Nano-enabled pesticides for sustainable agriculture and global food security.

Achieving sustainable agricultural productivity and global food security are two of the biggest challenges of the new millennium. Addressing these challenges requires innovative technologies that can uplift global food production, while minimizing collateral environmental damage and preserving the resilience of agroecosystems against a rapidly changing climate. Nanomaterials with the ability to encapsulate and deliver pesticidal active ingredients (AIs) in a responsive (for example, controlled, targeted and synchronized) manner offer new opportunities to increase pesticidal efficacy and efficiency when compared with conventional pesticides. Here, we provide a comprehensive analysis of the key properties of nanopesticides in controlling agricultural pests for crop enhancement compared with their non-nanoscale analogues. Our analysis shows that when compared with non-nanoscale pesticides, the overall efficacy of nanopesticides against target organisms is 31.5% higher, including an 18.9% increased efficacy in field trials. Notably, the toxicity of nanopesticides toward non-target organisms is 43.1% lower, highlighting a decrease in collateral damage to the environment. The premature loss of AIs prior to reaching target organisms is reduced by 41.4%, paired with a 22.1% lower leaching potential of AIs in soils. Nanopesticides also render other benefits, including enhanced foliar adhesion, improved crop yield and quality, and a responsive nanoscale delivery platform of AIs to mitigate various pressing biotic and abiotic stresses (for example, heat, drought and salinity). Nonetheless, the uncertainties associated with the adverse effects of some nanopesticides are not well-understood, requiring further investigations. Overall, our findings show that nanopesticides are potentially more efficient, sustainable and resilient with lower adverse environmental impacts than their conventional analogues. These benefits, if harnessed appropriately, can promote higher crop yields and thus contribute towards sustainable agriculture and global food security.

Evaluation of the Immobilization of Coexisting Heavy Metal Ions of Pb2+, Cd2+ , and Zn2+ from Water by Dairy Manure-Derived Biochar: Performance and Reusability.

Heavy metals including Cd, Pb, and Zn are prevalent stormwater and groundwater contaminants derived from natural and human activities, and there is a lack of cost-effective treatment for their removal. Recently, biochar has been increasingly recognized as a promising low-cost sorbent that can be used to remediate heavy metal contaminated water. This study evaluates the immobilization/release performance of dairy manure-derived biochar (DM-BC) as a sustainable material for competitive removal of coexisting heavy metal ions from water and explains the underlying mechanism for regeneration/reusability of biochar. Results showed that the metal ions exhibited competitive removal in the order of Pb2+ ≫ Zn2+ > Cd2+. The pH played a decisive role in influencing metal ion speciation affecting the electrostatic attraction/repulsion and surface complexation. Higher pH led to greater removal for Pb2+ and Cd2+, whereas Zn2+ showed maximum removal at pH ≈ 7.5. Diffuse reflectance infrared spectroscopy, scanning electron microscopy, and X-ray diffraction confirmed the interactions and precipitation reactions of oxygen-containing functional groups (e.g., ─OH, CO32-, and Si─O) as key participants in metal immobilization. Langmuir, Freundlich, and Redlich-Peterson isotherm modeling data showed varied and unique results depending on the metal ion and concentration. The removal kinetics and model fitting showed that the three steps of intraparticle diffusion might be more representative for describing the immobilization processes of metal ions on the external surface and internal pores. In the flow-through columns, DM-BC effectively retained the mixed metal ions of Cd2+, Pb2+, and Zn2+ showing 100% removal for the duration of the column run over three cycles of regeneration and reuse.

Surface heterogeneity mediated transport of hydrochar nanoparticles in heterogeneous porous media.

The effects of clay particles (montmorillonite, M) and phosphate (P) on the transport of hydrochar nanoparticles (NPs) in water-saturated porous media (uncoated and aluminum (Al) oxide-coated sands) were explored in NaCl (1-50 mM) solutions. Our results showed that the deposition behaviors of hydrochar NPs affected by M and phosphate were significantly different between pH 6.0 and pH 9.0, especially in Al oxide-coated sand. This can be attributed to their distinct surface characteristics: hydrochar agglomerates with a larger pore size distribution, more carboxylate groups, and less negative charges on the surface at pH 9.0 than those at pH 6.0. In Al oxide-coated sand, block adsorption of hydrochar was alleviated appreciably with the presence of M due to the preferential preoccupies of M on these favorable retention sites. On the contrary, M substantially increased the hydrochar retention on uncoated sand due to the formation of nanoaggregates between hydrochar and M. Differently, phosphate substantially enhanced the transport of hydrochar, even in coated sand, due to the strong phosphate adsorption onto Al oxide on the surface of sand and hydrochar. Our findings will provide useful insights into designing effective strategies for land application of hydrochar while minimizing potential environmental risks. Graphical abstract.

Facilitated transport of nTiO2-kaolin aggregates by bacteria and phosphate in water-saturated quartz sand.

The soil major component of clay plays an important role in governing the fate and transport of engineered nanomaterials (e.g., the most commonly used titanium dioxide nanoparticles; nTiO2) in the subsurface environments via forming nTiO2-clay aggregates. This research is designed to unravel the interplay of naturally-occurring bacteria (Escherichia coli) and phosphate on the transport and retention of nTiO2-kaolin aggregates in water-saturated porous media. Our results showed that nTiO2-nTiO2 homoaggregates and nTiO2-kaolin heteroaggregates dominated in the nTiO2-kaolin nanoaggregate suspension. Transport of nTiO2-kaolin aggregates was enhanced with the copresence of E. coli and phosphate, particularly at the low pH of 6.0. This effect is due to the greater adsorption of phosphate and thus the greater enhancement in repulsive interaction energies between aggregates and sand grains at pH 6.0 (vs. pH 9.0). The charged "soft layer" of E. coli cell surfaces changed the aggregation state and the heterogeneous distribution of nTiO2-kaolin aggregates, and subsequently stabilized the nTiO2-nTiO2 homoaggregates and nTiO2-kaolin heteroaggregates via TEM-EDX measurements and promoted the physical segregation between the aggregates (separation distance = 0.486 vs. 0.614 µm without vs. with the presence of E. coli) via 2D/3D AFM identifications, both of which caused greater mobility of nTiO2-kaolin aggregates with the presence of E. coli. Nonetheless, transport of nTiO2-kaolin aggregates was lower with the copresence of E. coli and phosphate vs. the singular presence of phosphate due to the competitive adsorption of less negatively charged E. coli (vs. phosphate) onto the aggregates. Taken altogether, our findings furnish new insights into better understanding the fate, transport, and potential risks of nTiO2 in real environmental settings (soil and sediment aquifer) where clay, bacteria, and phosphate ubiquitously cooccur.

Removal of Fluoride from Water Using a Calcium-Modified Dairy Manure-Derived Biochar.

This study investigated the removal of fluoride from water using a calcium-modified dairy manure-derived biochar (Ca-DM500). The Ca-DM500 showed a 3.82 - 8.86 times higher removal of fluoride from water than the original (uncoated) manure-derived biochar (DM500). This is primarily attributed to strong precipitation/complexation between fluoride and calcium. The Freundlich and Redlich-Peterson sorption isotherm models better described the experimental data than the Langmuir model. Additionally, the removal kinetics were well described by the intraparticle diffusion model. The Ca-DM500 showed high reactivity per unit surface area [0.0001, 0.03, 0.16 mg F per m2 for Douglas fir-derived biochar (DF-BC), DM500. and Ca-DM500, respectively] for retention of fluoride reflecting the importance of surface complexation. The copresence of anions reduced removal by Ca-DM500 in the order SO 4 2 - ≈ PO 4 3 - > NO 3 - . The sorption behavior of fluoride in a continuous fixed-bed column was consistent with the Thomas model. Column studies demonstrated that the Ca-DM500 shows a strong affinity for fluoride, a low release potential, and a stable (unreduced) removal capacity through regeneration and reuse cycles.

Removal of Arsenate and Arsenite in Equimolar Ferrous and Ferric Sulfate Solutions through Mineral Coprecipitation: Formation of Sulfate Green Rust, Goethite, and Lepidocrocite.

An improved understanding of in situ mineralization in the presence of dissolved arsenic and both ferrous and ferric iron is necessary because it is an important geochemical process in the fate and transformation of arsenic and iron in groundwater systems. This work aimed at evaluating mineral phases that could form and the related transformation of arsenic species during coprecipitation. We conducted batch tests to precipitate ferrous (133 mM) and ferric (133 mM) ions in sulfate (533 mM) solutions spiked with As (0-100 mM As(V) or As(III)) and titrated with solid NaOH (400 mM). Goethite and lepidocrocite were formed at 0.5-5 mM As(V) or As(III). Only lepidocrocite formed at 10 mM As(III). Only goethite formed in the absence of added As(V) or As(III). Iron (II, III) hydroxysulfate green rust (sulfate green rust or SGR) was formed at 50 mM As(III) at an equilibrium pH of 6.34. X-ray analysis indicated that amorphous solid products were formed at 10-100 mM As(V) or 100 mM As(III). The batch tests showed that As removal ranged from 98.65-100%. Total arsenic concentrations in the formed solid phases increased with the initial solution arsenic concentrations ranging from 1.85-20.7 g kg-1. Substantial oxidation of initially added As(III) to As(V) occurred, whereas As(V) reduction did not occur. This study demonstrates that concentrations and species of arsenic in the parent solution influence the mineralogy of coprecipitated solid phases, which in turn affects As redox transformations.

Toxicity of ZnO/TiO2 -conjugated carbon-based nanohybrids on the coastal marine alga Thalassiosira pseudonana.

Increasing consumption of metal-oxide nanoparticles (NPs) and carbon-based nanomaterials has caused significant concern about their potential hazards in aquatic environments. The release of NPs into aquatic environments could result in adsorption of NPs on microorganisms. While metal-oxide NP-conjugated carbon-based nanohybrids (NHs) may exhibit enhanced toxicity toward microorganisms due to their large surface area and the generation of reactive oxygen species (ROS), there is a lack of information regarding the ecotoxicological effects of NHs on marine diatom algae, which are an indicator of marine pollution. Moreover, there is scant information on toxicity mechanisms of NHs on aquatic organisms. In this study, four NHs (ie, ZnO-conjugated graphene oxide [GO], ZnO-conjugated carbon nanotubes [CNTs], TiO2 -conjugated GO, and TiO2 -conjugated CNT) that were synthesized by a hydrothermal method were investigated for their toxicity effects on a Thalassiosira pseudonana marine diatom. The in vitro cellular viability and ROS formation employed at the concentration ranges of 50 and 100 mg/L of NHs over 72 hours revealed that ZnO-GO had the most negative effect on T. pseudonana. The primary mechanism identified was the generation of ROS and GO-induced dispersion that caused electrostatic repulsion, preventing aggregation, and an increase in surface areas of NHs. In contrast to GO-induced dispersion, large aggregates were observed in ZnO/TiO2 -conjugated CNT-based NHs. The scanning electron microscopy images suggest that NHs covered algae cells and interacted with them (shading effects); this reduced light availability for photosynthesis. Detailed in vitro toxicity effects and mechanisms that cause high adverse acute toxicity on T. pseudonana were unveiled; this implied concerns about potential hazards of these mechanisms in aquatic ecosystems.

Antibacterial effects of graphene- and carbon-nanotube-based nanohybrids on Escherichia coli: Implications for treating multidrug-resistant bacteria.

Some nanomaterials including Fe0, Ag0, and ZnO are well known for their antibacterial effects. However, very few studies have examined antibacterial effects of nanohybrids. Given that metal oxides, mainly ZnO and TiO2, are known to increase mobility, surface area, and photocatalysis when combined with carbon-based nanomaterials, ZnO- and TiO2-conjugated carbon nanotube and graphene oxide nanohybrids were investigated for their antibacterial effects on Escherichia coli (DH5α, a multidrug-resistant coliform bacterium). Graphene-oxide (GO)-based nanohybrids (ZnO-GO and TiO2-GO) induced increased dispersion compared to carbon-nanotube (CNT)-based nanohybrids (ZnO-CNT and TiO2-CNT). Among the four types of nanohybrids, ZnO-conjugated nanohybrids exhibited a higher antibacterial property, resulting in the antibacterial effect (measured with growth inhibition of cells) in the order ZnO-GO > ZnO-CNT > TiO2-GO > TiO2-CNT. Among four possible antibacterial mechanisms (generation of reactive oxygen species (ROS), physicochemical characteristics, the steric effect, and release of metal ions), a primary mechanism-ROS generation-was identified; whereas, physicochemical characteristics and the steric effect were part of contributing mechanisms. The increasing dispersion of TiO2/ZnO on GO may have contributed to the antibacterial effects due to increasing surface areas. Similarly, significant damages to E. coli cell membranes were found by the GO sheet with its sharp edges. Our results suggest that applying GO-based ZnO or TiO2 could be an effective antibacterial method, especially for the treatment of multidrug-resistant bacteria in the water.

Next-Generation Multifunctional Carbon-Metal Nanohybrids for Energy and Environmental Applications.

Nanotechnology has unprecedentedly revolutionized human societies over the past decades and will continue to advance our broad societal goals in the coming decades. The research, development, and particularly the application of engineered nanomaterials have shifted the focus from "less efficient" single-component nanomaterials toward "superior-performance", next-generation multifunctional nanohybrids. Carbon nanomaterials (e.g., carbon nanotubes, graphene family nanomaterials, carbon dots, and graphitic carbon nitride) and metal/metal oxide nanoparticles (e.g., Ag, Au, CdS, Cu2O, MoS2, TiO2, and ZnO) combinations are the most commonly pursued nanohybrids (carbon-metal nanohybrids; CMNHs), which exhibit appealing properties and promising multifunctionalities for addressing multiple complex challenges faced by humanity at the critical energy-water-environment (EWE) nexus. In this frontier review, we first highlight the altered and newly emerging properties (e.g., electronic and optical attributes, particle size, shape, morphology, crystallinity, dimensionality, carbon/metal ratio, and hybridization mode) of CMNHs that are distinct from those of their parent component materials. We then illustrate how these important newly emerging properties and functions of CMNHs direct their performances at the EWE nexus including energy harvesting (e.g., H2O splitting and CO2 conversion), water treatment (e.g., contaminant removal and membrane technology), and environmental sensing and in situ nanoremediation. This review concludes with identifications of critical knowledge gaps and future research directions for maximizing the benefits of next-generation multifunctional CMNHs at the EWE nexus and beyond.

Effect of various chemical oxidation reagents on soil indigenous microbial diversity in remediation of soil contaminated by PAHs.

Chemical oxidation is a promising pretreatment step coupled with bioremediation for removal of polycyclic aromatic hydrocarbons (PAHs). The effectiveness of Fenton, modified Fenton, potassium permanganate and activated persulfate oxidation treatments on the real contaminated soils collected from a coal gas plant (263.6 ±â€¯73.3 mg kg-1 of the Σ16 PAHs) and a coking plant (385.2 ±â€¯39.6 mg kg-1 of the Σ16 PAHs) were evaluated. Microbial analyses showed only a slight impact on indigenous microbial diversity by Fenton treatment, but showed the inhibition of microbial diversity and delayed population recovery by potassium permanganate reagent. After potassium permanganate treatment, the microorganism mainly existed in the soil was Pseudomonas or Pseudomonadaceae. The results showed that total organic carbon (TOC) content in soil was significantly increased by adding modified Fenton reagent (1.4%-2.3%), while decreased by adding potassium permanganate (0.2%-1%), owing to the nonspecific and different oxidative properties of chemical oxidant. The results also demonstrated that the removal efficiency of total PAHs was ordered: permanganate (90.0%-92.4%) > activated persulfate (81.5%-86.54%) > modified Fenton (81.5%-85.4%) > Fenton (54.1%-60.0%). Furthermore, the PAHs removal efficiency was slightly increased on the 7th day after Fenton and modified Fenton treatments, about 14.6%, and 14.4% respectively, and the PAHs removal efficiency only enhanced 4.1% and 1.3% respectively from 1st to 15th day after potassium permanganate and activated persulfate treatments. The oxidants greatly affect the growth of soil indigenous microbes, which cause further influence for PAHs degradation by bioremediation.

Potential utility of graphene-based nano spinel ferrites as adsorbent and photocatalyst for removing organic/inorganic contaminants from aqueous solutions: A mini review.

Toxic substances such as heavy metals or persistent organic pollutants raise global environmental concerns. Thus, diverse water decontamination approaches using nano-adsorbents and/or photocatalysts based on nanotechnology are being developed. Particularly, many studies have examined the removal of organic and inorganic contaminants with novel graphene-based nano spinel ferrites (GNSFs) as potential cost-effective alternatives to traditionally used materials, owing to their enhanced physical and chemical properties. The introduction of magnetic spinel ferrites into 2-D graphene-family nanomaterials to form GNSFs brings various benefits such as inhibited particle agglomeration, enhanced active surface area, and easier magnetic separation for reuse, making the GNSFs highly efficient and eco-friendly materials. Here, we present a short review on the state-of-the-art progresses on developments of GNSFs, as well as their potential application for removing several recalcitrant contaminants including organic dyes, antibiotics, and heavy metal ions. Particularly, the mechanisms involved in the adsorptive and photocatalytic degradation are thoroughly reviewed, and the reusability of the GNSFs is also highlighted. This review concludes that the GNSFs hold great potential in remediating contaminated aquatic environments. Further studies are needed for their practical and large-scale applications.

Adsorptive Removal of Fluoride from Water Using Nanomaterials of Ferrihydrite, Apatite, and Brucite: Batch and Column Studies.

This study investigated the adsorptive removal of fluoride from simulated water pollution using various (hydro)oxide nanomaterials, which have the potential to be used as sorbents for surface water and groundwater remediation. Tested nanomaterials include hematite, magnetite, ferrihydrite, goethite, hematite-alpha, hydroxyapatite (HAP), brucite, and four titanium dioxides (TiO2-A [anatase], TiO2-B [rutile], TiO2-C [rutile], and TiO2-D [anatase]). Among 11 (hydro)oxide nanomaterials tested in this study, ferrihydrite, HAP, and brucite showed two to five times higher removal of fluoride than other nanomaterials from synthetic fluoride solutions. Freundlich and Redlich-Peterson adsorption isotherms better described the adsorptive capacity and mechanism than the Langmuir isotherm based on higher R 2 values, indicating better fit of the regression predictions. In addition, the adsorption kinetics were well described by the intraparticle diffusion model. Column studies in a fixed bed continuous flow through system were conducted to illustrate the adsorption and desorption behavior of fluoride on ferrihydrite, HAP, or brucite. Experimental results fitted well with the Thomas model because of the R 2 values at least 0.885 or higher. By comparisons of the adsorption capacity and the rate constant, columns packed with ferrihydrite exhibited not only faster rates but also higher sorption capacity than those packed with HAP or brucite. Desorption tests in deionized water showed that the adsorbed fluoride could be desorbed at a lower efficiency, ranging from 4.0% to 8.9%. The study implicated that (hydro)oxide nanomaterials of iron calcium and magnesium could be effective sorptive materials incorporated into filtration systems for the remediation of fluoride polluted water.

Evaluation of the colloidal stability and adsorption performance of reduced graphene oxide-elemental silver/magnetite nanohybrids for selected toxic heavy metals in aqueous solutions.

Reduced graphene oxide (rGO) hybridized with magnetite and/or elemental silver (rGO/magnetite, rGO/silver, and rGO/magnetite/silver) nanoparticles were evaluated as potential adsorbents for toxic heavy metal ions (Cd (II), Ni(II), Zn(II), Co(II), Pb(II), and Cu(II)). Although the deposition of iron oxide and silver nanoparticles on the rGO nanosheets played an inhibitory role in metal ion adsorption, the metal adsorption efficiency by the nanohybrids (NHs) was still higher than that reported for many other sorbents (e.g., activated biochar, commercial resins, and nanosized hydrated Zr(IV) oxide particles). X-ray photoelectron spectroscopy analyses revealed that complexation with deprotonated adsorbents and cation exchange was an important mechanism for Cd(II) ion removal by the rGO and NHs. Competitive adsorption tests using multi metals showed that the adsorption affinity of metal ions on the rGO and its NHs follows the order (Cu(II), Zn(II)) > Ni(II) > Co(II) > (Pb(II), Cd(II)), which is similar to the order observed for single-metal adsorption experiments. These results can be explained by the destabilization abilities of the rGO and NHs, as well as the ionic radii of the considered metal ions. Our findings demonstrate the feasibility of using rGO-based NHs as highly efficient adsorbents for heavy metal removal from water.

Enhanced degradation of polycyclic aromatic hydrocarbons by indigenous microbes combined with chemical oxidation.

In this study, the removal efficiency PAHs by chemical oxidation combined with microbe remediation was evaluated in two contaminated soils. The number of indigenous soil microbes decreased after the addition of chemical oxidants and then increased by nutrients addition. The total removal efficiencies of PAHs by chemical oxidation and nutrient addition followed the order: activated persulfate > potassium permanganate > modified Fenton reagent > Fenton reagent. There are 24.29-27.97%, 22.00-23.67%, 10.24-13.74% and 1.9-2.5% contributions separately due to nutrient treatment in Fenton, modified Fenton, activated persulfate and potassium permanganate treatment, which show significantly difference. The different chemical oxidants exhibited 78-90% removal efficiency for 5-6 rings PAHs, while 52-85% removal efficiency for 2-4 rings PAHs. With the addition of nutrients, the growth of indigenous microbes was enhanced significantly, and the contents of 2-4 rings PAHs in the soil were further decreased. Furthermore, the removal efficiencies of NAP and ANY were increased by more than 45%, while the removal efficiencies of ANE, FLE and PHE were about 30% at Fenton system. There was a complementary enhancing effect of microbial remediation for PAHs degradation after chemical oxidation.

Modeling the Transport of the "New-Horizon" Reduced Graphene Oxide-Metal Oxide Nanohybrids in Water-Saturated Porous Media.

Little is known about the fate and transport of the "new-horizon" multifunctional nanohybrids in the environment. Saturated sand-packed column experiments ( n = 66) were therefore performed to investigate the transport and retention of reduced graphene oxide (RGO)-metal oxide (Fe3O4, TiO2, and ZnO) nanohybrids under environmentally relevant conditions (mono- and divalent electrolytes and natural organic matter). Classical colloid science principles (Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and colloid filtration theory (CFT)) and mathematical models based on the one-dimensional convection-dispersion equation were employed to describe and predict the mobility of RGO-Fe3O4, RGO-TiO2, and RGO-ZnO nanohybrids in porous media. Results indicate that the mobility of the three nanohybrids under varying experimental conditions is overall explainable by DLVO theory and CFT. Numerical simulations suggest that the one-site kinetic retention model (OSKRM) considering both time- and depth-dependent retention accurately approximated the breakthrough curves (BTCs) and retention profiles (RPs) of the nanohybrids concurrently; whereas, others (e.g., two-site retention model) failed to capture the BTCs and/or RPs. This is primarily because blocking BTCs and exponential/hyperexponential/uniform RPs occurred, which is within the framework of OSKRM featuring time- (for kinetic Langmuirian blocking) and depth-dependent (for exponential/hyperexponential/uniform) retention kinetics. Employing fitted parameters (maximum solid-phase retention capacity: Smax = 0.0406-3.06 cm3/g; and first-order attachment rate coefficient: ka = 0.133-20.6 min-1) extracted from the OSKRM and environmentally representative physical variables (flow velocity (0.00441-4.41 cm/min), porosity (0.24-0.54), and grain size (210-810 µm)) as initial input conditions, the long-distance transport scenarios (in 500 cm long sand columns) of the three nanohybrids were predicted via forward simulation. Our findings address the existing knowledge gap regarding the impact of physicochemical factors on the transport of the next-generation, multifunctional RGO-metal oxide nanohybrids in the subsurface.

Heterogeneous activation of persulfate by reduced graphene oxide-elemental silver/magnetite nanohybrids for the oxidative degradation of pharmaceuticals and endocrine disrupting compounds in water.

Reduced graphene oxide hybridized with zero-valent silver and magnetite nanoparticles (NPs) (rGO-Ag0/Fe3O4 nanohybrids) prepared via in situ nucleation and crystallization was used to activate peroxydisulfate (PDS) for degradation of pharmaceuticals and endocrine disrupting compounds (phenol, acetaminophen, ibuprofen, naproxen, bisphenol A, 17ß-estradiol, and 17α-ethinyl estradiol). The deposition of Ag0 and Fe3O4 in rGO nanosheet enhanced the catalytic removal of phenol in the heterogeneous activation of PDS. The adsorption capacities of rGO-Ag0/Fe3O4 for 10 µM phenol were 1.76, 1.33, and 2.04 µmol g-1-adsorbent at pH 4, 7, and 10, respectively, which are much higher than those of single NPs studied (Ag0, nanoscale zero-valent iron, and rGO). The rGO-Ag0/Fe3O4 effectively activated PDS to produce strong oxidizing SO4·and facilitate an electron transfer on the surface of the nanohybrid. The initial pseudo-first-order rate (k ini) constant for phenol degradation in PDS/rGO-Ag0/Fe3O4 system was 0.46 h-1 at pH 7, which is approximately eight times higher than that in the presence of single NPs (k ini = 0.04-0.06 h-1) due to the synergistic effects between adsorption and catalytic oxidation. Among various organic contaminants tested, the simultaneous use of rGO-Ag0/Fe3O4 (0.1 g/L) and PDS (1 mM) achieved more than 99% degradation of acetaminophen and 17ß-estradiol at pH 7. The radical scavenging studies with methanol and natural organic matter indicated that phenol was more likely to be degraded via free SO4·- and ·OH formation or a non-radical oxidative pathway. Our findings indicate that the rGO-Ag0/Fe O nanohybrids can be used as an efficient magnetically-separable nanocatalyst for removal of organic compounds in water and wastewater treatment.

Pilot-scale application of shotblast dust for phosphorus removal.

Phosphorus contamination is a global issue, and cost-effective remediation is sought for removing phosphorus from water. We applied a novel use of waste material called shotblast dust in a pilot-scale reactor to remove phosphorus from water. Results indicate that shotblast dust was effective in treating phosphorus-laden water with 132 kg of the material treating 568 liters of 220 µg/L total phosphorus (T-P) water on a daily basis, achieving approximately 60% removal of T-P in 7 days.

Aggregation of reduced graphene oxide and its nanohybrids with magnetite and elemental silver under environmentally relevant conditions.

The aggregation and long-term (25 d) sedimentation behaviors of reduced graphene oxide (RGO) and its three successively self-assembled nanohybrids with magnetite (Fe3O4) and zerovalent silver (Ag0) nanoparticles have been investigated. The aggregation behaviors of the nanomaterials in NaCl and CaCl2 were found to be in good agreement with the Derjaguin-Landau-Verwey-Overbeek (DLVO)-type interactions and the Schulze-Hardy rule. The colloidal stability decreased with the increasing ratios of the edge-based functional groups (COO- and C=O) to the total oxygen-containing functional groups decorated on the basal planes (C-O) and edges of RGO, as quantified by X-ray photoelectron spectroscopy analysis. In the presence of natural organic matter (NOM), the aggregation of RGO and its nanohybrids was greatly inhibited as a result of the enhanced electrosteric repulsions arising from the adsorbed NOM macromolecules. The long-term sedimentation kinetics results showed that the RGO nanohybrids were less stable in synthetic groundwater containing higher electrolyte concentrations, which was likely because of the greater charge screening or neutralization effect imparted by higher monovalent and divalent electrolyte concentrations. Our findings have important implications for evaluating the environmental impact and toxicity of the emerging class of multifunctional nanohybrids whose environmental behaviors are currently largely unknown.

Carboxymethylcellulose Mediates the Transport of Carbon Nanotube-Magnetite Nanohybrid Aggregates in Water-Saturated Porous Media.

Carbon-metal oxide nanohybrids (NHs) are increasingly recognized as the next-generation, promising group of nanomaterials for solving emerging environmental issues and challenges. This research, for the first time, systematically explored the transport and retention of carbon nanotube-magnetite (CNT-Fe3O4) NH aggregates in water-saturated porous media under environmentally relevant conditions. A macromolecule modifier, carboxymethylcellulose (CMC), was employed to stabilize the NHs. Our results show that transport of the magnetic CNT-Fe3O4 NHs was lower than that of nonmagnetic CNT due to larger hydrodynamic sizes of NHs (induced by magnetic attraction) and size-dependent retention in porous media. Classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory can explain the mobility of NHs under varying experimental conditions. However, in contrast with colloid filtration theory, a novel transport feature-an initial lower and a following sharp-higher peaks occurred frequently in the NHs' breakthrough curves. The magnitude and location of both transport peaks varied with different experimental conditions, due to the interplay between variability of fluid viscosity and size-selective retention of the NHs. Promisingly, the estimated maximum transport distance of NHs ranged between ∼0.38 and 46 m, supporting the feasibility of employing the magnetically recyclable CNT-Fe3O4 NHs for in situ nanoremediation of contaminated soil, aquifer, and groundwater.

Role of solution chemistry in the retention and release of graphene oxide nanomaterials in uncoated and iron oxide-coated sand.

Understanding the fate and transport including remobilization of graphene oxide nanomaterials (GONMs) in the subsurface would enable us to expedite their benign use and evaluate their environmental impacts and health risks. In this study, the retention and release of GONMs were investigated in water-saturated columns packed with uncoated sand (Un-S) or iron oxide-coated sand (FeS) at environmentally relevant solution chemistries (1-100mM KCl and 0.1-10mM CaCl2 at pH7 and 11). Our results showed that increasing ionic strength (IS) inhibited GONMs' transport, and the impact of K+ was less than Ca2+. The positively charged iron oxide coating on sand surfaces immobilized the negatively charged GONMs (pH7) in the primary minimum, yielding hyperexponential retention profiles particularly in Ca2+. A stepwise decrease in pore-water IS caused detachment of previously retained GONMs. The mass of GONMs released during each detachment step correlated positively with the difference in secondary minimum depth (ΔΦmin2) at each IS, indicating that the released GONMs were retained in the secondary minimum. While most retained GONMs were re-entrained upon lowering pore-water IS in Un-S, decreasing IS only released limited GONMs in FeS, which were captured in the primary minimum. Introducing 1mM NaOH (pH11) released most retained GONMs in FeS; and average hydrodynamic diameters of the detached GONMs upon injecting NaOH were significantly smaller than those of GONMs in the influent and retentate, suggesting that NaOH induced GONMs disaggregation. Our findings advance current knowledge to better predict NMs' fate and transport under various solution chemistries such as during rainfall events or in the mixing zones between sea water and fresh water where transient IS changes drastically.