In vivo assessment of TiO2 based wear nanoparticles in periprosthetic tissues.

A multimodal approach combining inductively coupled plasma mass spectrometry (ICP-MS), single-particle ICP-MS (spICP-MS), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) and Raman spectroscopy enabled a deeper insight into the balance between total titanium (Ti), the soluble titanium fraction and titanium dioxide based particle fraction levels in periprosthetic tissues collected from patients undergoing revision surgery. Hydrofluoric acid usage in the sample digestion allowed for complete digestion of TiO2 particles, thus enabling accurate estimation of total Ti levels. The TiO2 fraction represents 38-94% of the titanium load in the six samples where particles were detected, and the fraction is present mainly in samples from patients with aseptically loosened total hip arthroplasty. Further attention was given to this fraction determining the elemental composition, particle count, particle size and modification of TiO2. The spICP-MS analysis confirmed the presence of the TiO2-derived (nano)particles (NPs) with a 39- to 187-nm median size and particle count up to 2.3 × 1011 particles per gram of tissue. On top of that, the SEM-EDS confirmed the presence of the TiO2 nanoparticles with 230-nm median size and an anatase crystal phase was determined by Raman spectroscopy. This study presents a novel multimodal approach for TiO2 particle determination and characterization in tissue samples and is the first in vivo study of this character.

Assessment of the Hormetic Effect of Arsenic on Growth and Physiology of Two Cultivars of Maize (Zea mays L.).

Although growth stimulation at low arsenic doses was observed in several plants, few studies have focused on this phenomenon in more detail. The effects of different concentrations of arsenic (0-50 mg kg-1 of soil: As0-As50) on the growth and selected physiological parameters of two maize cultivars (Zea mays L. cvs. Chapalu and MvNK 333) were tested. Cultivar MvNK 333 manifested a generally higher tolerance to As than cv. Chapalu, which may be related to the lower content of As in the tissues. The highest stimulatory effect of As was recorded at doses of As1 and As2 (cv. Chapalu), and at the As5 dose (MvNK 333), there was an increase in shoot elongation, biomass, and relative water content (RWC), as well as the content of photosynthetic pigments. The stimulatory effect of lower doses of As apparently represents an adaptation mechanism that is associated with water content regulation in the given conditions. The stomata of the studied cultivars were involved in this regulation in different ways. While cv. Chapalu exhibited increased numbers of stomata on both sides of leaves, cv. MvNK 333 instead responded to the given conditions with decreased stomata size. Although hormetic manifestations closely related to changes in stomatal number and size were observed, a typical stomatal hormetic response was not observed in the given range of As doses.

Monitoring of the impact of road salting on spruce forest ecosystem in the vicinity of the highway D1 in the Bohemian-Moravian Highlands, Czech Republic.

Monitoring of pollution in the vicinity of roads connected to winter road maintenance is one of the important tools for optimising winter maintenance technology and reducing its environmental impact. The aim of this study was to determine the relationship between winter road maintenance and the increased concentration of sodium ion to characterise the harm caused by the de-icing agents on selected types of individual components grown in the Norway spruce ecosystem. The model area is located in the immediate vicinity of the D1 motorway connecting Prague and Brno (Czech Republic), at 103 km. The area is thus exposed to long-term contamination from automobile transport, and the monitoring was carried out for 3 consecutive years. A clear effect of the de-icing agents on conifers near the road has been demonstrated by the symptoms of salt damage visually observed in close proximity to the road (at a sampling distance of 5 m). The needles of these spruce trees also showed increased sodium concentrations, regardless of the age of the needles. The study also confirms that sodium accumulates in all selected components of the analysed ecosystem (moos, humus, soil). The sodium concentration has been found to decrease with increasing distance from the road for all of the components.

Development of New Health Risk Assessment of Nanoparticles: EPA Health Risk Assessment Revised.

The concentration of nanoparticles in the ambient air can lead to induced toxicities; however, it appears that nanoparticles' unique properties are completely omitted when assessing health risks. This paper aims to enhance the EPA health risk assessment by incorporating two new variables that consider the size of nanoparticles: the toxicity multiplier and the size multiplier. The former considers the qualitative aspect of the size of particles within a concentration, whilst the latter takes into account the effects associated with the number of particles of the specific i-th size distribution interval. To observe the impact of the new variables, a case study was performed. The studied element was cadmium, which was measured using ICP-MS to discover concentrations of size fractions, ranging from <15.1 to <9830 nm. Next, the cadmium concentration is assessed using both the current state-of-the-art method and the proposed method with adjustments. Based on the new approach, the final risk was 1.1 × 10−5, which was almost 24 times higher compared with the current method. The contribution of nanoparticles to the risk value grew from barely 6% to an alarming 88%. Therefore, the enhanced method can lead to more realistic results when assessing the health risks of nanoparticles.

Assessment of Soil Contamination with Potentially Toxic Elements and Soil Ecotoxicity of Botanical Garden in Brno, Czech Republic: Are Urban Botanical Gardens More Polluted Than Urban Parks?

Though botanical gardens are an important and widely visited component of urban green spaces (UGS) worldwide, their pollution is rarely studied. The aim of this study was to assess botanical garden soil contamination and ecotoxicity and to evaluate whether urban botanical gardens are more contaminated than urban parks. Soil assessments showed serious contamination with Cd, Pb and Zn, emitted predominantly by traffic, agrochemicals and past construction and demolition waste. The discovery of hazardous historical ecological burden in the UGS calls for the necessity of detailed surveys of such areas. Despite prevailing moderate-to-heavy contamination, the soil was only slightly ecotoxic. Maximum immobilisation inhibition of Daphnia magna reached 15%. Growth of Sinapis alba L. was predominantly stimulated (73%), and Desmodesmus subspicatus Chodat was exclusively stimulated, possibly due to soil alkalinity and fertiliser-related nutrients. The hypothesis of a higher contamination of urban botanical gardens compared to urban parks was confirmed. However, urban parks can face a greater risk of soil ecotoxicity, hypothetically due to decreased activity of soil organisms resulting from adverse soil conditions caused by active recreation. The results highlight the need for an increased focus on botanical and ornamental gardens when assessing and managing UGS as areas potentially more burdened with contamination.

Occurrence, Seasonal Variation, and Size Resolved Distribution of Arsenic Species in Atmospheric Particulate Matter in an Urban Area in Southeastern Austria.

Extensive information is available on total arsenic in particulate matter (PM), but little is known about the relative contribution of each individual species. Recent studies often focus on inorganic arsenic as arsenite and arsenate, neglecting the organoarsenicals, i.e., methylarsine, dimethylarsine, and trimethylarsine or the corresponding oxidized forms methylarsonate, dimethylarsinate, and trimethylarsine oxide, although they were already first detected in PM in the mid-1970s. This work presents results from more than 300 daily PM10 and further size-resolved atmospheric PM samples in the size range from 15 nm to 10 µm collected in an urban environment in Austria during the course of a year. An ion-exchange-HPLC (with anion and cation exchange columns) and an ICPMS/MS system were used to study the seasonal variations of total arsenic and all species known to exist in PM. Inorganic arsenic was present in significant amounts in all samples with highest concentrations during winter, but also all organoarsenicals were detected throughout the year. We show that their contribution cannot be ignored, as particles smaller than <1 µm can contain up to 35% of the water+H2O2 extractable arsenic as methylated species, but only dimethylarsinate showed a clear seasonal trend throughout the year.

Impact of New Year's Eve fireworks on the size resolved element distributions in airborne particles.

New Year's Eve fireworks represent one of the most unusual atmospheric pollution events in the course of a year. A majority of particles aerosolized by burning of fireworks consist of metals and their compounds used in firework displays. In this study, ambient particulate matter was sampled using a 14 stage cascade impactor in two European cities during turn of the years 2016/17 and 2017/18. Concentrations of 33 elements were determined by inductively coupled plasma mass spectrometry. To assess the impact of New Year's Eve fireworks on ambient air quality, chemically resolved size distributions of particles with diameters between 15 nm and 10 µm collected during fireworks episodes were compared to ones collected in normal winter weeks. For some metals a distinct shift of their concentration maximum related to fireworks could be observed, which is in between the maxima for accumulation and coarse mode particles. Concentrations of these elements (Sr, Ba, Mg, Bi, Al, Cu and K) were also higher during weeks with fireworks episodes than during control weeks. Although New Year's Eve fireworks only take place once a year, these results show that air pollution caused by fireworks can be a potential health risk, especially for people with pre-existing diseases.

Arsenic speciation in aerosols of a respiratory therapeutic cave: A first approach to study arsenicals in ultrafine particles.

Arsenic is ubiquitous in the environment and of special concern due to its varying toxicity depending on the chemical form present. Less is known about arsenic in air, especially about organoarsenicals, their sources and fate. There is also a lack of knowledge regarding arsenic in airborne nanoparticles that are critical for understanding with respect to human health effects due to their size. Here we show results from an arsenic speciation analysis in size-resolved airborne particles with aerodynamic diameters down to 15 nm. Analysis of aerosols from a respiratory therapeutic cave showed temporarily higher concentrations of trimethylarsine oxide than inorganic arsenic and substantial amounts of organoarsenicals, especially in smaller particles. Our method provides guidance for future studies investigating arsenicals in ultrafine particles and their health implications. Furthermore, the method developed can be used to widely monitor particle-bound organoarsenicals to fully understand the importance of As biovolatilization in the environment.

Analysis of Means (ANOM) as a Tool for Comparison of Sample Treatment Methods: Testing Various Mineralization Procedures for Selenium Determination in Biological Materials.

Several mineralization methods for the determination of selenium using hydride generation optical emission spectrometry with inductively coupled plasma in biological samples (whole egg powder and pork liver) were compared using the analysis of means (ANOM) method. This statistical tool is suitable for graphical representation of testing on simple comparative experiments. The results yielded by ANOM are identical with those obtained with the commonly used analysis of variance (ANOVA) method; however, the graphical output of ANOM is more illustrative in comparison to ANOVA. Both methods indicated a significant discrepancy between the results obtained using muffle furnace ashing mineralization and the results provided by other mineralization methods. This is probably due to the loss of volatile selenium compounds during the decomposition of organic matter.

Bioluminescence determination of active caspase-3 in single apoptotic cells.

Caspase-3 is an executive caspase, in the central position within apoptotic machinery. Apoptosis as a way of programmed cell death is a physiological process that plays an essential role in the development and homeostasis maintenance; moreover, its deregulations are linked to tumor progression or various autoimmune disorders. Therefore, an investigation of apoptosis pathways on the level of individual cells is not only of biological but also medical importance. In this work we report on the development of a high-sensitivity instrumentation and protocol for detection of active caspase-3 in individual mammalian apoptotic cells. The technology is based on the specific cleavage of modified luciferin by caspase-3, an immediate bioluminescence reaction of free luciferin with luciferase followed by emissions of photons and their detection by photomultiplier tube working in the photon counting regime. Three different instrumental arrangements are compared for the determination of caspase-3 in free cells or tissue samples. Thus, in our best miniaturized system the mean amount as low as about 6.5 fg corresponding to 122 000 molecules of caspase-3 can be detected in individual apoptotic mouse leg cells.