Fullerenes toxicity and electronic properties

Nanotechnology globally represents a new direction within scientific development, where the atomic and electronic properties of molecules are used in a unique fashion to produce and construct new and exotic materials and products. Fullerenes (Bucky balls, C₆₀) constitute a particular group within the field of nanotechnology. Fullerenes find applications in medicine, industrial chemistry and electronics. However, there are several unanswered questions about fullerenes and their toxicological properties. Most toxicological studies on fullerenes evolve around the in vitro and in vivo aspects of pristine C₆₀ along with chemically modified C₆₀ molecules. We reviewed toxicology reports on C₆₀. We bring a critical and challenging evaluation of the electronic and quantum properties of C₆₀ molecules in context with the implications on cellular factors and metabolites. The evaluation shows that the reactivity and quantum chemical properties of C₆₀ can have unexpected effects in the cell, by principally absorbing metabolites, such as OH^? and H⁺ ions and alter its reactivity. We thus challenge the present view of C₆₀ solely based on empirical studies, based on the electronic properties of C₆₀ that vary considerably with their size and reaction path. A further example of this is the absorption of divalent zinc ions, which shows an increase in reactivity of the C₆₀ that presents an important pattern of chemical state, reactivity and toxicological potential. The results evaluate the toxicological potential of C₆₀ from a different angle than conventional, by applying a blend of critical review of the findings on C₆₀ toxicity, their chemical and electronic properties.     

Integrated Ambient and Microenvironment Model for Estimation of PM10 Exposures of Children in Annual and Episode Settings

Particulate matter air pollution is estimated to cause in the order of 350,000 excess deaths in the European Union calling for policy development and evaluation tools. In the current work, a model for PM₁₀ exposures of children is developed using microenvironment time activities and infiltration of ambient pollution indoors, both evaluated against observations earlier and integrated with city-wide air quality models in the current work. The model is demonstrated using data from two cities in Italy. High-end short-term exposures are characterized by an episode-day situation in Turin, and annual mean exposures in downtown Bologna. The air quality model was unable to capture the highest levels during the episode, and therefore, the exposure model was adjusted using observed–modeled ratio from a monitoring station. Air quality model performance for the annual levels was significantly better. Annual exposure variability within the target population was 1.5-fold in the downtown area Bologna and tenfold during the episode day in Turin.     

A new gas chromatographic determination of ethylenethiourea residues without derivatization

Abstract

A new gas chromatographic method reliable in the microgram range, was developed to measure ETU residues in various crops. Contrary to previously published procedures, this new method does not require prior derivatization of the ETU. The limit of sensitivity was shown to be 0.01 ppm using the flame photometric detector, FPD (sulfur mode, 394 nm).     

Personal monitoring of exposure to particulate matter with a high temporal resolution

Background

Continuous monitoring of air quality is implemented by government institutions at fixed ambient sites. However, the correlation between fixed site measurements and exposure of individual persons to air contaminants is likely to be weak.

Materials and methods

We measured particulate matter both outdoors and indoors by following the spatial movement of individuals. Sixteen test persons took part and carried a measurement backpack for a 24-h period. The backpack was comprised of a Grimm Aerosol Spectrometer model 1.109, a GPS device, and a video camera for tracking of human behavior. The spectrometer provided information about particle numbers and mass in 32-size classes with a high temporal resolution of 6 s.

Results

The personal exposure of individuals during 24 h could significantly exceed the outdoor particulate matter (PM)₁₀ concentrations measured at the fixed sites. The average 24-h exposure of all test persons for PM₁₀ varied from 27 to 322 ??g m^?3. Environmental tobacco smoke and cooking emissions were among the main indoor sources for PM. The amount of particulate matter a test person was exposed to was highly dependent on the spatial behavior and the surrounding microenvironment conditions.

Discussion

Large-scale experiments including personal measurements might help to improve modeling approaches to approximate the actual exposure on a statistically sound basis.     

Estimation of emission fluxes from a horizontal flux budget method, exemplified with determination of pesticide volatilization

The paper describes an experimental set-up designed to measure the volatilization of different pesticides after application under full-scale field conditions. The pesticides were sprayed around the circumference of a circle and measurements of meteorology and air concentrations of pesticides were taken in the centre of the circle. The paper describes how the dimensions like the radius of the circle and height of the mast in the experimental set-up are found from theoretical considerations. A method to increase the confidence of the flux calculations is described. It utilizes that several substances were applied simultaneously and that a certain parameter in the fitted concentration profiles depends on turbulence only and thus have the same value for all substances. The design was used during two campaigns, conducted on the same location, one during fall on bare soil and one in spring on a barley crop.     

Analysis of accumulation, extractability, and metabolization of five different phenylarsenic compounds in plants by ion chromatography with mass spectrometric detection and by atomic emission spectroscopy

Phenylated arsenic compounds occur as highly toxic contaminants in former military areas where they were formed as degradation products of chemical warfare agents. Some phenylarsenic compounds such as roxarsone and aminophenylarsonic acids were applied as food additive and veterinary drugs in stock-breeding and therefore pose an environmental risk in agricultural used sites. Very few data exist in the literature concerning uptake and effects of phenylarsenic compounds in plants growing on contaminated soils. In this study, the accumulation, extractability, and metabolization of five different phenylarsenic compounds, phenylarsonic acid, p- and o-aminophenylarsonic acid, phenylarsine oxide, and 3-nitro-4-hydroxyphenylarsonic acid called roxarsone, by the terrestrial plant Tropaeolum majus were investigated. Ion chromatography coupled to inductively coupled plasma mass spectrometry was used to differentiate these arsenic compounds, and inductively coupled plasma atomic emission spectroscopy was used for total arsenic quantification. All compounds considered were taken up by the roots and transferred to stalks, leaves, and flowers. The strongest accumulation was observed for unsubstituted phenylarsonic acid followed by its trivalent analogue phenylarsine oxide that was mostly oxidized in soil whereas the amino- or nitro- and hydroxy-substituted phenylarsonic acids were accumulated to a smaller degree.The highest extraction yield of 90% for ground leaf material was achieved by 0.1 M phosphate buffer, pH 7.7, in a two-step extraction with a total extraction time of 24 h. The extraction of higher amounts of arsenic (50–70% of total arsenic present in leaves depending on arsenic species application) from non-ground intact leaves with deionized water in comparison with the buffer (20–40% of total arsenic) is ascribed to osmotic effects. The arsenic species analysis revealed a cleavage of the amino groups from the phenyl ring for plants treated with aminophenylarsonic acids. A further important metabolic effect consisted in the production of inorganic arsenate and arsenite from the phenylated arsonic acid groups.     

Modelling of spatio-temporal population dynamics of earthworms under wetland conditions—An integrated approach

Both the effects of earthworms on soils and the effects of soil conditions on earthworms have been studied with the help of experiments and modelling. This paper provides a model architecture allowing coupling both effects to a dynamic interaction in changing environmental conditions. We chose for a spatio-temporally explicit model and focussed on wetland conditions. Soil temperature and humidity have been modelled by means of finite volumes and were used to determine the spatial habitat suitability. The life cycles of earthworms have been modelled by Leslie matrices where soil humidity, soil temperature and population densities have been used to parametrize survival and transition probabilities. Earthworm dispersion has been described by a cellular automaton of the domain providing spatial population densities for both the life cycle submodel and the soil conditions submodel.