Everything falls apart: How solids degrade and release nanomaterials, composite fragments, and microplastics.

To ensure the safe use of materials, one must assess the identity and quantity of exposure. Solid materials, such as plastics, metals, coatings and cements, degrade to some extent during their life cycle, and releases can occur during manufacturing, use and end-of-life. Releases (e.g., what is released, how does release happen, and how much material is released) depend on the composition and internal (nano)structures of the material as well as the applied stresses during the lifecycle. We consider, in some depth, releases from mechanical, weathering and thermal stresses and specifically address the use cases of fused-filament 3D printing, dermal contact, food contact and textile washing. Solid materials can release embedded nanomaterials, composite fragments, or micro- and nanoplastics, as well as volatile organics, ions and dissolved organics. The identity of the release is often a heterogenous mixture and requires adapted strategies for sampling and analysis, with suitable quality control measures. Control materials enhance robustness by enabling comparative testing, but reference materials are not always available as yet. The quantity of releases is typically described by time-dependent rates that are modulated by the nature and intensity of the applied stress, the chemical identity of the polymer or other solid matrix, and the chemical identity and compatibility of embedded engineered nanomaterials (ENMs) or other additives. Standardization of methods and the documentation of metadata, including all the above descriptors of the tested material, applied stresses, sampling and analytics, are identified as important needs to advance the field and to generate robust, comparable assessments. In this regard, there are strong methodological synergies between the study of all solid materials, including the study of micro- and nanoplastics. From an outlook perspective, we review the hazard of the released entities, and show how this informs risk assessment. We also address the transfer of methods to related issues such as tyre wear, advanced materials and advanced manufacturing, biodegradable polymers, and non-solid matrices. As the consideration of released entities will become more routine in industry via lifecycle assessment in Safe-and-Sustainable-by-Design practices, release assessments will require careful design of the study with quality controls, the use of agreed-on test materials and standardized methods where these exist and the adoption of clearly defined data reporting practices that enable data reuse, meta-analyses, and comparative studies.

Reproducibility of methods required to identify and characterize nanoforms of substances.

Nanoforms (NFs) of a substance may be distinguished from one another through differences in their physicochemical properties. When registering nanoforms of a substance for assessment under the EU REACH framework, five basic descriptors are required for their identification: composition, surface chemistry, size, specific surface area and shape. To make the risk assessment of similar NFs efficient, a number of grouping frameworks have been proposed, which often require assessment of similarity on individual physicochemical properties as part of the group justification. Similarity assessment requires an understanding of the achievable accuracy of the available methods. It must be demonstrated that measured differences between NFs are greater than the achievable accuracy of the method, to have confidence that the measured differences are indeed real. To estimate the achievable accuracy of a method, we assess the reproducibility of six analytical techniques routinely used to measure these five basic descriptors of nanoforms: inductively coupled plasma mass spectrometry (ICP-MS), Thermogravimetric analysis (TGA), Electrophoretic light scattering (ELS), Brunauer-Emmett-Teller (BET) specific surface area and transmission and scanning electron microscopy (TEM and SEM). Assessment was performed on representative test materials to evaluate the reproducibility of methods on single NFs of substances. The achievable accuracy was defined as the relative standard deviation of reproducibility (RSDR) for each method. Well established methods such as ICP-MS quantification of metal impurities, BET measurements of specific surface area, TEM and SEM for size and shape and ELS for surface potential and isoelectric point, all performed well, with low RSDR, generally between 5 and 20%, with maximal fold differences usually <1.5 fold between laboratories. Applications of technologies such as TGA for measuring water content and putative organic impurities, additives or surface treatments (through loss on ignition), which have a lower technology readiness level, demonstrated poorer reproducibility, but still within 5-fold differences. The expected achievable accuracy of ICP-MS may be estimated for untested analytes using established relationships between concentration and reproducibility, but this is not yet the case for TGA measurements of loss on ignition or water content. The results here demonstrate an approach to estimate the achievable accuracy of a method that should be employed when interpreting differences between NFs on individual physicochemical properties.

Refinement of the selection of physicochemical properties for grouping and read-across of nanoforms.

Before placing a new nanoform (NF) on the market, its potential adverse effects must be evaluated. This may e.g. be done via hazard and risk assessment. Grouping and read-across of NFs is a possible strategy to reduce resource consumption, maximising the use of existing data for assessment of NFs. The GRACIOUS project provides a framework in which possible grouping and read-across for NFs is mainly based on an evaluation of their similarity. The impact of NFs on human health and the environment depends strongly on the concentration of the NF and its physicochemical properties, such as chemical composition, size distribution, shape, etc. Hence, knowledge of the most relevant physicochemical properties is essential information for comparing similarity. The presented work aims to refine existing proposals for sets of descriptors (descriptor array) that are needed to describe distinct NFs of a material to identify the most relevant ones for grouping and read-across. The selection criteria for refining this descriptor array are explained and demonstrated. Relevant protocols and methods are proposed for each physicochemical property. The required and achievable measurement accuracies of the refined descriptor array are reviewed, as this information is necessary for similarity assessment of NFs based on individual physicochemical properties.

From bottle to microplastics: Can we estimate how our plastic products are breaking down?

Microplastics (MPs) have become an emerging new pollutant of rising concern due to the exponential growth of plastics in consumer products. Most MP and nanoplastic pollution comes from the fragmentation of plastics through mechanical stress, chemical reactions and biological degradation that occurs during use and after disposal. Models predicting the generation and behavior of MP in the environment are developing, however there is lack of data to predict the rates of MP generation as a function of the abrasive forces. A method to deliver scalable, quantitative release rates of MPs during mechanical stress throughout a plastic's life cycle (e.g., sanding, chewing, river and ocean disposal) is described. A custom abrasion machine was built with features to provide data to calculate power input. The generation rate of MPs through abrasion was tested for the following 3D printed polymers: polylactic acid (PLA), polycarbonate (PC), thermoplastic polyurethane 85A (TPU), polyethylene glycol terephthalate (PETG), high-impact polystyrene (HIPS), and nylon. Each material underwent tensile strength material tests to identify which mechanical properties drive their abrasion rate. Abrasion rate was not observed to correlate to macroscopic mechanic properties. Results indicate that the order of abrasion from most to least were HIPS, nylon, PC, PLA, PETG, and then TPU. This study will help comprehend and provide data to understand generation rates of MPs from consumer plastic products and macro-plastic debris. This will be instrumental in helping to better understand the release of MPs and nanoplastics into the environment and to provide data for fate and transport models, especially in order to predict the amount of plastic entering water systems. MP generation rates and power inputs can be correlated with each plastic's use to inform which release the most MPs and how to better change these products in order to reduce pollution in water sources.

Quantifying Mechanical Abrasion of MWCNT Nanocomposites Used in 3D Printing: Influence of CNT Content on Abrasion Products and Rate of Microplastic Production.

Manufactured nanomaterials (MNMs) are incorporated as "nanofillers" into consumer products to enhance properties of interest. Multiwalled carbon nanotubes (MWCNTs) are known for their unique properties and have many applications in polymers. However, the release of MWCNTs during the nanoenabled product life cycle is concerning. During the use phase, mechanical stresses can produce fragmented materials containing MNMs. The degree of MNM release, the resulting exposure to these materials, and the potential impacts of their release are active research topics. In this study, we describe methodological improvements to study the abrasion of plastics containing MNMs (nanocomposites) and report on characteristics of abrasion products produced and rates of microplastic production. The abrasion device developed for this work allows for the measurement of power inputs to determine scaled release rates. Abrasion rates for plastics used in 3D printing were found to be 0.27 g/m2/s for the PETG polymer and 0.3 g/m2/s for the 2% MWCNT-PETG nanocomposite. Embedded and protuberant MWCNTs appeared to impact the particle size, shape, hydrophobicity, and surface charge of the microplastics, while the inclusion of MWCNTs had a small effect on microplastic production. Measurements of power input to the abrasion process provided a basis for estimating microplastic production rates for these nanocomposites.

Importance of the number emission factor of combustion-generated aerosols from nano-enabled products.

Accidental or open waste burning and incineration of nano-enabled products (NEPs) might lead to the release of incidental aerosols in the nano size range into the environment resulting in harmful effects on humans. We have investigated combustion-generated aerosol release during accidental burning for several real-life NEPs such as paints with silica (SiO2) and spruce wood panels containing SiO2 and Fe2O3 nanomaterials (NMs), paper with SiO2 and Fe2O3 NMs and polymeric composites with CuPhthtalocyanine NMs in poly lactic acid (PLA), polyamide 6 (PA6) and thermoplastic pol-urethane (TPU) matrices. Chemical compositions, aerosols number emission factors (nefs) and concentrations of the signature elements of the NMs of the combustion-generated aerosols were investigated. In addition, the residual ash was analyzed. The outcomes of this study shed light on how NM and matrix types influenced the properties of the released aerosols. Based on our results it was established that the combustion-generated aerosols were composed of transformed NMs with modified physical-chemical characteristics compared to the pristine NMs. In addition to aerosols with transformed NMs, there were also particles due to incomplete combustion of the matrix. Types of the pristine NMs and matrices affected the characteristics of the released aerosols. Since the effect of the aerosols is related to the inhaled aerosol number concentration, the nef is an important parameter. Our results showed that the nefs in the size range of 5.6 to 560 nm depended strongly on the type of combusted NEP, which indicated that the NEPs could be categorized according to their potential to release aerosols in this size range when they were burnt. The generated release data facilitate the assessment of human and environmental exposure and the associated risk assessment of combustion-generated aerosols from NEPs.

Can an InChI for Nano Address the Need for a Simplified Representation of Complex Nanomaterials across Experimental and Nanoinformatics Studies?

Chemoinformatics has developed efficient ways of representing chemical structures for small molecules as simple text strings, simplified molecular-input line-entry system (SMILES) and the IUPAC International Chemical Identifier (InChI), which are machine-readable. In particular, InChIs have been extended to encode formalized representations of mixtures and reactions, and work is ongoing to represent polymers and other macromolecules in this way. The next frontier is encoding the multi-component structures of nanomaterials (NMs) in a machine-readable format to enable linking of datasets for nanoinformatics and regulatory applications. A workshop organized by the H2020 research infrastructure NanoCommons and the nanoinformatics project NanoSolveIT analyzed issues involved in developing an InChI for NMs (NInChI). The layers needed to capture NM structures include but are not limited to: core composition (possibly multi-layered); surface topography; surface coatings or functionalization; doping with other chemicals; and representation of impurities. NM distributions (size, shape, composition, surface properties, etc.), types of chemical linkages connecting surface functionalization and coating molecules to the core, and various crystallographic forms exhibited by NMs also need to be considered. Six case studies were conducted to elucidate requirements for unambiguous description of NMs. The suggested NInChI layers are intended to stimulate further analysis that will lead to the first version of a "nano" extension to the InChI standard.

Differential Reactivity of Copper- and Gold-Based Nanomaterials Controls Their Seasonal Biogeochemical Cycling and Fate in a Freshwater Wetland Mesocosm.

Reliable predictions of the environmental fate and risk of engineered nanomaterials (ENMs) require a better understanding of ENM reactivity in complex, biologically active systems for chronic low-concentration exposure scenarios. Here, simulated freshwater wetland mesocosms were dosed with ENMs to assess how their reactivity and seasonal changes in environmental parameters influence ENM fate in aquatic systems. Copper-based ENMs (Kocide), known to dissolve in water, and gold nanoparticles (AuNPs), stable against dissolution in the absence of specific ligands, were added weekly to mesocosm waters for 9 months. Metal accumulation and speciation changes in the different environmental compartments were assessed over time. Copper from Kocide rapidly dissolved likely associating with organic matter in the water column, transported to terrestrial soils and deeper sediment where it became associated with organic or sulfide phases. In contrast, Au accumulated on/in the macrophytes where it oxidized and transferred over time to surficial sediment. A dynamic seasonal accumulation and metal redox cycling were found between the macrophyte and the surficial sediment for AuNPs. These results demonstrate the need for experimental quantification of how the biological and chemical complexity of the environment, combined with their seasonal variations, drive the fate of metastable ENMs.

Kinome screen of ferroptosis reveals a novel role of ATM in regulating iron metabolism.

Ferroptosis is a specialized iron-dependent cell death that is associated with lethal lipid peroxidation. Modulation of ferroptosis may have therapeutic potential since it has been implicated in various human diseases as well as potential antitumor activities. However, much remains unknown about the underlying mechanisms and genetic determinants of ferroptosis. Given the critical role of kinases in most biological processes and the availability of various kinase inhibitors, we sought to systemically identify kinases essential for ferroptosis. We performed a forward genetic-based kinome screen against ferroptosis in MDA-MB-231 cells triggered by cystine deprivation. This screen identified 34 essential kinases involved in TNFα and NF-kB signaling. Unexpectedly, the DNA damage response serine/threonine kinase ATM (mutated in Ataxia-Telangiectasia) was found to be essential for ferroptosis. The pharmacological or genetic inhibition of ATM consistently rescued multiple cancer cells from ferroptosis triggered by cystine deprivation or erastin. Instead of the canonical DNA damage pathways, ATM inhibition rescued ferroptosis by increasing the expression of iron regulators involved in iron storage (ferritin heavy and light chain, FTH1 and FTL) and export (ferroportin, FPN1). The coordinated changes of these iron regulators during ATM inhibition resulted in a lowering of labile iron and prevented the iron-dependent ferroptosis. Furthermore, we found that ATM inhibition enhanced the nuclear translocation of metal-regulatory transcription factor 1 (MTF1), responsible for regulating expression of Ferritin/FPN1 and ferroptosis protection. Genetic depletion of MTF-1 abolished the regulation of iron-regulatory elements by ATM and resensitized the cells to ferroptosis. Together, we have identified an unexpected ATM-MTF1-Ferritin/FPN1 regulatory axis as novel determinants of ferroptosis through regulating labile iron levels.

Groundwater Chemistry Has a Greater Influence on the Mobility of Nanoparticles Used for Remediation than the Chemical Heterogeneity of Aquifer Media.

The application of nanoscale zerovalent iron (nano-ZVI) particles for groundwater remediation has spurred research into the influence of the collector heterogeneity on the nano-ZVI mobility. The chemical heterogeneity of surfaces within aquifer media affects their surface charge distribution and their affinity for nano-ZVI. The groundwater chemistry affects the properties of both aquifer surfaces and the nano-ZVI particles. Commercial poly(acrylic acid)-coated nano-ZVI (PAA-nano-ZVI) particles were tested in column experiments using two solution chemistries and silica collectors with different degrees of chemical heterogeneity, achieved by ferrihydrite coating. A porous media filtration model was used to determine the attachment efficiency of PAA-nano-ZVI particles, and the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was used to describe the interactions between PAA-nano-ZVI particles and the aquifer "collectors". The mobility of PAA-nano-ZVI particles suspended in ultrapure water depended on the extent of ferrihydrite coating on the collector surfaces. The mobility of PAA-nano-ZVI particles under environmentally relevant conditions was independent of the collector chemical heterogeneity. The size of PAA-nano-ZVI aggregates doubled, inducing gravitational sedimentation and possibly straining as mechanisms of particle deposition. There was no repulsive energy barrier between particles and collectors, and the DLVO theory was unable to explain the observed particle attachment. Our results suggest that the groundwater chemistry has a greater influence on the mobility of PAA-nano-ZVI particles than the collector chemical heterogeneity. A better understanding of polymer adsorption to nanoparticles and its conformation under natural groundwater conditions is needed to further elucidate nanoparticle-collector interactions.

Formulation and Validation of a Functional Assay-Driven Model of Nanoparticle Aquatic Transport.

Here, we present a model for the prediction of nanoparticle fate in aquatic environments, parametrized using functional assays that take into account conditions of the environmental media and nanoparticle properties. The model was used to explore scenarios for five nanomaterials in a freshwater wetland setting and compared with experimental results obtained in mesocosm studies. Material characteristics used in the model were size, density, dissolution rate constants, and surface attachment efficiencies. Model predictions and experimentally measured removal rate constants from the water column were strongly correlated, with Pearson correlation coefficient 0.993. Further, the model predicted removal rate constants quantitively very close to measured rates. Of particular importance for accurate predictions were two key processes beyond the usual heteroaggregation with suspended solids. These were homoaggregation of nanomaterials and nanomaterial attachment to aquatic plant surfaces. These results highlight the importance of including all relevant aggregation and deposition processes over short time scales for nanoparticle transport, while demonstrating the utility of functional assays for surface attachment as model inputs.

Incorporation of Cellulose Nanocrystals (CNCs) into the Polyamide Layer of Thin-Film Composite (TFC) Nanofiltration Membranes for Enhanced Separation Performance and Antifouling Properties.

To achieve greater separation performance and antifouling properties in a thin-film composite (TFC) nanofiltration membrane, cellulose nanocrystals (CNCs) were incorporated into the polyamide layer of a TFC membrane for the first time. The results of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the successful formation of the CNC-polyamide composite layer. Surface characterization results revealed differences in the morphologies of the CNC-TFC membranes compared with a control membrane (CNC-TFC-0). Streaming potential measurements and molecular weight cutoff (MWCO) characterizations showed that the CNC-TFC membranes exhibited a greater negative surface charge and a smaller MWCO as the CNC content increased. The CNC-TFC membranes showed enhanced hydrophilicity and increased permeability. With the incorporation of only 0.020 wt % CNCs, the permeability of the CNC-TFC membrane increased by 60.0% over that of the polyamide TFC without CNC. Rejection of Na2SO4 and MgSO4 by the CNC-TFC membranes was similar to that observed for the CNC-TFC-0 membrane, at values of approximately 98.7% and 98.8%, respectively, indicating that divalent salt rejection was not sacrificed. The monovalent ion rejection tended to increase as the CNC content increased. In addition, the CNC-TFC membranes exhibited enhanced antifouling properties due to their increased hydrophilicity and more negatively charged surfaces.

Gold nanoparticle biodissolution by a freshwater macrophyte and its associated microbiome.

Predicting nanoparticle fate in aquatic environments requires mimicking of ecosystem complexity to observe the geochemical processes affecting their behaviour. Here, 12 nm Au nanoparticles were added weekly to large-scale freshwater wetland mesocosms. After six months, ~70% of Au was associated with the macrophyte Egeria densa, where, despite the thermodynamic stability of Au0 in water, the pristine Au0 nanoparticles were fully oxidized and complexed to cyanide, hydroxyls or thiol ligands. Extracted biofilms growing on E. densa leaves were shown to dissolve Au nanoparticles within days. The Au biodissolution rate was highest for the biofilm with the lowest prevalence of metal-resistant taxa but the highest ability to release cyanide, known to promote Au0 oxidation and complexation. Macrophytes and the associated microbiome thus form a biologically active system that can be a major sink for nanoparticle accumulation and transformations. Nanoparticle biotransformation in these compartments should not be ignored, even for nanoparticles commonly considered to be stable in the environment.

Size-Based Differential Transport, Uptake, and Mass Distribution of Ceria (CeO2) Nanoparticles in Wetland Mesocosms.

Trace metals associated with nanoparticles are known to possess reactivities that are different from their larger-size counterparts. However, the relative importance of small relative to large particles for the overall distribution and biouptake of these metals is not as well studied in complex environmental systems. Here, we have examined differences in the long term fate and transport of ceria (CeO2) nanoparticles of two different sizes (3.8 vs 185 nm), dosed weekly to freshwater wetland mesocosms over 9 months. While the majority of CeO2 particles were detected in soils and sediments at the end of nine months, there were significant differences observed in fate, distribution, and transport mechanisms between the two materials. Small nanoparticles were removed from the water column primarily through heteroaggregation with suspended solids and plants, while large nanoparticles were removed primarily by sedimentation. A greater fraction of small particles remained in the upper floc layers of sediment relative to the large particles (31% vs 7%). Cerium from the small particles were also significantly more bioavailable to aquatic plants (2% vs 0.5%), snails (44 vs 2.6 ng), and insects (8 vs 0.07 µg). Small CeO2 particles were also significantly reduced from Ce(IV) to Ce(III), while aquatic sediments were a sink for untransformed large nanoparticles. These results demonstrate that trace metals originating from nanoscale materials have much greater potential than their larger counterparts to distribute throughout multiple compartments of a complex aquatic ecosystem and contribute to the overall bioavailable pool of the metal for biouptake and trophic transfer.

Non-linear release dynamics for a CeO2 nanomaterial embedded in a protective wood stain, due to matrix photo-degradation.

The release of CeO2-bearing residues during the weathering of an acrylic stain enriched with CeO2 nanomaterial designed for wood protection (Nanobyk brand additive) was studied under two different scenarios: (i) a standard 12-weeks weathering protocol in climate chamber, that combined condensation, water spraying and UV-visible irradiation and (ii) an alternative accelerated 2-weeks leaching batch assay relying on the same weathering factors (water and UV), but with a higher intensity of radiation and immersion phases. Similar Ce released amounts were evidenced for both scenarios following two phases: one related to the removal of loosely bound material with a relatively limited release, and the other resulting from the degradation of the stain, where major release occurred. A non-linear evolution of the release with the UV dose was evidenced for the second phase. No stabilization of Ce emissions was reached at the end of the experiments. The two weathering tests led to different estimates of long-term Ce releases, and different degradations of the stain. Finally, the photo-degradations of the nanocomposite, the pure acrylic stains and the Nanobyk additive were compared. The incorporation of Nanobyk into the acrylic matrix significantly modified the response of the acrylic stain to weathering.

Biochar and activated carbon act as promising amendments for promoting the microbial debromination of tetrabromobisphenol A.

The increasing occurrence of tetrabromobisphenol A (TBBPA) in the environment is raising questions about its potential environmental health impacts as it has been shown to cause various deleterious effects in humans. The fact that the highest concentrations of TBBPA have been reported in wastewater sludge is concerning as effluent discharge and biosolids land application are likely a route by which TBBPA can be further disbursed to the environment. Our objectives in this study were to evaluate the effect of biochar (BC) and activated carbon (AC) in promoting the biodegradation of TBBPA, and characterize the response of anaerobic sludge microbial communities following amendments. Both carbonaceous amendments were found to promote the reductive debromination of TBBPA. Nearly complete transformation of TBBPA to BPA was observed in the amended reactors ∼20 days earlier than in the control reactors. In particular, the transformation of diBBPA to monoBBPA, which appears to be the rate-limiting step, was accelerated in the presence of either amendment. Overall, microbial taxa responding to the amendments, i.e., 'sensitive responders', represented a small proportion of the community (i.e., 7.2%), and responded positively. However, although both amendments had a similar effect on TBBPA degradation, the taxonomic profile of the sensitive responders differed greatly from one amendment to the other. BC had a taxonomically broader and slightly more pronounced effect than AC. This work suggests that BC and AC show great potential to promote the biodegradation of TBBPA in anaerobic sludge, and their integration into wastewater treatment processes may be helpful for removing TBBPA and possibly other emerging hydrophobic contaminants.

Modeling the Concentration of Volatile and Semivolatile Contaminants in Direct Contact Membrane Distillation (DCMD) Product Water.

Direct contact membrane distillation (DCMD) is an emerging water treatment technology that has high salt rejection; however, its commercialization potential for applications such as seawater desalination or industrial wastewater reuse may be limited by low rejection of volatile and semivolatile contaminants. In this manuscript, a contaminant concentration (CC) model describing the transport of volatile and semivolatile contaminants for DCMD systems was developed and validated using data from the bench-scale DCMD treatment of synthetic wastewaters. The DCMD tests showed that the more volatile contaminants (methyl-tert-butyl ether, acetone, pentanone, butanol, and hexanol) accumulated in the permeate collection stream at greater concentrations than in the feed stream. The validated CC model (average normalized root mean squared error ≤11.3%) was then used to evaluate the product water quality from the large-scale DCMD treatment of oil and gas produced waters. The modeled product water contaminant concentrations exceeded the Environmental Protection Agency limits for discharging to publicly owned treatment works. This indicated that DCMD treatment of produced waters may require additional processing to meet discharge requirements.

Impact of Sodium Humate Coating on Collector Surfaces on Deposition of Polymer-Coated Nanoiron Particles.

The affinity between nanoscale zerovalent iron (nano-ZVI) and mineral surfaces hinders its mobility, and hence its delivery into contaminated aquifers. We have tested the hypothesis that the attachment of poly(acrylic acid)-coated nano-ZVI (PAA-nano-ZVI) to mineral surfaces could be limited by coating such surfaces with sodium (Na) humate prior to PAA-nano-ZVI injection. Na humate was expected to form a coating over favorable sites for PAA-nano-ZVI attachment and hence reduce the affinity of PAA-nano-ZVI for the collector surfaces through electrosteric repulsion between the two interpenetrating charged polymers. Column experiments demonstrated that a low concentration (10 mg/L) Na humate solution in synthetic water significantly improved the mobility of PAA-nano-ZVI within a standard sand medium. This effect was, however, reduced in more heterogeneous natural collector media from contaminated sites, as not an adequate amount of the collector sites favorable for PAA-nano-ZVI attachment within these media appear to have been screened by the Na humate. Na humate did not interact with the surfaces of acid-washed glass beads or standard Ottawa sand, which presented less surface heterogeneity. Important factors influencing the effectiveness of Na humate application in improving PAA-nano-ZVI mobility include the solution chemistry, the Na humate concentration, and the collector properties.

Enhanced transportability of zero valent iron nanoparticles in aquifer sediments: surface modifications, reactivity, and particle traveling distances.

In this study, we assessed the transportability of zero valent iron nanoparticles (nano-Fe0) coated with different organics (carboxy methyl cellulose (CMC), poly acrylic acid (PAA), and xanthan gum) in standard porous sand and in real aquifer sediments. Our results suggest that the organic surface coatings optimized for nano-Fe0 in porous sand media do not necessarily reflect the same transportability in real field aquifer sediment. Xanthan gum-coated nano-Fe0 showed highest transportability in standard porous sand, but the performance was much lower in real aquifer sediment, whereas the PAA-coated nano-Fe0 particle showed better transportability both in aquifer sediment and in porous sand media. Nano-Fe0 without organic surface coating exhibited very low transportability and was largely retained by the porous medium. Our results suggest that the molecular weight and surface charge density of the organic may play a role in transportability of these nanoparticles. To assess the impact of organic coating on the nanoparticle reactivity with contaminants, we also conducted batch tests to follow TCE degradation using different surface coatings and found no significant difference albeit a minor delay in kinetics. Using theoretical calculations, we also estimated the potential distance traveled by nanoparticles in porous sand as well as in aquifer sediment. Our results suggest that using xanthan gum and PAA as surface coating, nano-Fe0 could travel up to 9.8 and 4.1 m, respectively, in the porous sand media as compared to 0.2 and 0.9 m in real aquifer sediment, respectively. Graphical abstract Nanoparticle mobility in porous sand vs and aquifer sediment.

Comparison of Hydrophilicity and Mechanical Properties of Nanocomposite Membranes with Cellulose Nanocrystals and Carbon Nanotubes.

The inherent properties of hydrophilicity and mechanical strength of cellulose nanocrystals (CNCs) make them a possible alternative to carbon nanotubes (CNTs) that may present fewer objections to application water-treatment membranes. In this work, the hydrophilicity and mechanical properties of CNCs and CNTs nanocomposite poly(ether sulfone) (PES) membranes were characterized and compared. Membrane pore geometry was analyzed by scanning electron microscopy (SEM). Overall porosity and mean pore radius were calculated based on a wet-dry method. Results showed that PES polymers were loosely packed in the top layer of both the CNC- and CNT-composite membranes (CNC-M and CNT-M). The porosity of the CNC-M was greater than that of the CNT-M. Membrane hydrophilicity, measured by water-contact angle, free energy of cohesion, and water flux, was increased through the addition of either CNCs or functionalized CNTs to an otherwise hydrophobic polymer membrane. The hydrophilicity of the CNC-M was greater than the CNT-M. In addition, the Young's modulus and tensile strength was enhanced for both the CNC-M and CNT-M. While smaller concentrations of CNTs were required to achieve an equal increase in Young's modulus compared with the CNCs, the elasticity of the CNC-composite membranes was greater.