Yuxiong Huang

EDTA functionalized magnetic nanoparticle sorbents for cadmium and lead contaminated water treatment.

Cadmium (Cd(2+)) and lead (Pb(2+)) are toxic to human beings and other organisms, and the U.S. Environmental Protection Agency (EPA) has classified both as probable human carcinogens. In this study, a regenerable magnetic ligand particle (Mag-Ligand) which includes a metal-binding organic ligand (EDTA) attached to an iron oxide nanoparticle was developed for rapid removal of Cd(2+) and Pb(2+) as well as other metals from contaminated water. Mag-Ligand showed fast removal ability for both Cd(2+) (<2 h) and Pb(2+) (<15 min) with relatively high sorption capacity (79.4 and 100.2 mg/g for Cd(2+) and Pb(2+), respectively). The removal performance of Mag-Ligand was high across a wide pH range (3-10) as well as in the presence of competitive metal ions (Ca(2+) and Mg(2+)). In addition, Mag-Ligands can be easily regenerated (washed by 1% HCl) and reused several cycles with high sorption capacity. This study indicated that Mag-Ligand is a reusable sorbent for rapid, convenient, and efficient removal of Cd(2+) and Pb(2+) from contaminated aquatic systems.

1H NMR and GC-MS Based Metabolomics Reveal Defense and Detoxification Mechanism of Cucumber Plant under Nano-Cu Stress

Because copper nanoparticles are being increasingly used in agriculture as pesticides, it is important to assess their potential implications for agriculture. Concerns have been raised about the bioaccumulation of nano-Cu and their toxicity to crop plants. Here, the response of cucumber plants in hydroponic culture at early development stages to two concentrations of nano-Cu (10 and 20 mg/L) was evaluated by proton nuclear magnetic resonance spectroscopy ((1)H NMR) and gas chromatography-mass spectrometry (GC-MS) based metabolomics. Changes in mineral nutrient metabolism induced by nano-Cu were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Results showed that nano-Cu at both concentrations interferes with the uptake of a number of micro- and macro-nutrients, such as Na, P, S, Mo, Zn, and Fe. Metabolomics data revealed that nano-Cu at both levels triggered significant metabolic changes in cucumber leaves and root exudates. The root exudate metabolic changes revealed an active defense mechanism against nano-Cu stress: up-regulation of amino acids to sequester/exclude Cu/nano-Cu; down-regulation of citric acid to reduce the mobilization of Cu ions; ascorbic acid up-regulation to combat reactive oxygen species; and up-regulation of phenolic compounds to improve antioxidant system. Thus, we demonstrate that nontargeted (1)H NMR and GC-MS based metabolomics can successfully identify physiological responses induced by nanoparticles. Root exudates metabolomics revealed important detoxification mechanisms.

Heteroaggregation of nanoparticles with biocolloids and geocolloids

The application of nanoparticles has raised concern over the safety of these materials to human health and the ecosystem. After release into an aquatic environment, nanoparticles are likely to experience heteroaggregation with biocolloids, geocolloids, natural organic matter (NOM) and other types of nanoparticles. Heteroaggregation is of vital importance for determining the fate and transport of nanoparticles in aqueous phase and sediments. In this article, we review the typical cases of heteroaggregation between nanoparticles and biocolloids and/or geocolloids, mechanisms, modeling, and important indicators used to determine heteroaggregation in aqueous phase. The major mechanisms of heteroaggregation include electric force, bridging, hydrogen bonding, and chemical bonding. The modeling of heteroaggregation typically considers DLVO, X-DLVO, and fractal dimension. The major indicators for studying heteroaggregation of nanoparticles include surface charge measurements, size measurements, observation of morphology of particles and aggregates, and heteroaggregation rate determination. In the end, we summarize the research challenges and perspective for the heteroaggregation of nanoparticles, such as the determination of αhetero values and heteroaggregation rates; more accurate analytical methods instead of DLS for heteroaggregation measurements; sensitive analytical techniques to measure low concentrations of nanoparticles in heteroaggregation systems; appropriate characterization of NOM at the molecular level to understand the structures and fractionation of NOM; effects of different types, concentrations, and fractions of NOM on the heteroaggregation of nanoparticles; the quantitative adsorption and desorption of NOM onto the surface of nanoparticles and heteroaggregates; and a better understanding of the fundamental mechanisms and modeling of heteroaggregation in natural water which is a complex system containing NOM, nanoparticles, biocolloids and geocolloids.

Metabolomics to detect response of lettuce (Lactuca sativa) to Cu(OH)2 nanopesticides: Oxidative stress response and detoxification mechanisms

There has been an increasing influx of nanopesticides into agriculture in recent years. Understanding the interaction between nanopesticides and edible plants is crucial in evaluating the potential impact of nanotechnology on the environment and agriculture. Here we exposed lettuce plants to Cu(OH)2 nanopesticides (1050-2100 mg/L) through foliar spray for one month. Inductively coupled plasma-mass spectrometry (ICP-MS) results indicate that 97-99% (1353-2501 mg/kg) of copper was sequestered in the leaves and only a small percentage (1-3%) (17.5-56.9 mg/kg) was translocated to root tissues through phloem loading. Gas chromatography-time-of-flight mass spectrometry (GC-TOF-MS) based metabolomics combined with partial least squares-discriminant analysis (PLS-DA) multivariate analysis revealed that Cu(OH)2 nanopesticides altered metabolite levels of lettuce leaves. Tricarboxylic (TCA) cycle and a number of amino acid-related biological pathways were disturbed. Some antioxidant levels (cis-caffeic acid, chlorogenic acid, 3,4-dihydroxycinnamic acid, dehydroascorbic acid) were significantly decreased compared to the control, indicating that oxidative stress and a defense response occurred. Nicotianamine, a copper chelator, increased by 12-27 fold compared to the control, which may represent a detoxification mechanism. The up-regulation of polyamines (spermidine and putrescine) and potassium may mitigate oxidative stress and enhance tolerance. The data presented here provide a molecular-scale perspective on the response of plants to copper nanopesticides.

Citizen science as an approach for overcoming insufficient monitoring and inadequate stakeholder buy-in in adaptive management: criteria and evidence

Adaptive management is broadly recognized as critical for managing natural resources, yet in practice it often fails to achieve intended results for two main reasons: insufficient monitoring and inadequate stakeholder buy-in. Citizen science is gaining momentum as an approach that can inform natural resource management and has some promise for solving the problems faced by adaptive management. Based on adaptive management literature, we developed a set of criteria for successfully addressing monitoring and stakeholder related failures in adaptive management and then used these criteria to evaluate 83 citizen science case studies from peer-reviewed literature. The results suggest that citizen science can be a cost-effective method to collect essential monitoring information and can also produce the high levels of citizen engagement that are vital to the adaptive management learning process. The analysis also provides a set of recommendations for citizen science program design that addresses spatial and temporal scale, data quality, costs, and effective incentives to facilitate participation and integration of findings into adaptive management.

Plant-based green synthesis of metallic nanoparticles: scientific curiosity or a realistic alternative to chemical synthesis?

Currently, thousands of tons of metallic nanoparticles (MNPs) are produced and utilized in nano-enabled devises, personal care, medicinal, food and agricultural products. It is generally accepted that the reaction compounds and the techniques used in industrial production of MNPs are not environmentally friendly. The green synthesis has been proposed as an alternative to reduce the use of hazardous compounds and harsh reaction conditions in the production of MNPs. In this endeavor, investigators have used organic compounds, microbes, plants and plant-derived materials as reducing agents. Research papers are published every year, and each one of them stresses the benefits of the green approach and the advantages over the traditional syntheses. However, after almost two decades since the explosion of the reports about the new approach, the commercial production of green-synthesized nanoparticles does not seem to find a way to scale up commercial production. This review includes descriptions of the traditional and green synthesis and applications of MNPs and highlights the factors limiting the use of plant-based synthesis as a real alternative to the traditional synthesis of MNPs.

GC-TOF-MS based metabolomics and ICP-MS based metallomics of cucumber (Cucumis sativus) fruits reveal alteration of metabolites profile and biological pathway disruption induced by nano copper

Copper-based nanoparticles have wide application in agriculture as fungicides and bactericides. Due to the rapid increase in their use, it is imperative to understand their environmental impact, especially on agricultural crops. In this study, inductively coupled plasma mass spectrometry (ICP-MS) based metallomics and gas chromatography-time of flight mass spectrometry (GC-TOF-MS) based metabolomics were applied to detect metal and molecular changes in cucumber plants exposed to various environmentally-relevant levels of nano copper (nCu at 0, 200, 400, and 800 mg kg−1) until full maturity. Metallomics studies showed nCu caused the perturbation of Fe uptake in leaves. In fruit, Ca, K, S, P, Zn and Mg increased after exposure to 400 and 800 mg kg−1 nCu. Metabolomics and partial least-squares discriminant analysis (PLS-DA) revealed that the metabolite profile in cucumber fruits was distinctively altered due to exposure to nCu. A number of metabolites were either up-regulated (proline, glycine, valine, pelargonic acid, arachidic acid, xylose, benzoic acid) or down-regulated (citric acid, myo-inositol, ornithine, 1-kestose) in response to nCu exposure. Biological pathway analysis showed a number of C and N related pathways were changed, especially galactose metabolism and the tricarboxylic acid cycle, indicating C and N metabolism was perturbed by nCu. This study showed GC-TOF-MS based metabolomics combined with ICP-MS based metallomics provide the necessary preliminary data to conduct further mechanistic investigations.

1H NMR and GC-MS based metabolomics reveal nano-Cu altered cucumber (Cucumis sativus) fruit nutritional supply

It is imperative to study the interaction of nanoparticles residuals with crop plants in agricultural soils, due to the increased application of nanotechnology in agriculture. So far, a few studies have focused on the impact of nanoparticles on fruit quality and nutritional supply. In this work, a thorough and comprehensive analysis of metabolite changes of cucumber fruits from plants under nano-Cu stress was possible through the use of both 1H NMR and GC-MS. The results of supervised partial least-squares discriminant analysis from both platforms showed that cucumber fruit extracts samples were clearly grouped based on the nano-Cu level in soil. This indicates that the fruit metabolite profile was influenced by exposure to nano-Cu. GC-MS data showed concentrations of some sugars, organic acids, amino acids, and fatty acids were increased or decreased by nano-Cu. Several metabolites, such as methylnicotinamide (MNA), trigonelline, imidazole, quinolinate were only detected and quantified by 1H NMR. Our results showed that combining the two platforms provided a comprehensive understanding about the metabolites (nutrient supply) changes in cucumber fruits impacted by exposure to nano-Cu.

Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium- Contaminated Water Treatment

Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water.

Simultaneous removal of PAHs and metal contaminants from water using magnetic nanoparticle adsorbents

Many industrial wastewaters are contaminated with both heavy metal ions and organic compounds, posing a major threat to public health and the environment. In this study, magnetic nanoparticle adsorbents, namely Mag-PCMA-T, which contain a maghemite core and a silica mesoporous layer that permanently confines surfactant micelles within the mesopores, were synthesized to achieve simultaneous removal of polycyclic aromatic hydrocarbons (PAHs) (1mg/L) and metal contaminants (1mg/L). The individual removal efficiency of Cd(2+) and acenaphthene using Mag-PCMA-T was evaluated under a range of initial ion concentrations and adsorbent dosages, as well as the competitive adsorption with Cd(2+) and acenaphthene simultaneously present. The isotherms and kinetics of Cd(2+) and acenaphthene sorption onto Mag-PCMA-T were determined. Mag-PCMA-T removed >85% of the acenaphthene in <30min, with relatively high sorption capacity (up to 1060mg/kg). Mag-PCMA-T also exhibited high sorption capacity for Cd(2+) (up to 2250mg/kg). The simultaneous sorption performance was stable across a wide pH range (4-9) as well as in the presence of competitive metal ions (Ca(2+) and Mg(2+)) or natural organic matters. The Mag-PCMA-T can be regenerated and reused, providing a sustainable, fast, convenient, and efficient approach for water treatment.