Copper and zinc are metals that have been traditionally thought of as past contamination legacies. However, their industrial use is still extensive and current applications (e.g. nanoparticles and antifouling paints) have become additional marine environment delivery routes. Determining a pollutant's genotoxicity is an ecotoxicological priority, but in marine benthic systems putative substances responsible for sediment genotoxicity have rarely been identified. Studies that use sediment as the delivery matrix combined with exposures over life-history relevant timescales are also missing for metals. Here we assess copper and zinc's genotoxicity by exposing the ecologically important polychaete Alitta virens to sediment spiked with environmentally relevant concentrations for 9 months. Target bioavailable sediment and subsequent porewater concentrations reflect the global contamination range for coasts, whilst tissue concentrations, although elevated, were comparable with other polychaetes. Survival generally reduced as concentrations increased, but monthly analyses show that growth was not significantly different between treatments. The differential treatment mortality may have enabled the surviving worms in the high concentration treatments to capture more food thus removing any concentration treatment effects for biomass. Using the alkaline comet assay we confirm that both metals via the sediment are genotoxic at concentrations routinely found in coastal regions and this is supported by elevated DNA damage in worms from field sites. However, combined with the growth data it also highlights the tolerance of A. virens to DNA damage. Finally, using long term (decadal) monitoring data we show stable or increasing sediment concentrations of these metals for many areas. This will potentially mean coastal sediment is a significant mutagenic hazard to the benthic community for decades to come. An urgent reappraisal of the current input sources for these ‘old pollutants’ is, therefore, required.

Zinc oxide nanoparticles (ZnO NPs) have a wide range of applications in cosmetics, electrical, and optical industries. The wide range of applications of ZnO NPs, especially in personal care products, suggest they can reach major environmental matrices causing unforeseen effects. Recent literature has shown conflicting findings regarding the beneficial or detrimental effects of ZnO NPs towards terrestrial biota. In this review we carried out a comprehensive survey about beneficial, as well as detrimental aspects, of the ZnO NPs exposure toward various terrestrial plants. A careful scrutiny of the literature indicates that at low concentrations (about 50 mg/kg), ZnO NPs have beneficial effects on plants. Conversely, at concentrations above 500 mg/kg they may have detrimental effects, unless there is a deficiency of Zn in the growing medium. This review also remarks the critical role of the biotic and abiotic factors that may elevate or ameliorate the impact of ZnO NPs in terrestrial plants.

Oil pollution of waters is one of the most serious environmental problems globally. The long half-life and persistence within the environment makes oil particularly toxic and difficult to remediate. There is a significant need for efficient and cost-effective oil recovery technologies to be brought in to practice. In this study, we developed a facile and efficient magnetic separation method. The surface of 316L stainless steel nanoparticles was modified by plasma deposition of 1,7-octadiene and perfluorooctane, producing relatively hydrophobic coatings having water contact angles of 86 and 100°, respectively. Both coatings had high oil removal efficiency (ORE) of >99%. The captured oil could be easily separated by applying an external magnetic force. The ease of material preparation and separation from the water after the oil is captured, and its high ORE is a compelling argument for further development and optimization of the technology to possible utilization into practice. Furthermore, the capacity of plasma polymerization to deliver desired surface properties can extend the application of the technology to removing other chemical and biological contaminants from polluted waters.

An experiment was performed to explore the interactive impacts of zinc oxide nanoparticles (ZnO NPs) and cadmium (Cd) on growth, yield, antioxidant enzymes, Cd and zinc (Zn) concentrations in wheat (Triticum aestivum). The ZnO NPs were applied both in Cd-contaminated soil and foliar spray (in separate studies) on wheat at different intervals and plants were harvested after physiological maturity. Results depicted that ZnO NPs enhanced the growth, photosynthesis, and grain yield, whereas Cd and Zn concentrations decreased and increased respectively in wheat shoots, roots and grains. The Cd concentrations in the grains were decreased by 30–77%, and 16–78% with foliar and soil application of NPs as compared to the control, respectively. The ZnO NPs reduced the electrolyte leakage while increased SOD and POD activities in leaves of wheat. It can be concluded that ZnO NPs (levels used in the study) could effectively reduce the toxicity and concentration of Cd in wheat whereas increase the Zn concentration in wheat. Thus, ZnO NPs might be helpful in decreasing Cd and increasing Zn biofortification in cereals which might be effective to reduce the hidden hunger in humans owing the deficiency of Zn in cereals.

Particulate matter (PM) can strongly affect redox biochemistry and therefore induce the response of the immune system and aggravate the course of autoimmune diseases. Nanoparticles containing transition metal compounds possessing semiconductor properties (TiO2, ZnO) may act as photocatalysts and accelerate the generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS). In this study, the NIST standard reference material, SRM 1648a, has been analyzed in terms of this consideration. Organic compounds present in SRM 1648a were removed by cold oxygen plasma treatment. Samples of SRM 1648a with removed organic content (<2% of organic carbon, <1% of nitrogen) were obtained within 2 h of this treatment. The treatment did not affect the morphology of the powder. The reference material and PM2.5 collected in Kraków are composed of smaller particles and nanoparticles forming aggregates. The efficiency of (photo)generation of hydroxyl radicals and singlet oxygen was compared for original and organics-free samples. The analyzed samples showed the highest activity towards ROS generation when exposed to UV-vis-NIR light, moderate under UV irradiation, and the lowest in dark. Data collected in the present study suggest that the organic fraction is mostly responsible for singlet oxygen generation, as almost twice higher efficiency of 1O2 generation was observed for the original NIST sample compared to the material without the organic fraction. However, particulate matter collected in Kraków was found to have a five times higher activity in singlet oxygen generation (compared for original NIST and Kraków dust samples).

With increasing demand for recycled wastewater for irrigation purposes, there is a need to evaluate the potential for manufactured nanomaterials in waste water to impact crop production and agroecosystems. Copper oxide nanoparticles (CuO NPs) have previously been shown to negatively impact the growth of duckweed (Landoltia punctata) a model aquatic plant consumed by water fowl and widely found in agricultural runoff ditches in temperate climates. However, prior studies involving CuO NP toxicity to duckweed have focused on systems without the presence of dissolved organic matter (DOM). In the current study, duckweed growth inhibition was shown to be a function of aqueous Cu²⁺ concentration. Growth inhibition was greatest from aqueous CuCl₂ and, for particles, increased with decreasing CuO particle size. The dissolution of CuO NPs in ½ Hoagland's solution was measured to increase with decreasing particle size and in the presence of Suwannee river humic and fulvic acids (HA; FA). However, the current results suggest that HA, and to a lesser extent, FA, decrease the toxicity of both CuO NPs and free ionized Cu to duckweed, likely by inhibiting Cu availability through Cu-DOM complex formation. Such results are consistent with changes to Cu speciation as predicted by speciation modeling software and suggest that DOM changes Cu speciation and therefore toxicity in natural systems.

A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO₂ nanoparticles and TiO₂/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO₂ and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO₂ and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

Recently it has been shown that there are two types of magnetite particles in the human brain, some, which occur naturally and are jagged in appearance, and others that arise from industrial sources, such as coal fired power plants, and are spherical. In order to confirm the latter, the magnetic component of coal ash is first purified and characterized by XRD, showing that it is magnetite with an average particle size of 211 nm. Studies confirm the coal ash magnetic behavior, and that the magnetite is not bound to the other components of coal ash but exist as an isolatable component. SEM studies confirm that in the process of burning coal at very high temperatures for industrial uses, the magnetite formed is spherically shaped, as recent studies of brain tissues of highly exposed urban residents have found. As such, the use of coal for industrial applications such as coking in the production of steel and in power plants is indicated to be a major source of the spherical magnetic combustion-associated magnetite fine particle and nanoparticle environmental pollution. The capacity of these magnetic particles to penetrate and damage the blood-brain-barrier and the early development of Alzheimer's disease hallmarks in exposed populations calls for detail analysis of magnetic fine and nanoparticle distribution across the world.Summation: Industrial coal usage produces spherical magnetic particles and nanoparticles, identical to those associated with neurological disorders.

The abundance of silver nanoparticles (AgNPs) in consumer products has led to their environmental release and therefore to concern about their impact on human health. The ingestion of AgNP-contaminated soil from urban sites is an important exposure pathway, especially for children. Given the limited information on oral bioaccessibility of soil Ag, we used a physiologically based extraction test (PBET) to evaluate the bioaccessibility of AgNPs and AgNO₃ from soil digestion. The AgNPs underwent several biochemical transformations, including their simultaneous dissolution and agglomeration in gastric fluid followed by the disintegration in the intestinal fluid of the agglomerates into NPs containing silver and chlorine. Therefore, Ag-containing soil exposed the intestine to nanoparticulate Ag in forms that were structurally different from the original forms. The bioaccessibility of AgNPs (0.5 ± 0.05%–10.9 ± 0.7%) was significantly lower than that of AgNO₃ (4.7 ± 0.6%–14.4 ± 0.1%), as a result of the lower adsorption of nanoparticles to soil residues during the digestive process. For the soils tested, the bioaccessibility of AgNPs increased with decreasing clay contents and lower pH. By identifying the soil properties that control AgNP bioaccessibility, a more efficient and accurate screening can be performed of soil types that pose the greatest health risk associated with AgNP exposure.

CuO engineered nanoparticles (NPs) are of increasing concern due to their extensive use in daily life and adverse effect on aquatic organisms. The investigations on the toxicity of CuO NPs to aquatic plants through uptake from roots versus fronds are limited. This paper discusses the interactions of CuO NPs with Lemna minor, a floating plant. After CuO NPs (150 μg L⁻¹) exposure for 7 days, the frond number, frond surface area and dry weights of whole plants significantly decreased by 32%, 47% and 33%; the responses were dose-dependent. Microscopy imaging showed that the epidermis was severely damaged in fronds, edges were severely sloughed off and cell integrity was damaged in roots. Shrinkage of both chloroplast and starch grains were observed in the frond cells. Internalization of CuO NPs in root and frond cells during CuO NPs (1 mg L⁻¹) exposure was confirmed with the root Cu levels of Lemna minor being three times higher than the fronds by using transmission electron microscopy and flame atomic absorption spectrophotometry. Reactive oxygen species, mainly H₂O₂ (increased by 56%) and ·OH (increased by 57%), accumulated in Lemna minor tissues in response to CuO NPs exposure. Moreover, chloroplasts were confirmed as a site of ROS production. These findings are helpful for better understanding the biological responses of aquatic plants upon NPs exposure.