DNA Delivery by Virus-Like Nanocarriers in Plant Cells.

Tobacco mild green mosaic virus (TMGMV)-like nanocarriers were designed for gene delivery to plant cells. High aspect ratio TMGMVs were coated with a polycationic biopolymer, poly(allylamine) hydrochloride (PAH), to generate highly charged nanomaterials (TMGMV-PAH; 56.20 ± 4.7 mV) that efficiently load (1:6 TMGMV:DNA mass ratio) and deliver single-stranded and plasmid DNA to plant cells. The TMGMV-PAH were taken up through energy-independent mechanisms in Arabidopsis protoplasts. TMGMV-PAH delivered a plasmid DNA encoding a green fluorescent protein (GFP) to the protoplast nucleus (70% viability), as evidenced by GFP expression using confocal microscopy and Western blot analysis. TMGMV-PAH were inactivated (iTMGMV-PAH) using UV cross-linking to prevent systemic infection in intact plants. Inactivated iTMGMV-PAH-mediated pDNA delivery and gene expression of GFP in vivo was determined using confocal microscopy and RT-qPCR. Virus-like nanocarrier-mediated gene delivery can act as a facile and biocompatible tool for advancing genetic engineering in plants.

Targeted Delivery of Sucrose-Coated Nanocarriers with Chemical Cargoes to the Plant Vasculature Enhances Long-Distance Translocation.

Current practices for delivering agrochemicals are inefficient, with only a fraction reaching the intended targets in plants. The surfaces of nanocarriers are functionalized with sucrose, enabling rapid and efficient foliar delivery into the plant phloem, a vascular tissue that transports sugars, signaling molecules, and agrochemicals through the whole plant. The chemical affinity of sucrose molecules to sugar membrane transporters on the phloem cells enhances the uptake of sucrose-coated quantum dots (sucQD) and biocompatible carbon dots with ß-cyclodextrin molecular baskets (suc-ß-CD) that can carry a wide range of agrochemicals. The QD and CD fluorescence emission properties allowed detection and monitoring of rapid translocation (<40 min) in the vasculature of wheat leaves by confocal and epifluorescence microscopy. The suc-ß-CDs more than doubled the delivery of chemical cargoes into the leaf vascular tissue. Inductively coupled plasma mass spectrometry (ICP-MS) analysis showed that the fraction of sucQDs loaded into the phloem and transported to roots is over 6.8 times higher than unmodified QDs. The sucrose coating of nanoparticles approach enables unprecedented targeted delivery to roots with ≈70% of phloem-loaded nanoparticles delivered to roots. The use of plant biorecognition molecules mediated delivery provides an efficient approach for guiding nanocarriers containing agrochemicals to the plant vasculature and whole plants.

Characterizing the Stoichiometry of Individual Metal Sulfide and Phosphate Colloids in Soils, Sediments, and Industrial Processes by Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

Size and purity of metal phosphate and metal sulfide colloids can control the solubility, persistence, and bioavailability of metals in environmental systems. Despite their importance, methods for detecting and characterizing the diversity in the elemental composition of these colloids in complex matrices are missing. Here, we develop a single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-icpTOF-MS) approach to characterize the elemental compositions of individual metal phosphate and sulfide colloids extracted from complex matrices. The stoichiometry was accurately determined for particles of known composition with an equivalent spherical diameter of ≥∼200 nm. Assisted by machine learning (ML), the new method could distinguish particles of the copper sulfides covellite (CuS), chalcocite (Cu2S), and chalcopyrite particles (CuFeS2) with 75% (for Cu2S) to 99% (for CuFeS2) accuracy. Application of the sp-icpTOF-MS method to particles recovered from natural samples revealed that iron sulfide (FeS) particles in lake sediment contained ∼4% copper and zinc impurities, whereas pure pyrite (FeS2) was identified in hydraulic fracturing wastewater and confirmed by selected area electron diffraction. Colloidal mercury in an offshore marine sediment was present as pure mercury sulfide (HgS), whereas geogenic HgS recovered from an industrial process contained ∼0.08 wt % silver per Hg, enabling source apportionment of these colloids using ML. X-ray absorption spectroscopy confirmed that Hg was predominantly present as metacinnabar (ß-HgS) in the industrial process sample. The determination of impurities in individual colloids, such as zinc and copper in FeS, and silver in HgS may enable improved assessment of their origin, reactivity, and bioavailability potential.

Polymer Coatings Affect Transport and Remobilization of Colloidal Activated Carbon in Saturated Sand Columns: Implications for In Situ Groundwater Remediation.

Colloidal activated carbon (CAC) is an emerging technology for the in situ remediation of groundwater impacted by per- and polyfluoroalkyl substances (PFAS). In assessing the long-term effectiveness of a CAC barrier, it is crucial to evaluate the potential of emplaced CAC particles to be remobilized and migrate away from the sorptive barrier. We examine the effect of two polymer stabilizers, carboxymethyl cellulose (CMC) and polydiallyldimethylammonium chloride (PolyDM), on CAC deposition and remobilization in saturated sand columns. CMC-modified CAC showed high mobility in a wide ionic strength (IS) range from 0.1 to 100 mM, which is favorable for CAC delivery at a sufficient scale. Interestingly, the mobility of PolyDM-modified CAC was high at low IS (0.1 mM) but greatly reduced at high IS (100 mM). Notably, significant remobilization (release) of deposited CMC-CAC particles occurred upon the introduction of solution with low IS following deposition at high IS. In contrast, PolyDM-CAC did not undergo any remobilization following deposition due to its favorable interactions with the quartz sand. We further elucidated the CAC deposition and remobilization behaviors by analyzing colloid-collector interactions through the application of Derjaguin-Landau-Verwey-Overbeek theory, and the inclusion of a discrete representation of charge heterogeneity on the quartz sand surface. The classical colloid filtration theory was also employed to estimate the travel distance of CAC in saturated columns. Our results underscore the roles of polymer coatings and solution chemistry in CAC transport, providing valuable guidelines for the design of in situ CAC remediation with maximized delivery efficiency and barrier longevity.

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.

Effect of a Zinc Phosphate Shell on the Uptake and Translocation of Foliarly Applied ZnO Nanoparticles in Pepper Plants (Capsicum annuum).

Here, isotopically labeled 68ZnO NPs (ZnO NPs) and 68ZnO NPs with a thin 68Zn3(PO4)2 shell (ZnO_Ph NPs) were foliarly applied (40 µg Zn) to pepper plants (Capsicum annuum) to determine the effect of surface chemistry of ZnO NPs on the Zn uptake and systemic translocation to plant organs over 6 weeks. Despite similar dissolution of both Zn-based NPs after 3 weeks, the Zn3(PO4)2 shell on ZnO_Ph NPs (48 ± 12 nm; -18.1 ± 0.6 mV) enabled a leaf uptake of 2.31 ± 0.34 µg of Zn, which is 2.7 times higher than the 0.86 ± 0.18 µg of Zn observed for ZnO NPs (26 ± 8 nm; 14.6 ± 0.4 mV). Further, ZnO_Ph NPs led to higher Zn mobility and phloem loading, while Zn from ZnO NPs was stored in the epidermal tissues, possibly through cell wall immobilization as a storage strategy. These differences led to higher translocation of Zn from the ZnO_Ph NPs within all plant compartments. ZnO_Ph NPs were also more persistent as NPs in the exposed leaf and in the plant stem over time. As a result, the treatment of ZnO_Ph NPs induced significantly higher Zn transport to the fruit than ZnO NPs. As determined by spICP-TOFMS, Zn in the fruit was not in the NP form. These results suggest that the Zn3(PO4)2 shell on ZnO NPs can help promote the transport of Zn to pepper fruits when foliarly applied. This work provides insight into the role of Zn3(PO4)2 on the surface of ZnO NPs in foliar uptake and in planta biodistribution for improving Zn delivery to edible plant parts and ultimately improving the Zn content in food for human consumption.

Path to autonomous soil sampling and analysis by ground-based robots.

Good site characterization is essential for the selection of remediation alternatives for impacted soils. The value of site characterization is critically dependent on the quality and quantity of the data collected. Current methods for characterizing impacted soils rely on expensive manual sample collection and off-site analysis. However, recent advances in terrestrial robotics and artificial intelligence offer a potentially revolutionary set of tools and methods that will help to autonomously explore natural environments, select sample locations with the highest value of information, extract samples, and analyze the data in real-time without exposing humans to potentially hazardous conditions. A fundamental challenge to realizing this potential is determining how to design an autonomous system for a given investigation with many, and often conflicting design criteria. This work presents a novel design methodology to navigate these criteria. Specifically, this methodology breaks the system into four components - sensing, sampling, mobility, and autonomy - and connects design variables to the investigation objectives and constraints. These connections are established for each component through a survey of existing technology, discussion of key technical challenges, and highlighting conditions where generality can promote multi-application deployment. An illustrative example of this design process is presented for the development and deployment of a robotic platform characterizing salt-impacted oil & gas reserve pits. After calibration, the relationship between the in situ robot chloride measurements and laboratory-based chloride measurements had a good linear relationship (R2-value = 0.861) and statistical significance (p-value = 0.003).

Decoupling Fe0 Application and Bioaugmentation in Space and Time Enables Microbial Reductive Dechlorination of Trichloroethene to Ethene: Evidence from Soil Columns.

Fe0 is a powerful chemical reductant with applications for remediation of chlorinated solvents, including tetrachloroethene and trichloroethene. Its utilization efficiency at contaminated sites is limited because most of the electrons from Fe0 are channeled to the reduction of water to H2 rather than to the reduction of the contaminants. Coupling Fe0 with H2-utilizing organohalide-respiring bacteria (i.e., Dehalococcoides mccartyi) could enhance trichloroethene conversion to ethene while maximizing Fe0 utilization efficiency. Columns packed with aquifer materials have been used to assess the efficacy of a treatment combining in space and time Fe0 and aD. mccartyi-containing culture (bioaugmentation). To date, most column studies documented only partial conversion of the solvents to chlorinated byproducts, calling into question the feasibility of Fe0 to promote complete microbial reductive dechlorination. In this study, we decoupled the application of Fe0 in space and time from the addition of organic substrates andD. mccartyi-containing cultures. We used a column containing soil and Fe0 (at 15 g L-1 in porewater) and fed it with groundwater as a proxy for an upstream Fe0 injection zone dominated by abiotic reactions and biostimulated/bioaugmented soil columns (Bio-columns) as proxies for downstream microbiological zones. Results showed that Bio-columns receiving reduced groundwater from the Fe0-column supported microbial reductive dechlorination, yielding up to 98% trichloroethene conversion to ethene. The microbial community in the Bio-columns established with Fe0-reduced groundwater also sustained trichloroethene reduction to ethene (up to 100%) when challenged with aerobic groundwater. This study supports a conceptual model where decoupling the application of Fe0 and biostimulation/bioaugmentation in space and/or time could augment microbial trichloroethene reductive dechlorination, particularly under oxic conditions.

Particle-Scale Understanding of Arsenic Interactions with Sulfidized Nanoscale Zerovalent Iron and Their Impacts on Dehalogenation Reactivity.

Co-occurrence of organic contaminants and arsenic oxoanions occurs often at polluted groundwater sites, but the effect of arsenite on the reactivity of sulfidized nanoscale zerovalent iron (SNZVI) used to remediate groundwater has not been evaluated. Here, we study the interaction of arsenite [As(III)] with SNZVI at the individual-particle scale to better understand the impacts on the SNZVI properties and reactivity. Surface and intraparticle accumulation of As was observed on hydrophilic FeS-Fe0 and hydrophobic FeS2-Fe0 particles, respectively. X-ray absorption spectroscopy indicated the presence of realgar-like As-S and elemental As0 species at low and high As/Fe concentration ratios, respectively. Single-particle inductively coupled plasma time-of-flight mass spectrometry analysis identified As-containing particles both with and without Fe. The probability of finding As-containing particles without Fe increased with the S-induced hydrophobicity of SNZVI. The interactions of SNZVI materials with coexisting arsenite inhibited their reactivity with water (∼5.8-230.7-fold), trichloroethylene (∼3.6-67.5-fold), and florfenicol (∼1.1-5.9-fold). However, the overall selectivity toward trichloroethylene and florfenicol relative to water was improved (up to 9.0-fold) because the surface-associated As increased the SNZVI hydrophobicity. These results indicate that reactions of SNZVI with arsenite can remove As from groundwater and improve the properties of SNZVI for dehalogenation selectivity.

Charge, Aspect Ratio, and Plant Species Affect Uptake Efficiency and Translocation of Polymeric Agrochemical Nanocarriers.

An incomplete understanding of how agrochemical nanocarrier properties affect their uptake and translocation in plants limits their application for promoting sustainable agriculture. Herein, we investigated how the nanocarrier aspect ratio and charge affect uptake and translocation in monocot wheat (Triticum aestivum) and dicot tomato (Solanum lycopersicum) after foliar application. Leaf uptake and distribution to plant organs were quantified for polymer nanocarriers with the same diameter (∼10 nm) but different aspect ratios (low (L), medium (M), and high (H), 10-300 nm long) and charges (-50 to +15 mV). In tomato, anionic nanocarrier translocation (20.7 ± 6.7 wt %) was higher than for cationic nanocarriers (13.3 ± 4.1 wt %). In wheat, only anionic nanocarriers were transported (8.7 ± 3.8 wt %). Both low and high aspect ratio polymers translocated in tomato, but the longest nanocarrier did not translocate in wheat, suggesting a phloem transport size cutoff. Differences in translocation correlated with leaf uptake and interactions with mesophyll cells. The positive charge decreases nanocarrier penetration through the leaf epidermis and promotes uptake into mesophyll cells, decreasing apoplastic transport and phloem loading. These results suggest design parameters to provide agrochemical nanocarriers with rapid and complete leaf uptake and an ability to target agrochemicals to specific plant organs, with the potential to lower agrochemical use and the associated environmental impacts.

Application of Isotopically Labeled Engineered Nanomaterials for Detection and Quantification in Soils via Single-Particle Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

Finding and quantifying engineered nanomaterials (ENMs) in soil are challenging because of the abundance of natural nanomaterials (NNMs) with the same elemental composition, for example, TiO2. Isotopically enriched ENMs may be distinguished from NNMs with the same elemental composition using single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOF-MS) to measure multiple isotopes simultaneously within each ENM and NNM in soil, but the minimum isotope enrichment needed for detection of ENMs in soil is not known. Here, we determined the isotope enrichment needed for 47Ti-enriched TiO2 ENMs to be detectable in soil and assessed the effects of weathering on those requirements for less soluble TiO2 and more soluble CuO ENMs. The isotope-enriched ENMs were dosed into two different soils and were extracted and measured by spICP-TOF-MS after 1, 7, and 30 days. Isotope-enriched ENMs were recovered and detected for all three time points. The 47Ti-enriched TiO2 ENMs were detectable in Lufa 2.2 soil at a nominal dosed concentration of 10 mg-TiO2 kg-1 which is an environmentally relevant concentration in biosolid-amended soils. For distinguishing an ∼70 nm diameter TiO2 ENM from TiO2 NNMs in Lufa 2.2 soil, an ∼10 wt % 47Ti isotope-enrichment was required, and this enrichment requirement increases as the particle size decreases. This study is the first to evaluate the tracking ability of isotope-enriched ENMs at an individual particle level in soil and provides guidance on the isotope enrichment requirements for quantification of ENMs made from Earth-abundant elements in soils.

Distinguishing Engineered TiO2 Nanomaterials from Natural Ti Nanomaterials in Soil Using spICP-TOFMS and Machine Learning.

Identifying engineered nanomaterials (ENMs) made from earth-abundant elements in soils is difficult because soil also contains natural nanomaterials (NNMs) containing similar elements. Here, machine learning models using elemental fingerprints and mass distributions of three TiO2 ENMs and Ti-based NNMs recovered from three natural soils measured by single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS) was used to identify TiO2 ENMs in soil. Synthesized TiO2 ENMs were unassociated with other elements (>98%), while 40% of Ti-based ENM particles recovered from wastewater sludge had distinguishable elemental associations. All Ti-based NNMs extracted from soil had a similar chemical fingerprint despite the soils being from different regions, and >60% of Ti-containing NNMs had no measurable associated elements. A machine learning model best distinguished NNMs and ENMs when differences in Ti-mass distribution existed between them. A trained LR model could classify 100 nm TiO2 ENMs at concentrations of 150 mg kg-1 or greater. The presence of TiO2 ENMs in soil could be confirmed using this approach for most ENM-soil combinations, but the absence of a unique chemical fingerprint in a large fraction of both TiO2 ENMs and Ti-NNMs increases model uncertainty and hinders accurate quantification.

Critical Review: Role of Inorganic Nanoparticle Properties on Their Foliar Uptake and in Planta Translocation.

There is increasing pressure on global agricultural systems due to higher food demand, climate change, and environmental concerns. The design of nanostructures is proposed as one of the economically viable technological solutions that can make agrochemical use (fertilizers and pesticides) more efficient through reduced runoff, increased foliar uptake and bioavailability, and decreased environmental impacts. However, gaps in knowledge about the transport of nanoparticles across the leaf surface and their behavior in planta limit the rational design of nanoparticles for foliar delivery with controlled fate and limited risk. Here, the current literature on nano-objects deposited on leaves is reviewed. The different possible foliar routes of uptake (stomata, cuticle, trichomes, hydathodes, necrotic spots) are discussed, along with the paths of translocation, via the phloem, from the leaf to the end sinks (mature and developing tissues, roots, rhizosphere). This review details the interplays between morphological constraints, environmental stimuli, and physical-chemical properties of nanoparticles influencing their fate, transformation, and transport after foliar deposition. A metadata analysis from the existing literature highlighted that plant used for testing nanoparticle fate are most often dicotyledon plants (75%), while monocotyledons (as cereals) are less considered. Correlations on parameters calculated from the literature indicated that nanoparticle dose, size, zeta potential, and affinity to organic phases correlated with leaf-to-sink translocation, demonstrating that targeting nanoparticles to specific plant compartments by design should be achievable. Correlations also showed that time and plant growth seemed to be drivers for in planta mobility, parameters that are largely overlooked in the literature. This review thus highlights the material design opportunities and the knowledge gaps for targeted, stimuli driven deliveries of safe nanomaterials for agriculture.

Phosphate Polymer Nanogel for Selective and Efficient Rare Earth Element Recovery.

Demand for rare earth elements (REEs) is increasing, and REE production from ores is energy-intensive. Recovering REEs from waste streams can provide a more sustainable approach to help meet REE demand but requires materials with high selectivity and capacity for REEs due to the low concentration of REEs and high competing ion concentrations. Here, we developed a phosphate polymer nanogel (PPN) to selectively recover REEs from low REE content waste streams, including leached fly ash. A high phosphorus content (16.2 wt % P as phosphate groups) in the PPN provides an abundance of coordination sites for REE binding. In model solutions, the distribution coefficient (Kd) for all REEs ranged from 1.3 × 105 to 3.1 × 105 mL g-1 at pH = 7, and the sorption capacity (qm) for Nd, Gd, and Ho were ∼300 mg g-1. The PPN was selective toward REEs, outcompeting cations (Ca, Mg, Fe, Al) at up to 1000-fold excess concentration. The PPN had a Kd of ∼105-106 mL g-1 for lanthanides in coal fly ash leachate (pH = 5), orders of magnitude higher than the Kd of major competing ions (∼103-104 mL g-1). REEs were recovered from the PPN using 3.5% HNO3, and the material remained effective over three sorption-elution cycles. The high REE capacity and selectivity and good durability in a real waste stream matrix suggest its potential to recover REEs from a broad range of secondary REE stocks.

Star Polymer Size, Charge Content, and Hydrophobicity Affect their Leaf Uptake and Translocation in Plants.

Determination of how the properties of nanocarriers of agrochemicals affect their uptake and translocation in plants would enable more efficient agent delivery. Here, we synthesized star polymer nanocarriers poly(acrylic acid)-block-poly(2-(methylsulfinyl)ethyl acrylate) (PAA-b-PMSEA) and poly(acrylic acid)-block-poly((2-(methylsulfinyl)ethyl acrylate)-co-(2-(methylthio)ethyl acrylate)) (PAA-b-P(MSEA-co-MTEA)) with well-controlled sizes (from 6 to 35 nm), negative charge content (from 17% to 83% PAA), and hydrophobicity and quantified their leaf uptake, phloem loading, and distribution in tomato (Solanum lycopersicum) plants 3 days after foliar application of 20 µL of a 1g L-1 star polymer solution. In spite of their property differences, ∼30% of the applied star polymers translocated to other plant organs, higher than uptake of conventional foliar applied agrochemicals (<5%). The property differences affected their distribution in the plant. The ∼6 nm star polymers exhibited 3 times higher transport to younger leaves than larger ones, while the ∼35 nm star polymer had over 2 times higher transport to roots than smaller ones, suggesting small star polymers favor symplastic unloading in young leaves, while larger polymers favor apoplastic unloading in roots. For the same sized star polymer, a smaller negative charge content (yielding ζ ∼ -12 mV) enhanced translocation to young leaves and roots, whereas a larger negative charge (ζ < -26 mV) had lower mobility. Hydrophobicity only affected leaf uptake pathways, but not translocation. This study can help design agrochemical nanocarriers for efficient foliar uptake and targeting to desired plant organs, which may decrease agrochemical use and environmental impacts of agriculture.

Unveiling the Role of Sulfur in Rapid Defluorination of Florfenicol by Sulfidized Nanoscale Zero-Valent Iron in Water under Ambient Conditions.

Groundwater contamination by halogenated organic compounds, especially fluorinated ones, threatens freshwater sources globally. Sulfidized nanoscale zero-valent iron (SNZVI), which is demonstrably effective for dechlorination of groundwater contaminants, has not been well explored for defluorination. Here, we show that SNZVI nanoparticles synthesized via a modified post-sulfidation method provide rapid dechlorination (∼1100 µmol m-2 day-1) and relatively fast defluorination (∼6 µmol m-2 day-1) of a halogenated emerging contaminant (florfenicol) under ambient conditions, the fastest rates that have ever been reported for Fe0-based technologies. Batch reactivity experiments, material characterizations, and theoretical calculations indicate that coating S onto the metallic Fe surface provides a highly chemically reactive surface and changes the primary dechlorination pathway from atomic H for nanoscale zero-valent iron (NZVI) to electron transfer for SNZVI. S and Fe sites are responsible for the direct electron transfer and atomic H-mediated reaction, respectively, and ß-elimination is the primary defluorination pathway. Notably, the Cl atoms in florfenicol make the surface more chemically reactive for defluorination, either by increasing florfenicol adsorption or by electronic effects. The defluorination rate by SNZVI is ∼132-222 times higher with chlorine attached compared to the absence of chlorine in the molecule. These mechanistic insights could lead to new SNZVI materials for in situ groundwater remediation of fluorinated contaminants.

Impacts of Sediment Particle Grain Size and Mercury Speciation on Mercury Bioavailability Potential.

Particle-specific properties, including size and chemical speciation, affect the reactivity of mercury (Hg) in natural systems (e.g., dissolution or methylation). Here, terrestrial, river, and marine sediments were size-fractionated and characterized to correlate particle-specific properties of Hg-bearing solids with their bioavailability potential and measured biomethylation. Marine sediments contained ∼20-50% of the total Hg in the <0.5 µm size fraction, compared to only 0.5 and 3.0% in this size fraction for terrestrial and river sediments, respectively. X-ray absorption spectroscopy (XAS) analysis indicated that metacinnabar (ß-HgS) was the main mercury species in a marine sediment, whereas organic Hg-thiol (Hg(SR)2) was the main mercury species in a terrestrial sediment. Single-particle inductively coupled plasma time-of-flight mass spectrometry analysis of the marine sediment suggests that half of the Hg in the <0.5 µm size fraction existed as individual nanoparticles, which were ß-HgS based on XAS analyses. Glutathione-extractable mercury was higher for samples containing Hg(SR)2 species than ß-HgS species and correlated well with the amount of Hg biomethylation. This particle-scale understanding of how Hg speciation and particle size affect mercury bioavailability potential helps explain the heterogeneity in Hg methylation in natural sediments.

Amphiphilic Thiol Polymer Nanogel Removes Environmentally Relevant Mercury Species from Both Produced Water and Hydrocarbons.

Technologies for removal of mercury from produced water and hydrocarbon phases are desired by oil and gas production facilities, oil refineries, and petrochemical plants. Herein, we synthesize and demonstrate the efficacy of an amphiphilic, thiol-abundant (11.8 wt % S, as thiol) polymer nanogel that can remove environmentally relevant mercury species from both produced water and the liquid hydrocarbon. The nanogel disperses in both aqueous and hydrocarbon phases. It has a high sorption affinity for dissolved Hg(II) complexes and Hg-dissolved organic matter complexes found in produced water and elemental (Hg0) and soluble Hg-alkyl thiol species found in hydrocarbons. X-ray absorption spectroscopy analysis indicates that the sorbed mercury is transformed to a surface-bound Hg(SR)2 species in both water and hydrocarbon regardless of its initial speciation. The nanogel had high affinity to native mercury species present in real produced water (>99.5% removal) and in natural gas condensate (>85% removal) samples, removing majority of the mercury species using only a 50 mg L-1 applied dose. This thiolated amphiphilic polymeric nanogel has significant potential to remove environmentally relevant mercury species from both water and hydrocarbon at low applied doses, outperforming reported sorbents like sulfur-impregnated activated carbons because of the mass of accessible thiol groups in the nanogel.

Methanol-based extraction protocol for insoluble and moderately water-soluble nanoparticles in plants to enable characterization by single particle ICP-MS.

The detection and characterization of soluble metal nanoparticles in plant tissues are an analytical challenge, though a scientific necessity for regulating nano-enabled agrichemicals. The efficacy of two extraction methods to prepare plant samples for analysis by single particle ICP-MS, an analytical method enabling both size determination and quantification of nanoparticles (NP), was assessed. A standard enzyme-based extraction was compared to a newly developed methanol-based approach. Au, CuO, and ZnO NPs were extracted from three different plant leaf materials (lettuce, corn, and kale) selected for their agricultural relevance and differing characteristics. The enzyme-based approach was found to be unsuitable because of changes in the recovered NP size distribution of CuO NP. The MeOH-based extraction allowed reproducible extraction of the particle size distribution (PSD) without major alteration caused by the extraction. The type of leaf tissue did not significantly affect the recovered PSD. Total metal losses during the extraction process were largely due to the filtration step prior to analysis by spICP-MS, though this did not significantly affect PSD recovery. The methanol extraction worked with the three different NPs and plants tested and is suitable for studying the fate of labile metal-based nano-enabled agrichemicals.

Multistep Method to Extract Moderately Soluble Copper Oxide Nanoparticles from Soil for Quantification and Characterization.

The objective of this study is to assess how method parameters impact the extraction of moderately soluble CuO nanoparticles (NPs) from a standard natural soil (LUFA 2.1) suitable for chemical analysis. The extraction procedure is comprised of three steps: (i) preconditioning the soil to increase the sodium adsorption ratio, (ii) extracting colloids/NPs from the soil matrix using sonication and a dispersing agent, and (iii) separating the dissolved and nanoparticulate CuO fractions using cloud point extraction. Method parameters of the extraction procedure, including sonication, number of extraction cycles, and dispersing agent, were adjusted to achieve the highest extraction of CuO NPs, while minimizing dissolution. The maximum recovery of CuO NPs ranged from 31% to 42% for an amended concentration range of 10-250 mg-Cu (kg soil)-1 using a preconditioning step to exchange divalent cations for monovalent ions, 0.2% carboxymethyl cellulose (CMC) 700 kg mol-1 as the dispersing agent, probe sonication for 1 min, 3 extraction cycles, and a 1:10 soil-to-liquid ratio. CuO NPs that are polyvinylpyrrolidone (PVP)-coated with a greater stability against aggregation had significantly higher extractability and dissolution. This procedure is the first to effectively extract moderately soluble NPs from soil and experimentally separate them from their dissolved fraction and can be applied to other moderately soluble metal containing natural, incidental, or engineered NPs in soil.