Influence of CuO Nanoparticle Aspect Ratio and Surface Charge on Disease Suppression in Tomato (Solanum lycopersicum).

Nanoparticles (NPs) have been shown to deliver micronutrients to plants to improve health, increase biomass, and suppress disease. Nanoscale properties such as morphology, size, composition, and surface chemistry have all been shown to impact nanomaterial interactions with plant systems. An organic-ligand-free synthesis method was used to prepare positively charged copper oxide (CuO) nanospikes, negatively charged CuO nanospikes, and negatively charged CuO nanosheets with exposed (001) crystal faces. X-ray photoelectron spectroscopy measurements show that the negative charge correlates to increased surface concentration of O on the NP surface, whereas relatively higher Cu concentrations are observed on the positively charged surfaces. The NPs were then used to treat tomato (Solanum lycopersicum) grown in soil infested with Fusarium oxysporum f. sp. lycopersici under greenhouse conditions. The negatively charged CuO significantly reduced disease progression and increased biomass, while the positively charged NPs and a CuSO4 salt control had little impact on the plants. Self-assembled monolayers were used to mimic the leaf surface to understand the intermolecular interactions between the NPs and the plant leaf; the data demonstrate that NP electrostatics and hydrogen-bonding interactions play an important role in adsorption onto leaf surfaces. These findings have important implications for the tunable design of materials as a strategy for the use of nano-enabled agriculture to increase food production.

Role of Foliar Biointerface Properties and Nanomaterial Chemistry in Controlling Cu Transfer into Wild-Type and Mutant Arabidopsis thaliana Leaf Tissue.

Seven Arabidopsis thaliana mutants with differences in cuticle thickness and stomatal density were foliar exposed to 50 mg L-1 Cu3(PO4)2 nanosheets (NS), CuO NS, CuO nanoparticles, and CuSO4. Three separate fractions of Cu (surface-attached, cuticle, interior leaf) were isolated from the leaf at 0.25, 2, 4, and 8 h. Cu transfer from the surface through the cuticle and into the leaf varied with mutant and particle type. The Cu content on the surface decreased significantly over 8 h but increased in the cuticle. Cu derived from the ionic form had the greatest cuticle concentration, suggesting greater difficulty in moving across this barrier and into the leaf. Leaf Cu in the increased-stomatal mutants was 8.5-44.9% greater than the decreased stomatal mutants, and abscisic acid to close the stomata decreased Cu in the leaf. This demonstrates the importance of nanomaterial entry through the stomata and enables the optimization of materials for nanoenabled agriculture.

Fate, cytotoxicity and cellular metabolomic impact of ingested nanoscale carbon dots using simulated digestion and a triculture small intestinal epithelial model.

Carbon dots (CDs) are a promising material currently being explored in many industrial applications in the biomedical and agri-food areas; however, studies supporting the environmental health risk assessment of CDs are needed. This study focuses on various CD forms including iron (FeCD) and copper (CuCD) doped CDs synthesized using hydrothermal method, their fate in gastrointestinal tract, and their cytotoxicity and potential changes to cellular metabolome in a triculture small intestinal epithelial model. Physicochemical characterization revealed that 75% of Fe in FeCD and 95% of Cu in CuCD were dissolved during digestion. No significant toxic effects were observed for pristine CDs and FeCDs. However, CuCD induced significant dose-dependent toxic effects including decreases in TEER and cell viability, increases in cytotoxicity and ROS production, and alterations in important metabolites, including D-glucose, L-cysteine, uridine, citric acid and multiple fatty acids. These results support the current understanding that pristine CDs are relatively non-toxic and the cytotoxicity is dependent on the doping molecules.

Effects of engineered lignin-graft-PLGA and zein-based nanoparticles on soybean health.

The majority of published research on the effect of engineered nanoparticles on terrestrial plant species is focused on inorganic nanoparticles, with the effects of organic polymeric nanoparticles (NP) on plants remaining largely unexplored. It is critical to understand the impact of polymeric NPs on plants if these particles are to be used as agrochemical delivery systems. This study investigates the effect of biodegradable polymeric lignin-based nanoparticles (LNPs) and zein nanoparticles (ZNP) on soybean plant health. The LNPs (114 ± 3.4 nm, -53.8 ± 6.9 mV) were synthesized by emulsion evaporation from lignin-graft-poly(lactic-co-glycolic) acid, and ZNPs (142 ± 3.9 nm and + 64.5 ± 4.7 mV) were synthesized by nanoprecipitation. Soybeans were grown hydroponically and treated with 0.02, 0.2, and 2 mg/ml of LNPs or ZNPs at 28 days after germination. Plants were harvested after 1, 3, 7 and 14 days of particle exposure and analyzed for root and stem length, chlorophyll concentration, dry biomass of roots and stem, nutrient uptake and plant ROS. Root and stem length, chlorophyll and stem biomass did not differ significantly between treatments and controls for LNPs-treated plants at all concentrations, and at low doses of ZNPs. At 2 mg/ml ZNPs, the highest concentration tested, after 7 days of treatment chlorophyll levels and root biomass increased and stem length was reduced in comparison to the control. Nutrient uptake was largely unaffected at 0.02 and 0.2 mg/ml NPs. A concentration-dependent increase in the oxidative stresss was detected, especially in the ZNP treated plants. Overall, LNPs and ZNPs had a minimum impact on soybean health especially at low and medium doses. To our knowledge this is the first study to show the effect of zein and lignin based polymeric NPs designed for agrochemical delivery on soybean plant health.

Software Comparison for Nontargeted Analysis of PFAS in AFFF-Contaminated Soil.

Per- and polyfluoroalkyl substances (PFAS) are an emerging class of toxic environmental contaminants. Over 7500 PFAS exist, but reference standards are available for less than 2% of compounds. Nontargeted analysis using liquid chromatography-high-resolution tandem mass spectrometry is therefore an essential technique for increasing the analytical coverage of PFAS present in environmental samples. However, typical nontargeted data analysis is laborious and has a steep learning curve. Recently, FluoroMatch, a new open source, vendor neutral software, was published specifically for automating data processing for nontargeted analysis of PFAS and generating PFAS libraries. Here, we analyze soil contaminated with PFAS based aqueous film forming foam (AFFF) and compare the results produced by data analysis workflows using FluoroMatch and Compound Discoverer, an established nontargeted analysis program. High-confidence PFAS annotations were nearly identical between the methods, with 27 out of 32 compounds found using both Compound Discoverer and the modular version of FluoroMatch. Twenty-two high-confidence annotations were found using the comprehensive FluoroMatch Flow. The FluoroMatch method was faster and required significantly less manual curation than the Compound Discoverer method. Both platforms produced high-quality data that were useful for assessing PFAS contamination in the soil.

Seed Biofortification by Engineered Nanomaterials: A Pathway To Alleviate Malnutrition?

Micronutrient deficiencies in global food chains are a significant cause of ill health around the world, particularly in developing countries. Agriculture is the primary source of nutrients required for sound health, and as the population has continued to grow, the agricultural sector has come under pressure to improve crop production, in terms of both quantity and quality, to meet the global demands for food security. The use of engineered nanomaterial (ENM) has emerged as a promising technology to sustainably improve the efficiency of current agricultural practices as well as overall crop productivity. One promising approach that has begun to receive attention is to use ENM as seed treatments to biofortify agricultural crop production and quality. This review highlights the current state of the science for this approach as well as critical knowledge gaps and research needs that must be overcome to optimize the sustainable application of nano-enabled seed fortification approaches.

Uptake, transport, and effects of nano-copper exposure in zucchini (Cucurbita pepo).

Numerous studies on short term effects of copper-based nanomaterials on plants have been published, however investigations with plants grown in a complex soil medium are lacking. In this study Grey Zucchini (Cucurbita pepo) was grown in an environmental growth chamber using a 1:1 (v/v) potting mix native soil mixture amended with Kocide 3000, nCuO, bCuO, or Cu NPs. After 3 weeks Cu concentrations in the root, stem, and leaves of treated plants were significantly higher than control plants. This increase in Cu concentration did not adversely affect plant growth or chlorophyll production. The activity ascorbate peroxidase (APX) in the roots tissues of plants treated with Kocide 3000, nCuO, and bCuO decreased by at least 45%. Catalase (CAT) activity in root tissues of plants treated with 50 mg/kg of Cu NP decreased by 77%, while those treated at 200 mg/kg were reduced by 80%, compared to controls. The activity of APX and CAT in the leaves of all treated plants remained similar to control plants. Based on the endpoints used in this study, with the exception of a decrease in the accumulation of Zn and B in the roots, the exposure of zucchini to the tested copper compounds resulted in no negative effects.

Use of the sea hare (Aplysia fasciata) in marine pollution biomonitoring of harbors and bays.

Our study evaluated heavy metal concentrations in soft tissues of sea hare, Aplysia fasciata, from the Lower Laguna Madre, Texas. Heavy metals in tissues followed Se>As>Pb>Cd. Concentrations ranged As (BDL-28.08), Cd (BDL-5.50), Pb (BDL-12.85) and Se (4.25-93.43ppm). Median As, Cd, Pb, and Se tissue levels exceeded exposure levels. Significant relationships occurred in metal-metal (AsCd, AsPb, CdPb, CdSe, and PbSe), metal-tissue (significant Se uptake by inhalant and exhalant siphons and As in the hepatopancreas), and metal-metal within tissue (AsPb in the hepatopancreas and CdPb in the digestive cecum) analyses (p<0.05). Bioaccumulation factors (BAF) suggested the inhalant siphon, hepatopancreas, and digestive cecum function as macroconcentrators of Cd, hepatopancreas and digestive cecum as macroconcentrators of Pb, and all tissues were deconcentrators for As and Se. As a bioaccumulator of heavy metals, Aplysia was evaluated as a bioindicator of marine pollution in harbors and bays.

Removal of Cu (II) and Pb (II) from Aqueous Solution using engineered Iron Oxide Nanoparticles.

Nano-sized Fe3O4 and Fe2O3 were synthesized using a precipitation method. The nanomaterials were tested as adsorbents for the removal of both Cu2+ and Pb2+ ions. The nanomaterials were characterized using X-ray powder diffraction to determine both the phase and the average grain size of the synthesized nanomaterials. Batch pH studies were performed to determine the optimum binding pH for both the Cu2+ and Pb2+ to the synthesized nanomaterials. The optimum binding was observed to occur at pH 4 and above. Time dependency studies for Cu2+ and Pb2+ showed the binding occurred within the first five minutes of contact and remained constant up to 2 hours of contact. Isotherm studies were utilized to determine the binding capacity of each of the nanomaterials for Cu2+ and Pb2+. The binding capacity of Fe3O4 with Cu2+ and Pb2+ were 37.04 mg/g and 166.67 mg/g, respectively. The binding capacities of the Fe2O3 nanomaterials with Cu2+ and Pb2+ were determined to be 19.61 mg/g and 47.62 mg/g, respectively. In addition, interference studies showed no significant reduction in the binding of either Cu2+ or Pb2+ to the Fe3O4 or Fe2O3 nanomaterials in the presence of solutions containing the individual ions Na+, K+, Mg2+ and Ca2+ or a solution consisting of a combination of all the aforementioned cations in one solution.

Wastewater compounds in urban shallow groundwater wells correspond to exfiltration probabilities of nearby sewers.

Wastewater compounds are frequently detected in urban shallow groundwater. Sources include sewage or reclaimed wastewater, but origins are often unknown. In a prior study, wastewater compounds were quantified in waters sampled from shallow groundwater wells in a small coastal California city. Here, we resampled those wells and expanded sample analyses to include sewage- or reclaimed water-specific indicators, i.e. pharmaceutical and personal care product chemicals or disinfection byproducts. Also, we developed a geographic information system (GIS)-based model of sanitary sewer exfiltration probability--combining a published pipe failure model accounting for sewer pipe size, age, materials of construction, with interpolated depths to groundwater--to determine if sewer system attributes relate to wastewater compounds in urban shallow groundwater. Across the wells, groundwater samples contained varying wastewater compounds, including acesulfame, sucralose, bisphenol A, 4-tert-octylphenol, estrone and perfluorobutanesulfonic acid (PFBS). Fecal indicator bacterial concentrations and toxicological bioactivities were less than known benchmarks. However, the reclaimed water in this study was positive for all bioactivity tested. Excluding one well intruded by seawater, the similarity of groundwater to sewage, based on multiple indicators, increased with increasing sanitary sewer exfiltration probability (modeled from infrastructure within ca. 300 m of each well). In the absence of direct exfiltration or defect measurements, sewer exfiltration probabilities modeled from the collection system's physical data can indicate potential locations where urban shallow groundwater is contaminated by sewage.

Differential Toxicity of Bare and Hybrid ZnO Nanoparticles in Green Pea (Pisum sativum L.): A Life Cycle Study.

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.