting soil amended with bare and citric acid coated nanoceria (nCeO2, nCeO2+CA), cerium acetate (CeAc), bulk cerium oxide (bCeO2) and citric acid (CA) at 0–500 mg kg−1. Fruits were collected year-round until the harvesting time (210 days). Results showed that nCeO2+CA at 62.5, 250 and 500 mg kg−1 reduced dry weight by 54, 57, and 64% and total sugar by 84, 78, and 81%. At 62.5, 125, and 500 mg kg−1 nCeO2+CA decreased reducing sugar by 63, 75, and 52%, respectively and at 125 mg kg−1 reduced starch by 78%, compared to control. The bCeO2 at 250 and 500 mg kg−1, increased reducing sugar by 67 and 58%. In addition, when compared to controls, nCeO2 at 500 mg kg−1 reduced B (28%), Fe (78%), Mn (33%), and Ca (59%). At 125 mg kg−1 decreased Al by 24%; while nCeO2+CA at 125 and 500 mg kg−1 increased B by 33%. On the other hand, bCeO2 at 62.5 mg kg−1 increased Ca (267%), but at 250 mg kg−1 reduced Cu (52%), Mn (33%), and Mg (58%). Fruit macromolecules were mainly affected by nCeO2+CA, while nutritional elements by nCeO2; however, all Ce treatments altered, in some way, the nutritional quality of tomato fruit. To our knowledge, this is the first study comparing effects of uncoated and coated nanoceria on tomato fruit quality.

Multiple applications of metal oxide nanoparticles (MONPs) could result in their accumulation in soil, threatening higher terrestrial plants. Several reports have shown the effects of MONPs on plants. In this review, we analyze the most recent reports about the physiological and biochemical responses of plants to stress imposed by MONPs. Findings demonstrate that MONPs may be taken up and accumulated in plant tissues causing adverse or beneficial effects on seed germination, seedling elongation, photosynthesis, antioxidative stress response, agronomic, and yield characteristics. Given the importance of determining the potential risks of MONPs on crops and other terrestrial higher plants, research questions about field long-term conditions, transgenernational phytotoxicity, genotype specific sensitivity, and combined pollution problems should be considered.

Little is known about the interaction of nanoparticles (NPs) with soil constituents and their effects in plants. Boron (B), an essential micronutrient that reduces crop production at both deficiency and excess, has not been investigated with respect to its interaction with cerium oxide NPs (nano-CeO 2 ). Considering conflicting results on the nano-CeO 2 toxicity and protective role as antioxidant, their possible modulation on B toxicity in sunflower ( Helianthus annuus L.) was investigated. Sunflower was cultivated for 30 days in garden pots containing original or B-spiked soil amended with nano-CeO 2 at 0–800 mg kg −1 . At harvest, Ce and B concentrations in tissues, biomass, and activities of stress enzymes in leaves were determined. Results showed that in the original soil, Ce accumulated mainly in roots, with little translocation to stems and leaves, while reduced root Ce was observed in plants from B-spiked soil. In the original soil, higher levels of nano-CeO 2 reduced plant B concentration. Although morphological effects were not visible, changes in biomass and oxidative stress response were observed. Sunflower leaves from B-spiked soil showed visible symptoms of B toxicity, such as necrosis and chlorosis in old leaves, as well as an increase of superoxide dismutase (SOD) activity. However, at high nano-CeO 2 level, SOD activity decreased reaching values similar to that of the control. This study has shown that nano-CeO 2 reduced both the B nutritional status of sunflower in original soil and the B phytotoxicity in B-spiked soil.

Recent investigations show that carbon-based and metal-based engineered nanomaterials (ENMs), components of consumer goods and agricultural products, have the potential to build up in sediments and biosolid-amended agricultural soils. In addition, reports indicate that both carbon-based and metal-based ENMs affect plants differently at the physiological, biochemical, nutritional, and genetic levels. The toxicity threshold is species-dependent and responses to ENMs are driven by a series of factors including the nanomaterial characteristics and environmental conditions. Effects on the growth, physiological and biochemical traits, production and food quality, among others, have been reported. However, a complete understanding of the dynamics of interactions between plants and ENMs is not clear enough yet. This review presents recent publications on the physiological and biochemical effects that commercial carbon-based and metal-based ENMs have in terrestrial plants. This document focuses on crop plants because of their relevance in human nutrition and health. We have summarized the mechanisms of interaction between plants and ENMs as well as identified gaps in knowledge for future investigations.

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.

Hybrid nanocomposites based on Cu-BTC MOF, graphene oxide (GO), carbon nanotubes (CNTs), and Fe3O4 magnetic nanoparticles (MNPs) were developed via a simple green solvothermal method, at which GO and CNT were used as platforms to load nanostructured Cu-BTC MOF and Fe3O4 MNPs. The as-synthesized hybrid nanocomposites were characterized by XRD, SEM, TEM, XPS, IR, Raman, TGA, and BET techniques. XRD measurements show highly crystalline structures for the prepared hybrid nanocomposites. Morphological analyses carried out by SEM and TEM also confirm successful growth of Fe3O4 MNPs and nanoparticulate Cu-BTC MOF over the carbon-based platforms. Chemical, elemental, and TGA analyses verify chemical bonding and successful compositing of the parent materials. Nitrogen isotherms show a cumulative pore volume of 0.360 cm3 g−1 for the hybrid nanocomposite of Fe3O4/Cu-BTC@GO compared to 0.030 cm3 g−1 of the sole Cu-BTC MOF, which suggests potential uses towards small molecule adsorption. We have found that use of GO and CNT substrates (i) diminish the aggregation and increases dispersive forces within the MOFs, (ii) lead to MOFs with different morphology and size, and (iii) result in formation of small pores between the MOF and the platforms. Adsorption capacity of the prepared nanomaterials was examined over methylene blue (MB) as a model organic pollutant. The developed hybrid nanomaterials show enhanced pollutant adsorption capacity compared to that of the parent materials. The improved adsorption capacity is attributed to the synergetic effect of covalent bonding between the parent materials as well as to the unique features of the nanoscale MOF. Overall, these novel materials may be considered as excellent candidates towards a variety of environmental applications such as water remediation.

Ornamental grasses are commonly used in urban landscapes in Utah and the Intermountain West of the United States. The relative salt tolerance of Eragrostis spectabilis (Pursh) Steud. (purple love grass), Miscanthus sinensis Andersson ‘Gracillimus’ (maiden grass), Panicum virgatum L. ‘Northwind’ (switchgrass), and Schizachyrium scoparium (Michx.) Nash (little bluestem) were evaluated in a greenhouse. Plants were irrigated with a nutrient solution at an electrical conductivity (EC) of 1.2 dS·m–1 (control), or saline solution at an EC of 5.0 or 10.0 dS·m–1. At harvest (65 days after the initiation of treatment), P. virgatum and S. scoparium exhibited no foliar salt damage, and E. spectabilis and M. sinensis had minimal foliar salt damage when irrigated with saline solution at an EC of 5.0 dS·m–1. At an EC of 10.0 dS·m–1, P. virgatum and S. scoparium still had no foliar salt damage, but E. spectabilis and M. sinensis displayed slight foliar salt damage, with visual scores greater than 3 (0 = dead; 5 = excellent). Compared with the control, saline solution at an EC of 5.0 and 10.0 dS·m–1 reduced the shoot dry weight of all ornamental grasses by 25% and 46%, respectively. The leaf sodium (Na+) concentration of E. spectabilis, M. sinensis, P. virgatum, and S. scoparium irrigated with saline solution at an EC of 10.0 dS·m–1 increased 14.3, 52.6, 5.3, and 1.7 times, respectively, and the chloride (Cl–) concentration increased by 9.4, 11.1, 2.8, and 2.7 times, respectively. As a result of the salt-induced water deficit, plant height, leaf area, number of inflorescences and tillers, net photosynthesis rate (Pn), stomatal conductance (gS), and transpiration rate of four tested ornamental grasses decreased to some extent. Although high Na+ and Cl– accumulated in the leaf tissue, all ornamental grass species still had a good visual quality, with average visual scores greater than 3. In conclusion, all ornamental grasses showed a very strong tolerance to the salinity levels used in this research.

Drought is a major environmental event affecting crop productivity and nutritional quality, and potentially, human nutrition. This study evaluated drought effects on performance and nutrient acquisition and distribution in sorghum; and whether ZnO nanoparticles (ZnO-NPs) might alleviate such effects. Soil was amended with ZnO-NPs at 1, 3, and 5 mg Zn/kg, and drought was imposed 4 weeks after seed germination by maintaining the soil at 40% of field moisture capacity. Flag leaf and grain head emergence were delayed 6-17 days by drought, but the delays were reduced to 4-5 days by ZnO-NPs. Drought significantly (p 0.05) reduced (76%) grain yield; however, ZnO-NP amendment under drought improved grain (22-183%) yield. Drought inhibited grain nitrogen (N) translocation (57%) and total (root, shoot and grain) N acquisition (22%). However, ZnO-NPs (5 mg/kg) improved (84%) grain N translocation relative to the drought control and restored total N levels to the non-drought condition. Shoot uptake of phosphorus (P) was promoted (39%) by drought, while grain P translocation was inhibited (63%); however, ZnO-NPs lowered total P acquisition under drought by 11-23%. Drought impeded shoot uptake (45%), grain translocation (71%) and total acquisition (41%) of potassium (K). ZnO-NP amendment (5 mg/kg) to drought-affected plants improved total K acquisition (16-30%) and grain K (123%), relative to the drought control. Drought lowered (32%) average grain Zn concentration; however, ZnO-NP amendments improved (94%) grain Zn under drought. This study represents the first evidence of mitigation of drought stress in full-term plants solely by exposure to ZnO-NPs in soil. The ability of ZnO-NPs to accelerate plant development, promote yield, fortify edible grains with critically essential nutrients such as Zn, and improve N acquisition under drought stress has strong implications for increasing cropping systems resilience, sustaining human/animal food/feed and nutrition security, and reducing nutrient losses and environmental pollution associated with N-fertilizers.

Abiotic and biotic stress induce the production of reactive oxygen species (ROS), which limit crop production. Little is known about ROS reduction through the application of exogenous scavengers. In this study, C60 fullerol, a free radical scavenger, was foliar applied to three-week-old cucumber plants (1 or 2 mg/plant) before exposure to copper ions (5 mg/plant). Results showed that C60 fullerols augmented Cu toxicity by increasing the influx of Cu ions into cells (170% and 511%, respectively, for 1 and 2 mg of C60 fullerols/plant). We further use metabolomics and proteomics to investigate the mechanism of plant response to C60 fullerols. Metabolomics revealed that C60 fullerols up-regulated antioxidant metabolites including 3-hydroxyflavone, 1,2,4-benzenetriol, and methyl trans-cinnamate, among others, while it down-regulated cell membrane metabolites (linolenic and palmitoleic acid). Proteomics analysis revealed that C60 fullerols up-regulated chloroplast proteins involved in water photolysis (PSII protein), light-harvesting (CAB), ATP production (ATP synthase), pigment fixation (Mg-PPIX), and electron transport ( Cyt b6f). Chlorophyll fluorescence measurement showed that C60 fullerols significantly accelerated the electron transport rate in leaves (13.3% and 9.4%, respectively, for 1 and 2 mg C60 fullerols/plant). The global view of the metabolic pathway network suggests that C60 fullerols accelerated electron transport rate, which induced ROS overproduction in chloroplast thylakoids. Plant activated antioxidant and defense pathways to protect the cell from ROS damaging. The revealed benefit (enhance electron transport) and risk (alter membrane composition) suggest a cautious use of C60 fullerols for agricultural application.

The Paso del Norte region is characterized by its dynamic industries and active agriculture. Throughout the years, urban and agricultural soils from this region have been exposed to xenobiotics, heavy metals, and excess of hydrocarbons. In this study, samples of urban [domestic workshops (DW)] and agricultural-intended (AI) soils from different sites of Ciudad Juárez, Mexico were evaluated for their fertility, element content, and microbial diversity. Chemical analyses showed that nitrites, nitrates, P, K, Mg, and Mn were predominantly higher in AI soils, compared to DW soils (p ≤ 0.05). The composition of soil microbial communities showed that Proteobacteria phylum was the most abundant in both soils (67%, p ≤ 0.05). In AI soils, Paracoccus denitrificans was reduced (p ≤ 0.05), concurring with an increment in nitrates, while the content of nitrogen was negatively correlated with the rhizobium group (r2 = −0.65, p ≤ 0.05). In DW soils, the Firmicutes phylum represented up to ~25%, and the relative abundance of Proteobacteria strongly correlated with a higher Cu content (r2 = 0.99, p ≤ 0.0001). The monotypic genus Sulfuricurvum was found only in oil-contaminated soil samples. Finally, all samples showed the presence of the recently created phylum Candidatus saccharibacteria. These results describe the productivity parameters of AI soils and its correlation to the microbial diversity, which are very important to understand and potentiate the productivity of soils. The data also suggest that soils impacted with hydrocarbons and metal(oid)s allow the reproduction of microorganisms with the potential to alleviate contaminated sites. Keywords: Heavy metals, Hydrocarbons, Microbial diversity, Macro and micronutrients, Fertility

The production and environmental release of surface-modified titanium dioxide nanoparticles (nTiO2) have increased. Hence, crops may be directly exposed to the nTiO2 in soil. In this study, we grew carrots in soils amended with pristine, hydrophilic and hydrophobic surface-coated nTiO2 at 100, 200, and 400 mg kg-1 until full-plant maturity. The content of Ti in plant secondary roots treated with different nTiO2 at 400 mg kg-1 was in the order of hydrophobic > hydrophilic > pristine treatments, with values of 140.1, 100.5, and 64.3 mg kg-1, respectively. The fresh biomass of the taproot was significantly decreased by all nTiO2 forms at 400 mg kg-1 by up to 56 %, compared to control. Pristine nTiO2 at 100 mg kg-1 enhanced the fresh weight of leaves by 51 % with respect to control. Remarkably, an abnormal increase of taproot splitting was found in plants treated with all nTiO2 forms. In carrots treated with the surface-coated nTiO2, the accumulation of Ca, Mg, Fe, and Zn increased in leaves; but Mg, Mn, and Zn decreased in taproots. These results suggest that future regulation of nTiO2 release into soils should consider its surface coating properties since the phytotoxicity effects depend on nTiO2 outer structure.

In the present study, Zea mays seedlings grown under nano Cu(OH)2 (nCu), bulk Cu(OH)2 (bCu), and ionic CuSO4 (iCu) compound exposure were harvested after six days. The nutritional profile was determined to be significantly disrupted in the roots by 1000 ppm bCu treatment, resulting in a 58.7% reduction in potassium compared to the control. In the shoots, a significant decrease of manganese was observed for 10 and 1000 ppm iCu treatments with 55.7% and 64.2% reductions, respectively. The overall protein content and catalase (CAT) enzymatic activity, however, remained unaffected in either roots or shoots, while an absence of polyphenol oxidase (PPO) activity was observed for all samples. The genetic expression of defense-related genes, metallothionein (MT), CAT, ascorbate peroxidase (APX), and PPO was assessed. The genetic expression of MT was upregulated 50-fold in roots treated with 1000 ppm bCu. There were no significant differences in CAT transcripts among the various treatments, while APX was upregulated 28 and 19-fold in shoots treated with 10 ppm bCu and 10 ppm nCu, respectively. Meanwhile, APX mRNA levels were downregulated five-fold in shoots treated with 1000 ppm iCu. Thus, indicating that the role of APX in plant defense was reinforced in seedlings exposed to low concentration of particulate Cu compounds. Remarkably, no PPO expression was found in any of the treatments and controls, which suggests this enzyme is expressed only under specific external factors or seedlings have an “immature” cascade signaling activation of the PPO system. Taken together, these results show that bCu and nCu treatments at a low concentration do not compromise vital cell machinery but rather elicit the enhancement of defense responses as observed through the increase in APX expression. Furthermore, under optimal concentrations, these Cu treatments show promise in enhancing corn defense responses, which can ultimately lead to increases in future global crop yields.

The expansion of nanotechnology and its ubiquitous applications has fostered unavoidable interaction between engineered nanomaterials (ENMs) and plants. Recent research has shown ambiguous results with regard to the impact of ENMs in plants. On one hand, there are reports that show hazardous effects, while on the other hand, some reports highlight positive effects. This uncertainty whether the ENMs are primarily hazardous or whether they have a potential for propitious impact on plants, has raised questions in the scientific community. In this review, we tried to demystify this ambiguity by citing various exposure studies of different ENMs (nano-Ag, nano-Au, nano-Si, nano-CeO2, nano-TiO2, nano-CuO, nano-ZnO, and CNTs, among others) and their effects on various groups of plant families. After scrutinizing the most recent literature, it seems that the divergence in the research results may be possibly attributed to multiple factors such as ENM properties, plant species, soil dynamics, and soil microbial community. The analysis of the literature also suggests that there is a knowledge gap on the effects of ENMs towards changes in color, texture, shape, and nutritional aspects on ENM exposed plants.

There is lack of information about the effects of foliar applied nanoparticles on fruit quality. In this study, three week-old soil grown cucumber seedlings were foliar-exposed to nCeO2, nCuO, and corresponding bulk counterparts at 50, 100, and 200mg/L. Respective suspensions/solutions were sprayed to experimental units in a volume of 250ml. Net photosynthesis rate (Pn), stomatal conductance (Gs), and transpiration rate (E) were measured 15days after treatment application and in 74day-old plants. Yield, fruit characteristics (size, weight, and firmness), Ce, Cu, and nutritional elements were also measured. Results showed a nano-specific decrement on Pn (22% and 30%) and E (11% and 17%) in seedling leaves exposed to nCeO2 and nCuO at 200mg/L, respectively, compared with control. nCeO2 at 50mg/L, bCeO2 at 200mg/L, and all Cu treatments, except nCuO at 100mg/L, significantly reduced fruit firmness (p≤0.05), compared with control. However, nCuO at 200mg/L and bCuO at 50mg/L significantly increased fruit fresh weight (p≤0.05). At 200mg/L, nCeO2 and bCeO2 reduced fruit Zn by 25%, while nCuO and bCuO reduced fruit Mo by 51% and 44%, respectively, compared with control. This study has shown that when the route of exposure is the foliage, differences in particle size are less significant, compared to root-based exposure. To the authors' knowledge, this is the first report on the effect of foliar application of nCeO2 and nCuO upon yield and nutritional quality of cucumber.

© 2016 American Chemical Society. Engineered nanomaterials (ENMs) are increasingly entering the environment with uncertain consequences including potential ecological effects. Various research communities view differently whether ecotoxicological testing of ENMs should be conducted using environmentally relevant concentrations - where observing outcomes is difficult - versus higher ENM doses, where responses are observable. What exposure conditions are typically used in assessing ENM hazards to populations? What conditions are used to test ecosystem-scale hazards? What is known regarding actual ENMs in the environment, via measurements or modeling simulations? How should exposure conditions, ENM transformation, dose, and body burden be used in interpreting biological and computational findings for assessing risks? These questions were addressed in the context of this critical review. As a result, three main recommendations emerged. First, researchers should improve ecotoxicology of ENMs by choosing test end points, duration, and study conditions - including ENM test concentrations - that align with realistic exposure scenarios. Second, testing should proceed via tiers with iterative feedback that informs experiments at other levels of biological organization. Finally, environmental realism in ENM hazard assessments should involve greater coordination among ENM quantitative analysts, exposure modelers, and ecotoxicologists, across government, industry, and academia.