Clay minerals affect the stability of surfactant-facilitated carbon nanotube suspensions

Carbon nanotubes (CNTs), because of their wide application, will inevitably enter aquatic systems, but the fate and transport of their suspensions in the environment are largely unknown. Clay minerals are expected to interact with CNT suspensions, affecting their fate and bioavailability. This study investigated the influence of clay minerals (kaolinite and montmorillonite) on the stability of surfactant (SDBS, CTAB, and TX100) facilitated multiwalled CNT (MWCNT) suspensions. Adsorption of the surfactants by MWCNTs and clay minerals was also examined. This is a first study on the interaction between clay minerals and surfactant-CNT suspensions. Sorption of SDBS by clay minerals and MWCNTs followed the order MWCNTs > montmorillonite approximately kaolinite; but sorption of CTAB and TX100 followed the order montmorillonite > MWCNTs > kaolinite. For SDBS suspended MWCNTs, introduction of montmorillonite and kaolinite could not change their stability; for CTAB suspended MWCNTs, both montmorillonite and kaolinite greatly deposited the suspended MWCNTs; for TX100 suspended MWCNTs, montmorillonite could partially deposit the suspended MWCNTs, whereas kaolinite showed minimal effect. Two mechanisms of clay minerals affecting MWCNT suspensions are (1) removal of surfactants by clay minerals from solution and MWCNT surface and (2) bridging between clay mineral and MWCNTs by surfactant.     

Are carbon nanotube effects on green algae caused by shading and agglomeration?

Due to growing production, carbon nanotubes (CNT) may soon be found in a broad range of products and thus in the environment. In this work, an algal growth test was developed to determine effects of pristine and oxidized CNT on the green algae Chlorella vulgaris and Pseudokirchneriella subcapitata. CNT suspensions were prepared in algal test medium and characterized taking into account the suspension age, the reduced light transmittance of nanoparticle suspensions defined as shading of CNT and quantified by UV/vis spectroscopy, and the agglomeration of the CNT and of the algal cells. Growth inhibition and photosynthetic activity were investigated as end points. Growth of C. vulgaris was inhibited with effect concentrations of 50% (EC(50)) values of 1.8 mg CNT/L and of 24 mg CNT/L in well dispersed and in agglomerated suspensions, respectively, and 20 mg CNT/L and 36 mg CNT/L for P. subcapitata, respectively. However, the photosynthetic activity was not affected. Growth inhibition was highly correlated with the shading of CNT and the agglomeration of algal cells. This suggests that the reduced algal growth might be caused mainly by indirect effects, i.e. by reduced availability of light and different growth conditions caused by the locally elevated algal concentration inside of CNT agglomerates.     

Effects of polyethyleneimine-mediated functionalization of multi-walled carbon nanotubes on earthworm bioaccumulation and sorption by soils

Carbon nanotubes (CNTs) are often modified for different intended potential applications to enhance their aqueous stability or change properties such as surface charge. Such changes may also profoundly impact their environmental behaviors. Herein, we report the effects of modifying (14)C-labeled multiwalled carbon nanotubes (MWCNTs) with polyetheyleneimine (PEI) surface coatings to render them more stable in solution and to give them positive, negative, or neutral surface charges. These carbon nanotubes were used to test their sorption by soils and uptake and elimination behaviors by earthworms. Sorption results indicate nearly linear sorption isotherms for regular MWCNTs and nonlinear isotherms for modified MWCNTs, indicating that the PEI coatings influenced MWCNT interactions with soils. Nevertheless, there were minimal differences in the sorption results among the different soils for each type of nanotube despite differences in the soil organic carbon and cation exchange capacities. Differences in uptake behaviors by earthworms were not apparent among different types of PEI-MWCNTs and MWCNTs with limited absorption into organism tissues consistently observed. Elimination patterns were well fit with an exponential decay model suggesting that the worms can readily eliminate any accumulated MWCNTs.     

Analysis of Saccharomyces cerevisiae null allele strains identifies a larger role for DNA damage versus oxidative stress pathways in growth inhibition by selenium

Selenium toxicity is a growing environmental concern due to widespread availability of high-dose selenium supplements and the development of high-selenium agricultural drainage basins. To begin to analyze the effects of selenium toxicity at the genetic level, we have systematically determined which genes are involved in responding to high environmental selenium using a collection of viable haploid null allele strains of Saccharomyces cerevisiae representing three major stress pathways: the RAD9-dependent DNA repair pathway, the RAD6/RAD18 DNA damage tolerance pathway, and the oxidative stress pathway. A total of 53 null allele strains were tested for growth defects in the presence of a range of sodium selenite and selenomethionine (SeMet) concentrations. Our results show that approximately 64-72% of the strains lacking RAD9-dependent DNA repair or RAD6/RAD18 DNA damage tolerance pathway genes show reduced growth in sodium selenite versus approximately 28-36% in SeMet. Interestingly both compounds reduced growth in approximately 21-25% of the strains lacking oxidative stress genes. These data suggest that both selenite and SeMet are likely inducing DNA damage by generating reactive species. The anticipated effects of loss of components of the oxidative stress pathway were not observed, likely due to apparent redundancies in these gene products that may keep the damaging effects in check.     

Pulmonary surfactant suppressed phenanthrene adsorption on carbon nanotubes through solubilization and competition as examined by passive dosing technique

Adsorption of phenanthrene on carbon nanotubes (CNTs) was examined in the presence of pulmonary surfactant (Curosurf) and its main components, dipalmitoyl phosphatidylcholine (DPPC) and bovine serum albumin (BSA). A passive-dosing method based on equilibrium partitioning from a preloaded polymer was successfully employed to measure phenanthrene binding and speciation at controlled freely dissolved concentrations while avoiding phase separation steps. Curosurf, DPPC, and BSA could all linearly solubilize phenanthrene, and phenanthrene solubilization by Curosurf was 4 times higher than individual components (DPPC or BSA). In the presence of Curosurf, DPPC or BSA, adsorption of phenanthrene by multiwalled CNTs (MWCNTs) was suppressed, showing competitive adsorption between pulmonary surfactant (or DPPC, BSA) and phenanthrene. Competitive adsorption between Curosurf and phenanthrene was the strongest. Therefore, when phenanthrene-adsorbed CNTs enter the respiratory tract, phenanthrene can be desorbed due to both solubilization and competition. The bioaccessibility of phenanthrene adsorbed on three MWCNTs in the respiratory tract would be positively related to the size of their outer diameters. Moreover, the contribution of solubilization and competition to desorption of phenanthrene from MWCNTs was successfully separated for the first time. These findings demonstrate the two mechanisms on how pulmonary surfactants can enhance desorption and thus possibly biological absorption of phenanthrene adsorbed on CNTs.     

Influence of surface oxidation of multiwalled carbon nanotubes on the adsorption affinity and capacity of polar and nonpolar organic compounds in aqueous phase

Adsorption of organic contaminants on carbon nanotubes (CNTs) is a critical behavior in the environmental application of CNTs as sorbents and in the environmental risk assessment of both organic contaminants and CNTs. Oxidation of CNTs may introduce oxygen-containing groups on CNTs' surface and then alter the adsorption of organic contaminants. In this study, adsorption of polar and nonpolar organic compounds on four multiwalled carbon nanotubes (MWCNTs) containing varied amounts of surface oxygen-containing groups were investigated to examine the influence of CNTs' surface oxidation on adsorption. We observed that surface oxidation of MWCNTs reduced the surface area-normalized adsorption capacity of organic compounds significantly because of the competition of water molecules but did not alter the adsorption affinity. The interactions (i.e., hydrophobic effect, π-π bonds, and hydrogen bonds) and the interaction strength for adsorption of organic molecules on MWCNTs could not be altered by the surface oxidation of MWCNTs and thus were responsible for the unaltered adsorption affinity. In addition, the decrease of surface area-normalized adsorption capacity of the organic compound with more polarity and higher adsorption affinity by surface oxidation was less because of the heterogeneous nature of hydrophilic sites of MWCNTs' surface.     

Impact of porous media grain size on the transport of multi-walled carbon nanotubes

Nanoparticles possess unique physical, electrical, and chemical properties which make them attractive for use in a wide range of consumer products. Through their manufacturing, usage, and eventual disposal, nanoparticles are expected to ultimately be released to the environment after which point they may pose environmental and human health risks. One critical component of understanding and modeling those potential risks is their transport in the subsurface environment. This study investigates the mobility of one important nanoparticle (multi-walled carbon nanotubes or MWCNTs) through porous media, and makes the first measurements on the impact of mean collector grain size (d(50)) on MWCNT retention. Results from one-dimensional column experiments conducted under various physical and chemical conditions coupled with results of numerical modeling assessed the suitability of traditional transport models to predict MWCNT mobility. Findings suggest that a dual deposition model coupled with site blocking greatly improves model fits compared to traditional colloid filtration theory. Of particular note is that the MWCNTs traveled through porous media ranging in size from fine sand to silt resulting in normalized concentrations of MWCNTs in the effluent in excess of 60% of the influent concentration.     

油相结构化对大豆蛋白藻油纳米乳液氧化稳定性的影响

利用蜂蜡结构化藻油结合大豆分离蛋白-甜菊糖（soy protein isolate-stevioside,SPI-STE）复合体系的乳化特性,制备高稳态的藻油纳米乳液体系。藻油凝胶的微观结构观察、热性质测试以及流变学分析表明,当藻油中蜂蜡添加量达到4%(m/m)时,大量晶体组装成稳固的网络结构,从而构筑出稳定的油凝胶。进一步以SPI-STE为稳定剂制备藻油纳米乳液,研究了藻油结构化对纳米乳液形成及稳定性的影响。结果表明,油相中添加蜂蜡对纳米乳液的形成没有显著影响。随着藻油中蜂蜡质量分数的增大（0%～6%）,乳液的物理稳定性逐渐提高;但在高蜂蜡添加量（8%）下,刚性较强的凝胶网络破坏了油滴界面层,乳液稳定性变差。热促氧化及光促氧化结果显示,蜂蜡油相结构化明显提高了纳米乳液的氧化稳定性,其中油相中含有6%蜂蜡的样品延缓氧化的效果最明显。本研究可为食品工业构建高稳态的藻油纳米乳液载体及产品提供一定技术支持。     

Mechanism of silver nanoparticle toxicity is dependent on dissolved silver and surface coating in Caenorhabditis elegans

The rapidly increasing use of silver nanoparticles (Ag NPs) in consumer products and medical applications has raised ecological and human health concerns. A key question for addressing these concerns is whether Ag NP toxicity is mechanistically unique to nanoparticulate silver, or if it is a result of the release of silver ions. Furthermore, since Ag NPs are produced in a large variety of monomer sizes and coatings, and since their physicochemical behavior depends on the media composition, it is important to understand how these variables modulate toxicity. We found that a lower ionic strength medium resulted in greater toxicity (measured as growth inhibition) of all tested Ag NPs to Caenorhabditis elegans and that both dissolved silver and coating influenced Ag NP toxicity. We found a linear correlation between Ag NP toxicity and dissolved silver, but no correlation between size and toxicity. We used three independent and complementary approaches to investigate the mechanisms of toxicity of differentially coated and sized Ag NPs: pharmacological (rescue with trolox and N-acetylcysteine), genetic (analysis of metal-sensitive and oxidative stress-sensitive mutants), and physicochemical (including analysis of dissolution of Ag NPs). Oxidative dissolution was limited in our experimental conditions (maximally 15% in 24 h) yet was key to the toxicity of most Ag NPs, highlighting a critical role for dissolved silver complexed with thiols in the toxicity of all tested Ag NPs. Some Ag NPs (typically less soluble due to size or coating) also acted via oxidative stress, an effect specific to nanoparticulate silver. However, in no case studied here was the toxicity of a Ag NP greater than would be predicted by complete dissolution of the same mass of silver as silver ions.     

Cooling effect of MWCNT-containing composite coatings on cotton fabrics

Multiwalled carbon nanotubes (MWCNTs) were dispersed in an aqueous solution of epichlohydrin based resin with the aid of a surfactant. The MWCNT-resin solutions were applied onto cotton fabrics to form a thin coating with different MWCNT contents (0, 11.1, 20.0, 33.3, and 50%). The thermal conductivity of the fabrics was measured based on the Newton’s law of cooling. The coating containing 50% MWCNTs showed 151% increase in the thermal conductivity. Infrared thermography was used to characterize the heating/cooling behavior of the fabrics. On contact with a 50°C hot surface, coated fabric that had 50% MWCNTs in the coating layer showed a 3.9°C lower equilibrium surface temperature than the untreated fabric. The cooling rate increased with increasing the MWCNT content within the coating layer. Such an effective cooling performance was attributed to the increased thermal conductivity and surface emissivity of the MWCNT-containing coating layer. The coating showed little influence on water contact angle of the coated fabrics, but slightly decreased the air permeability.     

Potential release pathways, environmental fate, and ecological risks of carbon nanotubes

Carbon nanotubes (CNTs) are currently incorporated into various consumer products, and numerous new applications and products containing CNTs are expected in the future. The potential for negative effects caused by CNT release into the environment is a prominent concern and numerous research projects have investigated possible environmental release pathways, fate, and toxicity. However, this expanding body of literature has not yet been systematically reviewed. Our objective is to critically review this literature to identify emerging trends as well as persistent knowledge gaps on these topics. Specifically, we examine the release of CNTs from polymeric products, removal in wastewater treatment systems, transport through surface and subsurface media, aggregation behaviors, interactions with soil and sediment particles, potential transformations and degradation, and their potential ecotoxicity in soil, sediment, and aquatic ecosystems. One major limitation in the current literature is quantifying CNT masses in relevant media (polymers, tissues, soils, and sediments). Important new directions include developing mechanistic models for CNT release from composites and understanding CNT transport in more complex and environmentally realistic systems such as heteroaggregation with natural colloids and transport of nanoparticles in a range of soils.     

Modifying mechanical properties of carbon textiles reinforced epoxy composite using multi-wall carbon nanotubes (MWCNT)

The influence of multi-walled carbon nanotubes (MWCNT) on the mechanical performance of epoxy reinforced with carbon textile was investigated. Initially, the impact of using MWCNT and its concentration on the tensile and flexural properties of the epoxy were studied. Then, the optimum concentration was applied to reinforce the epoxy and make a composite of carbon textile with five layers. It was found that an increase in the MWCNT concentration results in the enhancement of the mechanical performance of the epoxy composites. Moreover, the incorporation of 0.15 wt% epoxy, MWCNTs in the epoxy reinforced with carbon textile improve its tensile and flexural behaviour approximately by 7.56 and 8.63%, respectively, in comparison with the carbon textile composite. However, the composite weight increment is negligible.     

Improving the Surface Performance of Electrospun Air Filter Paper Using Multi-walled Carbon Nanotubes

In this study, air filter base paper (P) was used as the receiving substrate, polyvinyl alcohol (PVA) and PVA/multi-walled carbon nanotube (MWCNT) spinning solutions were used to prepare electrospun air filter papers (P-PVA and P-PVA/MWCNT, respectively). Then, P-PVA/MWCNT was calendered under different pressures. The effect of MWCNTs on the surface performance of P-PVA/MWCNT was explored and the influence of calendering technology on their structure and filtration characteristics was analyzed. Electron scanning microscope observation showed that the PVA nanofibers on the surface of P-PVA/MWCNT had no beading, and MWCNTs weakened the surface electrostatic phenomenon and had a good micromorphology. During the calendering process, with an increase in pressure, the mean pore size and surface roughness of P-PVA/MWCNT decreased, the initial resistance increased, and the filtration efficiency changed slightly.     

Effects of copper nanoparticles exposure in the mussel Mytilus galloprovincialis

CuO NPs are widely used in various industrial and commercial applications. However, little is known about their potential toxicity or fate in the environment. In this study the effects of copper nanoparticles were investigated in the gills of mussels Mytilus galloprovincialis, comparative to Cu(2+). Mussels were exposed to 10 μg Cu·L(-1) of CuO NPs and Cu(2+) for 15 days, and biomarkers of oxidative stress, metal exposure and neurotoxicity evaluated. Results show that mussels accumulated copper in gills and responded differently to CuO NPs and Cu(2+), suggesting distinct modes of action. CuO NPs induced oxidative stress in mussels by overwhelming gills antioxidant defense system, while for Cu(2+) enzymatic activities remained unchanged or increased. CuO NPs and Cu(2+) originated lipid peroxidation in mussels despite different antioxidant efficiency. Moreover, an induction of MT was detected throughout the exposure in mussels exposed to nano and ionic Cu, more evident in CuO NPs exposure. Neurotoxic effects reflected as AChE inhibition were only detected at the end of the exposure period for both forms of copper. In overall, these findings show that filter-feeding organisms are significant targets for nanoparticle exposure and need to be included when evaluating the overall toxicological impact of nanoparticles in the aquatic environment.     

Sorption of peat humic acids to multi-walled carbon nanotubes

Sorption of humic acids (HAs) from a peat soil by multiwalled carbon nanotubes (MWCNTs) was examined in this work. Sorption rate of HAs to MWCNTs was dominantly controlled by their diffusion from liquid-MWCNT boundary to MWCNT surfaces. Size exclusion chromatography analysis did not detect preferential sorption of HA fractions to MWCNTs at equilibrium, whereas the components with lower molecular weight in some HA fractions (e.g., HA1) would more preferentially be sorbed to MWCNTs at the initial sorption stage. Equilibrium sorption intensity of HAs by MWCNTs was dependent on their surface area and a sum of meso- and macropore volume. The surface area and sum of meso- and macroporosity-normalized sorption coefficient (K(d)) values of a given HA by MWCNTs increased with increasing outer diameter of MWCNTs, because MWCNTs with larger outer diameter were more strongly dispersed by HAs thereby making more sorption sites exposed for HA sorption. Van der Waals interaction between the alkyl components rather than the aromatic ones of HAs with MWCNTs was likely the key driving force for their sorption. This study highlights the sorption rate-controlling step of HAs from a same source to MWCNTs and the major factors affecting their sorption intensity at equilibrium.     

Caged multiwalled carbon nanotubes as the adsorbents for affinity-based elimination of ionic dyes

Multiwalled carbon nanotubes (MWCNTs) were used as the active elements for the first time for affinity-based elimination of ionic dyes. MWCNTs were encapsulated in cross-linked alginate (ALG) microvesicles using Ba2+ as the bridging ion. The Ba2+-alginate matrix constitutes a cage which holds the physically trapped MWCNTs. The cage carries negative charges on its surface. The cage restricts the access of anions of large molecular weight, such as humic acids, because of electrostatic repulsion. The cage also restricts the access of colloids of large size, because of size exclusion. Ionic dyes partition into the cage and then are captured by MWCNTs probably on the basis of van der Waals interactions occurring between the hexagonally arrayed carbon atoms in the graphite sheet of MWCNTs and the aromatic backbones of the dyes. As a result of these interactions the target species, namely, the ionic dyes, are eliminated efficiently by the MWCNTs of Ba2+-ALG/MWCNT composite adsorbents. The adsorptive capacities for elimination of acridine orange, ethidium bromide, eosin bluish, and orange G (the model species used for this study) were found as high as 0.44, 0.43, 0.33, and 0.31 micromol, respectively, for 1.0 mg of the caged MWCNTs. Adsorptive experiments with carbon nanofibers and activated carbons as the adsorbents were also performed. The MWCNT-based adsorbents provided the best capability for the affinity-based elimination of these targeted species. Biocompatibility experiments performed in vitro and in vivo provided promising results, suggesting potential applications of the caged MWCNTs in in situ environmental remediation.     

Differential Oxidative Stress of Octahedral and Cubic Cu(2)O Micro/Nanocrystals to Daphnia magna

This study attempts to understand the impact of different shapes of an individual micro/nanomaterial on their biotoxicities to aquatic organisms. Two differently shaped Cu(2)O micro/nanocrystals (cubes and octahedrons with side lengths of 900 nm) were exposed to Daphnia magna for 72 h, afterward several antioxidant biomarkers such as reactive oxygen species (ROS), catalase (CAT), total antioxidant capacity (T-AOC), and malondialdehyde (MDA) in D. magna were measured. We demonstrated the differential influences of two crystallographic Cu(2)O nanocrystals on the antioxidant process. Specifically, octahedral Cu(2)O nanocrystals showed a higher level of oxidative stress, possibly because of its larger surface area and higher reaction activity of the octahedron. The biomarker results further showed that the oxidative stress and antioxidant mechanism process involved three stages-antioxidant response, oxidation inhibition, and antioxidant inactivation. Furthermore, the accumulation of MDA was mainly responsible for the ROS-induced toxicity.     

Roles of stress response-related signaling and its contribution to the toxicity of zearalenone in mammals

Zearalenone (ZEA) is a mycotoxin frequently found in cereal crops and cereal-derived foodstuffs worldwide. It affects plant productivity, and is also a serious hazard to humans and animals if being exposed to food/feed contaminated by ZEA. Studies over the last decade have shown that the toxicity of ZEA in animals is mainly mediated by the various stress responses, such as endoplasmic reticulum (ER) stress, oxidative stress, and others. Accumulating evidence shows that oxidative stress and ER stress signaling are actively implicated in and contributes to the pathophysiology of various diseases. Biochemically, the deleterious effects of ZEA are associated with apoptosis, DNA damage, and lipid peroxidation by regulating the expression of genes implicated in these biological processes. Despite these findings, the underlying mechanisms responsible for these alterations remain unclear. This review summarized the characteristics, metabolism, toxicity and the deleterious effects of ZEA exposure in various tissues of animals. Stress response signaling implicated in the toxicity as well as potential therapeutic options with the ability to reduce the deleterious effects of ZEA in animals were highlighted and discussed.     

Exposure of engineered nanoparticles to human lung epithelial cells: influence of chemical composition and catalytic activity on oxidative stress

The chemical and catalytic activity of nanoparticles has strongly contributed to the current tremendous interest in engineered nanomaterials and often serves as a guiding principle for the design of functional materials. Since it has most recently become evident that such active materials can enter into cells or organisms, the present study investigates the level of intracellular oxidations after exposure to iron-, cobalt-, manganese-, and titania-containing silica nanoparticles and the corresponding pure oxides in vitro. The resulting oxidative stress was quantitatively measured as the release of reactive oxygen species (ROS). The use of thoroughly characterized nanoparticles of the same morphology, comparable size, shape, and degree of agglomeration allowed separation of physical (rate of particle uptake, agglomeration, sedimentation) and chemical effects (oxidations). Three sets of control experiments elucidated the role of nanoparticles as carriers for heavy metal uptake and excluded a potential interference of the biological assay with the nanomaterial. The present results indicate that the particles could efficiently enter the cells by a Trojan-horse type mechanism which provoked an up to eight times higher oxidative stress in the case of cobalt or manganese if compared to reference cultures exposed to aqueous solutions of the same metals. A systematic investigation on iron-containing nanoparticles as used in industrial fine chemical synthesis demonstrated that the presence of catalytic activity could strongly alter the damaging action of a nanomaterial. This indicates that a proactive development of nanomaterials and their risk assessment should consider chemical and catalytic properties of nanomaterials beyond a mere focus on physical properties such as size, shape, and degree of agglomeration.     

The effect of multiwalled carbon nanotube (MWCNT) ratio on electrical properties and electromagnetic shielding effectiveness of PA 6/MWCNT-coated cotton fabrics

Polyamide 6 (PA 6)/multiwalled carbon nanotube (MWCNT)-coated cotton fabrics having varying amounts of MWCNTs (10, 12, 14 and 16?wt.%) in PA 6 (10, 15 and 20?wt.%) were fabricated with dip coating method to investigate the electromagnetic shielding properties in the frequency range of 15–3000 MHz. The effects of MWCNT loading on electrical resistivity, electromagnetic interference shielding effectiveness and also shielding mechanism have been studied. The highest electromagnetic shielding effectiveness value was obtained at 20?wt.% MWCNT loading in 10?wt.% PA 6 and the PA 6/MWCNT-coated composites showed the absoprtion-dominated shielding mechanism.