Nanoparticle interactions with co-existing contaminants: joint toxicity, bioaccumulation and risk

<p>With their growing production and application, engineered nanoparticles (NPs) are increasingly discharged into the environment. The released NPs can potentially interact with pre-existing contaminants, leading to biological effects (bioaccumulation and/or toxicity) that are poorly understood. Most studies on NPs focus on single analyte exposure; the existing literature on joint toxicity of NPs and co-existing contaminants is rather limited but beginning to develop rapidly. This is the first review paper evaluating the current state of knowledge regarding the joint effects of NPs and co-contaminants. Here, we review: (1) methods for investigating and evaluating joint effects of NPs and co-contaminants; (2) simultaneous toxicities from NPs co-exposed with organic contaminants, metal/metalloid ions, dissolved organic matter (DOM), inorganic ligands and additional NPs; and (3) the influence of NPs co-exposure on the bioaccumulation of organic contaminants and heavy metal ions, as well as the influence of contaminants on NPs bioaccumulation. In addition, future research needs are discussed so as to better understand risk associated with NPs-contaminant co-exposure.</p

Physiological and Biochemical Changes Imposed by CeO₂ Nanoparticles on Wheat: A Life Cycle Field Study

Interactions of <i>n</i>CeO₂ with plants have been mostly evaluated at seedling stage and under controlled conditions. In this study, the effects of <i>n</i>CeO₂ at 0 (control), 100 (low), and 400 (high) mg/kg were monitored for the entire life cycle (about 7 months) of wheat plants grown in a field lysimeter. Results showed that at high concentration <i>n</i>CeO₂ decreased the chlorophyll content and increased catalase and superoxide dismutase activities, compared with control. Both concentrations changed root and leaf cell microstructures by agglomerating chromatin in nuclei, delaying flowering by 1 week, and reduced the size of starch grains in endosperm. Exposed to low concentration produced embryos with larger vacuoles, while exposure to high concentration reduced number of vacuoles, compared with control. There were no effects on the final biomass and yield, Ce concentration in shoots, as well as sugar and starch contents in grains, but grain protein increased by 24.8% and 32.6% at 100 and 400 mg/kg, respectively. Results suggest that more field life cycle studies are needed in order to better understand the effects of <i>n</i>CeO₂ in crop plants

Carbonaceous Nanomaterials Have Higher Effects on Soybean Rhizosphere Prokaryotic Communities During the Reproductive Growth Phase than During Vegetative Growth

Carbonaceous nanomaterials (CNMs) can affect agricultural soil prokaryotic communities, but how the effects vary with the crop growth stage is unknown. To investigate this, soybean plants were cultivated in soils amended with 0, 0.1, 100, or 1000 mg kg^–1 of carbon black, multiwalled carbon nanotubes (MWCNTs), or graphene. Soil prokaryotic communities were analyzed by Illumina sequencing at day 0 and at the soybean vegetative and reproductive stages. The sequencing data were functionally annotated using the functional annotation of prokaryotic taxa (FAPROTAX) database. The prokaryotic communities were unaffected at day 0 and were altered at the plant vegetative stage only by 0.1 mg kg^–1 MWCNTs. However, at the reproductive stage, when pods were filling, most treatments (except 1000 mg kg^–1 MWCNTs) altered the prokaryotic community composition, including functional groups associated with C, N, and S cycling. The lower doses of CNMs, which were previously shown to be less agglomerated and thus more bioavailable in soil relative to the higher doses, were more effective toward both overall communities and individual functional groups. Taken together, prokaryotic communities in the soybean rhizosphere can be significantly phylogenetically and functionally altered in response to bioavailable CNMs, especially when soybean plants are actively directing resources to seed production

Enhanced Formation of Silver Nanoparticles in Ag⁺‑NOM-Iron(II, III) Systems and Antibacterial Activity Studies

This work reports the role of iron redox pair (Fe³⁺/Fe²⁺) in the formation of naturally occurring silver nanoparticles (AgNPs) in the aquatic environment. The results showed that Fe³⁺ or Fe²⁺ ions in the mixtures of Ag⁺ and natural organic matter enhanced the formation of AgNPs. The formation of AgNPs depended on pH and types of organic matter. Increase in pH enhanced the formation of AgNPs, and humic acids as ligands showed higher formation of AgNPs compared to fulvic acids. The observed results were described by considering the potentials of redox pairs of silver and iron species and the possible species involved in reducing silver ions to AgNPs. Dynamic light scattering and transmission electron microscopy measurements of AgNPs revealed mostly bimodal size distribution with decrease in size of AgNPs due to iron species in the reaction mixture. Minimum inhibitory concentration of AgNPs needed to inhibit the growth of various bacterial species suggested the role of surfaces of tested Gram-positive and Gram-negative bacteria. Stability study of AgNPs, formed in Ag⁺-humic acid/fulvic acids-Fe³⁺ mixtures over a period of several months showed high stability of the particles with significant increase in surface plasmon resonance peak. The environmental implications of the results in terms of fate, transport, and ecotoxicity of organic-coated AgNPs are briefly presented

Cerium Biomagnification in a Terrestrial Food Chain: Influence of Particle Size and Growth Stage

Mass-flow modeling of engineered nanomaterials (ENMs) indicates that a major fraction of released particles partition into soils and sediments. This has aggravated the risk of contaminating agricultural fields, potentially threatening associated food webs. To assess possible ENM trophic transfer, cerium accumulation from cerium oxide nanoparticles (nano-CeO₂) and their bulk equivalent (bulk-CeO₂) was investigated in producers and consumers from a terrestrial food chain. Kidney bean plants (Phaseolus vulgaris var. red hawk) grown in soil contaminated with 1000–2000 mg/kg nano-CeO₂ or 1000 mg/kg bulk-CeO₂ were presented to Mexican bean beetles (Epilachna varivestis), which were then consumed by spined soldier bugs (Podisus maculiventris). Cerium accumulation in plant and insects was independent of particle size. After 36 days of exposure to 1000 mg/kg nano- and bulk-CeO₂, roots accumulated 26 and 19 μg/g Ce, respectively, and translocated 1.02 and 1.3 μg/g Ce, respectively, to shoots. The beetle larvae feeding on nano-CeO₂ exposed leaves accumulated low levels of Ce since ∼98% of Ce was excreted in contrast to bulk<i>-</i>CeO₂. However, in nano-CeO₂ exposed adults, Ce in tissues was higher than Ce excreted. Additionally, Ce content in tissues was biomagnified by a factor of 5.3 from the plants to adult beetles and further to bugs

Cerium Oxide Nanoparticles Impact Yield and Modify Nutritional Parameters in Wheat (Triticum aestivum L.)

The implications of engineered nanomaterials on crop productivity and food quality are not yet well understood. The impact of cerium oxide nanoparticles (<i>n</i>CeO₂) on growth and yield attributes and nutritional composition in wheat (Triticum aestivum L.) was examined. Wheat was cultivated to grain production in soil amended with 0, 125, 250, and 500 mg of <i>n</i>CeO₂/kg (control, <i>n</i>CeO₂-L, <i>n</i>CeO₂-M, and <i>n</i>CeO₂-H, respectively). At harvest, grains and tissues were analyzed for mineral, fatty acid, and amino acid content. Results showed that, relative to the control, <i>n</i>CeO₂-H improved plant growth, shoot biomass, and grain yield by 9.0%, 12.7%, and 36.6%, respectively. Ce accumulation in roots increased at increased <i>n</i>CeO₂ concentration but did not change across treatments in leaves, hull, and grains, indicating a lack of Ce transport to the above-ground tissues. <i>n</i>CeO₂ modified S and Mn storage in grains. <i>n</i>CeO₂-L modified the amino acid composition and increased linolenic acid by up to 6.17% but decreased linoleic acid by up to 1.63%, compared to the other treatments. The findings suggest the potential of nanoceria to modify crop physiology and food quality with unknown consequences for living organisms

Targeting Metal Impurities for the Detection and Quantification of Carbon Black Particles in Water via spICP-MS

Carbon black (CB) is a nanomaterial with numerous industrial applications and high potential for integration into nano-enabled water treatment devices. However, few analytical techniques are capable of measuring CB in water at environmentally relevant concentrations. Therefore, we intended to establish a quantification method for CB with lower detection limits through utilization of trace metal impurities as analytical tracers. Various metal impurities were investigated in six commercial CB materials, and the Monarch 1000 CB was chosen as a model for further testing. The La impurity was chosen as a tracer for spICP-MS analysis based on measured concentration, low detection limits, and lack of polyatomic interferences. CB stability in water and adhesion to the spICP-MS introduction system presented a challenge that was mitigated by the addition of a nonionic surfactant to the matrix. Following optimization, the limit of detection (64 μg/L) and quantification (122 μg/L) for Monarch 1000 CB demonstrated the applicability of this approach to samples expected to contain trace amounts of CB. When compared against gravimetric analysis and UV–visible absorption spectroscopy, spICP-MS quantification exhibited similar sensitivity but with the ability to detect concentrations an order of magnitude lower. Method detection and sensitivity was unaffected when dissolved La was spiked into CB samples at environmentally relevant concentrations. Additionally, a more complex synthetic matrix representative of drinking water caused no appreciable impact to CB quantification. In comparison to existing quantification techniques, this method has achieved competitive sensitivity, a wide working range for quantification, and high selectivity for tracing possible release of CB materials with known metal contents

Targeting Metal Impurities for the Detection and Quantification of Carbon Black Particles in Water via spICP-MS

Carbon black (CB) is a nanomaterial with numerous industrial applications and high potential for integration into nano-enabled water treatment devices. However, few analytical techniques are capable of measuring CB in water at environmentally relevant concentrations. Therefore, we intended to establish a quantification method for CB with lower detection limits through utilization of trace metal impurities as analytical tracers. Various metal impurities were investigated in six commercial CB materials, and the Monarch 1000 CB was chosen as a model for further testing. The La impurity was chosen as a tracer for spICP-MS analysis based on measured concentration, low detection limits, and lack of polyatomic interferences. CB stability in water and adhesion to the spICP-MS introduction system presented a challenge that was mitigated by the addition of a nonionic surfactant to the matrix. Following optimization, the limit of detection (64 μg/L) and quantification (122 μg/L) for Monarch 1000 CB demonstrated the applicability of this approach to samples expected to contain trace amounts of CB. When compared against gravimetric analysis and UV–visible absorption spectroscopy, spICP-MS quantification exhibited similar sensitivity but with the ability to detect concentrations an order of magnitude lower. Method detection and sensitivity was unaffected when dissolved La was spiked into CB samples at environmentally relevant concentrations. Additionally, a more complex synthetic matrix representative of drinking water caused no appreciable impact to CB quantification. In comparison to existing quantification techniques, this method has achieved competitive sensitivity, a wide working range for quantification, and high selectivity for tracing possible release of CB materials with known metal contents

Agglomeration Determines Effects of Carbonaceous Nanomaterials on Soybean Nodulation, Dinitrogen Fixation Potential, and Growth in Soil

The potential effects of carbonaceous nanomaterials (CNMs) on agricultural plants are of concern. However, little research has been performed using plants cultivated to maturity in soils contaminated with various CNMs at different concentrations. Here, we grew soybean for 39 days to seed production in soil amended with 0.1, 100, or 1000 mg kg^–1 of either multiwalled carbon nanotubes (MWCNTs), graphene nanoplatelets (GNPs), or carbon black (CB) and studied plant growth, nodulation, and dinitrogen (N₂) fixation potential. Plants in all CNM treatments flowered earlier (producing 60% to 372% more flowers when reproduction started) than the unamended controls. The low MWCNT-treated plants were shorter (by 15%) with slower leaf cover expansion (by 26%) and less final leaf area (by 24%) than the controls. Nodulation and N₂ fixation potential appeared negatively impacted by CNMs, with stronger effects at lower CNM concentrations. All CNM treatments reduced the whole-plant N₂ fixation potential, with the highest reductions (by over 91%) in the low and medium CB and the low MWCNT treatments. CB and GNPs appeared to accumulate inside nodules as observed by transmission electron microscopy. CNM dispersal in aqueous soil extracts was studied to explain the inverse dose–response relationships, showing that CNMs at higher concentrations were more agglomerated (over 90% CNMs settled as agglomerates >3 μm after 12 h) and therefore proportionally less bioavailable. Overall, our findings suggest that lower concentrations of CNMs in soils could be more impactful to leguminous N₂ fixation, owing to greater CNM dispersal and therefore increased bioavailability at lower concentrations

Evidence of Translocation and Physiological Impacts of Foliar Applied CeO₂ Nanoparticles on Cucumber (<i>Cucumis sativus</i>) Plants

Currently, most of the nanotoxicity studies in plants involve exposure to the nanoparticles (NPs) through the roots. However, plants interact with atmospheric NPs through the leaves, and our knowledge on their response to this contact is limited. In this study, hydroponically grown cucumber (<i>Cucumis sativus</i>) plants were aerially treated either with nano ceria powder (<i>n</i>CeO₂) at 0.98 and 2.94 g/m³ or suspensions at 20, 40, 80, 160, and 320 mg/L. Fifteen days after treatment, plants were analyzed for Ce uptake by using ICP-OES and TEM. In addition, the activity of three stress enzymes was measured. The ICP-OES results showed Ce in all tissues of the CeO₂ NP treated plants, suggesting uptake through the leaves and translocation to the other plant parts. The TEM results showed the presence of Ce in roots, which corroborates the ICP-OES results. The biochemical assays showed that catalase activity increased in roots and ascorbate peroxidase activity decreased in leaves. Our findings show that atmospheric NPs can be taken up and distributed within plant tissues, which could represent a threat for environmental and human health