The most common mass spectrometry approach analyzing contamination of the environment deals with targeted analysis, i.e. detection and quantification of the selected (priority) pollutants. However non-targeted analysis is becoming more often the method of choice for environmental chemists. It involves implementation of modern analytical instrumentation allowing for comprehensive detection and identification of the wide variety of compounds of the environmental interest present in the sample, such as pharmaceuticals and their metabolites, musks, nanomaterials, perfluorinated compounds, hormones, disinfection by-products, flame retardants, personal care products, and many others emerging contaminants. The paper presents the results of detection and identification of previously unreported organic compounds in snow samples collected in Moscow in March 2016. The snow analysis allows evaluation of long-term air pollution in the winter period. Gas chromatography coupled to a high resolution time-of-flight mass spectrometer has enabled us with capability to detect and identify such novel analytes as iodinated compounds, polychlorinated anisoles and even Ni-containing organic complex, which are unexpected in environmental samples. Some considerations concerning the possible sources of origin of these compounds in the environment are discussed.

This study sought to evaluate the toxicological effects of graphene oxide (GO) through tests with Danio rerio (zebrafish) embryos, considering the influence of the base washing treatment and the interaction with natural organic matter (i.e., humic acid, HA). A commercial sample of GO was refluxed with NaOH to remove oxidation debris (OD) byproducts, which resulted in a base washed GO sample (bw-GO). This process decreased the total oxygenated groups in bw-GO and its stability in water compared to GO. When tested in the presence of HA, both GO and bw-GO stabilities were enhanced in water. Although the embryo exposure showed no acute toxicity or malformation, the larvae exposed to GO showed a reduction in their overall length and acetylcholinesterase activity. In the presence of HA, GO also inhibited acid phosphatase activity. Our findings indicate a mitigation of material toxicity after OD removal. The difference in the biological effects may be related to the materials’ bioavailability and biophysicochemical interactions. This study reports for the first time the critical influence of OD on the GO material biological reactivity and HA interaction, providing new data for nanomaterial environmental risk assessment and sustainable nanotechnology.

A means for identifying and prioritising the treatment of uncertainty (UnISERA) in environmental risk assessments (ERAs) is tested, using three risk domains where ERA is an established requirement and one in which ERA practice is emerging. UnISERA's development draws on 19 expert elicitations across genetically modified higher plants, particulate matter, and agricultural pesticide release and is stress tested here for engineered nanomaterials (ENM). We are concerned with the severity of uncertainty; its nature; and its location across four accepted stages of ERAs. Using an established uncertainty scale, the risk characterisation stage of ERA harbours the highest severity level of uncertainty, associated with estimating, aggregating and evaluating expressions of risk. Combined epistemic and aleatory uncertainty is the dominant nature of uncertainty. The dominant location of uncertainty is associated with data in problem formulation, exposure assessment and effects assessment. Testing UnISERA produced agreements of 55%, 90%, and 80% for the severity level, nature and location dimensions of uncertainty between the combined case studies and the ENM stress test. UnISERA enables environmental risk analysts to prioritise risk assessment phases, groups of tasks, or individual ERA tasks and it can direct them towards established methods for uncertainty treatment.

Nanomaterials are increasingly being used to improve the properties and functions of common building materials. A new type of self-cleaning cement incorporating TiO2 nanomaterials (TiO2-NMs) with photocatalytic properties is now marketed. This promising cement might provide air pollution-reducing properties but its environmental impact must be validated. During cement use and aging, an altered surface layer is formed that exhibits increased porosity. The surface layer thickness alteration and porosity increase with the cement degradation rate. The hardened cement paste leaching behavior has been fully documented, but the fate of incorporated TiO2-NMs and their state during/after potential release is currently unknown. In this study, photocatalytic cement pastes with increasing initial porosity were leached at a lab-scale to produce a range of degradation rates concerning the altered layer porosity and thickness. No dissolved Ti was released during leaching, only particulate TiO2-NM release was detected. The extent of release from this batch test simulating accelerated worst-case scenario was limited and ranged from 18.7 ± 2.1 to 33.5 ± 5.1 mg of Ti/m2 of cement after 168 h of leaching. TiO2-NMs released into neutral aquatic media (simulate pH of surface water) were not associated or coated by cement minerals. The TiO2-NM release mechanism is suspected to start from freeing of TiO2-NMs in the altered layer pore network due to partial cement paste dissolution followed by diffusion into the bulk pore solution to the surface. The extent of TiO2-NM release was not solely related to the cement degradation rate.

With the extensive application of graphene oxide (GO), it is noticeable that part of GO is directly/indirectly released into the environment and widespread research indicated that it had adverse influences on human health and ecological balance. In this work, a novel nanobelt-like Ca/Al layered double hydroxides (CA-LDH) was synthesized and applied as efficient coagulant for the removal of GO from aqueous solutions. The results indicated that neutral pH, co-existing cations and higher temperature were beneficial to the coagulation of GO. The sequence of cation effect for promoting of GO coagulation was Ca2+ > Mg2+ > K+ > Na+, whereas the effect of anions on GO coagulation was PO43− > CO32− > SO42− > Cl−. Comparing with anions, the cations showed more dominate effect for GO coagulation than anions. Hydrogen bonds and electrostatic interaction were the main coagulation mechanisms for GO coagulation, which were evidenced by FT-IR and XPS analysis. Specifically, for the first time, the reclaimed product of CA-LDH after GO coagulation (CA-LDH + GO) was applied as adsorbents for the secondary application in the removal of heavy metal ions from aqueous solutions. Interestingly, the CA-LDH + GO still had high adsorption capacities, i.e., the maximum adsorption capacities (qmax) for Cu(II), Pb(II), and Cr(VI) were 122.7 mg/g, 221.2 mg/g and 64.4 mg/g, respectively, higher than other similar materials. This paper highlighted the LDH-based nanomaterials are promising materials for the elimination of environmental pollutants and the migration and transformation of carbon nanomaterials in the natural environment.

Toxicity and uptake of nano-CeO2 (nCeO2) in edible vegetables are not yet fully understood. In the present study, we grew romaine lettuce in sand amended with nCeO2. At high concentrations (1000 and 2000 mg/kg), nCeO2 diminished the chlorophyll content by 16.5% and 25.8%, respectively, and significantly inhibited the biomass production. nCeO2 (≥100 mg/kg) altered antioxidant enzymatic activities and malondialdehyde levels in the plants. nCeO2 (≥500 mg/kg) triggered a remarkable increase of nitrate-N level in the shoots, which can be converted to toxic nitrite in humans thereby posed risk to human health. Concentration dependent accumulation of Ce in the plant tissues was observed. X ray absorption near edge spectroscopy (XANES) results indicate that Ce presented as nCeO2 and CePO4 in the roots while as nCeO2 and Ce carboxylates in the shoots. Chelation of Ce3+ by citric acid or precipitation of Ce3+ by PO43− reduced the translocation and toxicity of nCeO2, indicating that release of Ce3+ played a critical role in the toxicity nCeO2.

Nanomaterials have been widely used in a number of applications; however, these nanomaterials may potentially be risky for human health, particularly for the respiratory system. In this study, we used a mouse asthma model to study whether graphene oxide (GO), a promising carbonaceous nanomaterial with unique physicochemical properties, aggravates allergic asthma via the oxidative stress pathway. Mice were sensitized with ovalbumin (OVA) to trigger immune reactions, while vitamin E (Ve) was administered as an antioxidant. Our results showed that GO aggravated OVA-induced allergic asthma in mice, as suggested by increased reactive oxygen species (ROS), elevated total immunoglobulin E (IgE), upregulated Th2 response, and the aggravation of allergic asthma symptoms, such as airway remolding, collagen deposition with mucus hypersecretion, and airway hyperresponsiveness (AHR). The administration of Ve dramatically attenuated all of the above effects. In conclusion, Ve showed anti-allergic properties in antagonizing the exacerbation of allergic asthma induced by GO, providing a new possibility for the treatment of allergic asthma.

In this study, the kinetic data of the adsorption of two antibiotics onto three nanoadsorbents was modeled using the Brouers–Sotolongo fractal model. The model parameters were calculated at different initial antibiotic concentrations using various approximations of the kinetic equation for two quantities of practical relevance: the sorption power and the half-time characteristic of the sorption. The merits of the nanomaterial were then compared in terms of their application in the elimination of dangerous antibiotic wastes. We also developed a formula to calculate the effective rate of the best adsorbent. This study presents the modeling method in detail and has a pedagogical value for similar researches.

Toxicity data of substances to higher plants is needed for the purpose of risk assessment, site evaluation, phytoremediation, and plant protection. However, the results from the most common phytotoxicity tests, like the OECD algae and Lemna test, are not necessarily valid for higher terrestrial plants. The willow tree toxicity test uses inhibition of transpiration (aside of growth and water use efficiency) of willow cuttings grown in spiked solutions or soils as end point to quantify toxicity. This overview presents results from 60 studies including 24 new unpublished experiments for 56 different chemicals or substrates. Highest toxicity (EC₅₀ < 1 mg/L) was observed from exposure to heavy metals like copper and cadmium. Also, organotins and free cyanide showed very high toxicity. The toxic effect of chlorophenols on willows was comparable to that on duck weed (Lemna) and green algae, while volatile compounds like chlorinated solvents or benzene, toluene, ethylbenzene, and xylene had less effect on trees than on these aquatic plants, due to volatilization from leaves and test media. In particular low (g/L range) toxicity was observed for tested nanomaterials. Effects of pharmaceuticals (typically weak acids or bases) depended strongly of the solution pH. Like for algae, baseline toxicity was observed for willows, which is related to the water solubility of the compounds, with absolute chemical activity ranging from 0.01 to 0.1, but with several exceptions. We conclude that the willow tree toxicity test is a robust method for relating uptake, accumulation, and metabolism of substances to the toxicity to trees.

Solubility is a critical component of physicochemical characterisation of engineered nanomaterials (ENMs) and an important parameter in their risk assessments. Standard testing methodologies are needed to estimate the dissolution behaviour and biodurability (half-life) of ENMs in biological fluids. The effect of pH, particle size and crystal form on dissolution behaviour of zinc metal, ZnO and TiO₂ was investigated using a simple 2 h solubility assay at body temperature (37 °C) and two pH conditions (1.5 and 7) to approximately frame the pH range found in human body fluids. Time series dissolution experiments were then conducted to determine rate constants and half-lives. Dissolution characteristics of investigated ENMs were compared with those of their bulk analogues for both pH conditions. Two crystal forms of TiO₂ were considered: anatase and rutile. For all compounds studied, and at both pH conditions, the short solubility assays and the time series experiments consistently showed that biodurability of the bulk analogues was equal to or greater than biodurability of the corresponding nanomaterials. The results showed that particle size and crystal form of inorganic ENMs were important properties that influenced dissolution behaviour and biodurability. All ENMs and bulk analogues displayed significantly higher solubility at low pH than at neutral pH. In the context of classification and read-across approaches, the pH of the dissolution medium was the key parameter. The main implication is that pH and temperature should be specified in solubility testing when evaluating ENM dissolution in human body fluids, even for preliminary (tier 1) screening.