Novel Tough Crystalline Blends of Polylactide with Ethylene Glycol Derivative of POSS

Blending of polylactide (PLA) with low stereoregularity and polyhedral oligomeric silsesquioxane grafted with arms of poly(ethylene glycol) methyl ether, acting as a plasticizer, allowed us previously to obtain a novel stable elastomeric-like material. The present contribution focuses on the properties of semi-crystalline PLA plasticized with this compound. Melt blends of PLA with 5–15 wt% of the plasticizer, were compression molded, quenched and annealed, which enabled cold-crystallization. The glass transition temperature of the blends and their drawability depended on their crystallinity and plasticizer content. The best ductility was reached at the plasticizer content of 15 wt%; the achieved strain at break was 6.5 (650%) and 1.3 (130%), for the quenched and annealed material, respectively. The latter value exceeded 20 times the strain at break of neat crystalline PLA. The tensile toughness of the annealed 15 wt% blend was 12 times larger than that of crystalline PLA. Moreover, annealing of 15 wt% blend improved its yield strength by 40%. Despite the two peaks of the loss modulus, indicating the two glass transitions in this blend, no heterogeneities were found by scanning electron microscopy, indicating that the plasticizer enriched phase formed instead of distinct inclusions of the plasticizer.     

The monitoring of cadmium,zinc and copper in the kidneys and liver of humans deceased in the region of Cracow (Poland)

Cadmium, zinc and copper levels were determined in the renal cortex and liver of 60 inhabitants of Cracow, Poland. Cadmium levels in the renal cortex were contained in broad limits of 5–176 g/g, mean 50.6 g/g (wet weight). Maximum levels were found in the age group of about 50–60 years. The levels were slightly higher in men (53 g/g) than in women (45 g/g), with no effect of location within the region. The levels in smokers (62 g/g) were much higher than in non-smokers (32 g/g). The above relations were less pronounced for cadmium levels in the liver. Whole body retention of cadmium followed the pattern of cadmium in renal cortex. The level of zinc in renal cortex reflected those of cadmium. A significant proportion of the population (54% in smokers, 9% in non-smokers) showed cadmium levels in renal cortex exceeding the reference level of 50 g/g recently accepted for general population. In the view of the authors the exposure to cadmium of the population of Cracow is excessive and calls for attention.The study was performed under a KBN grant No 40106 91 01.     

Proposal of new convenient extractant for assessing phytoavailability of heavy metals in contaminated sandy soil

Environmental Science and Pollution Research - The aim of the study was to compare the usefulness of 1 M HCl with aqua regia, EDTA, and CaCl2 for the extraction of phytoavailable forms of...     

Air toxics in Canada measured by the National Air Pollution Surveillance (NAPS) program and their relation to ambient air quality guidelines

This study reports ambient concentrations of 63 air toxics that were measured in Canada by the National Air Pollution Surveillance (NAPS) program over the period 2009–2013. Measured concentrations are compared with ambient air quality guidelines from Canadian jurisdictions, and compounds that exceeded guidelines are identified and discussed. Although this study does not assess risk or cumulative effects, air toxics that approached guidelines are also identified so that their potential contribution to ambient air toxics pollution can be considered. Eleven air toxics exceeded at least one guideline, and an additional 16 approached guidelines during the study period. Four compounds were measured using methods whose detection limits exceeded a guideline value, three of which could not be compared with guidelines, since they were not detected in any samples. The assessment of several metal(loid) concentrations is tentative, since they were measured only in fine particulate matter (PM) but compared with guidelines based on coarse or total PM. Improvements to sampling and analysis techniques for the latter compounds as well as for those whose methods are subject to known uncertainties would improve confidence in reported concentrations and their relation to applicable guidelines. Analysis of sampling strategies for all compounds found to exceed or approach guidelines would contribute to ensuring that their spatiotemporal coverage is adequate. Examination of the air toxics not measured by NAPS but having guidelines in Canadian jurisdictions or being included in other programs such as the U.S. National-Scale Air Toxics Assessment (NATA) would contribute to ensuring that the full suite of pollutants relevant to ambient air quality in Canada is subject to adequate study. The results of this study can be applied to evaluating the effectiveness of toxic substances management in Canada.

Implications: Recent measurements of 63 air toxics in Canada by the National Air Pollution Surveillance (NAPS) program showed that 11 compounds exceeded daily or annual ambient air quality guidelines and that an additional 16 compounds approached such guidelines within an order of magnitude. The results of this study can be applied to evaluating the effectiveness of toxic substances management in Canada and to identifying compounds that merit further investigation.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Heavy metal accumulation and distribution in Phragmites australis seedlings tissues originating from natural and urban catchment

The retention of heavy metal (HM) was studied in root and rhizomes (BLG), stems (ST), and leaves (LF) of Phragmites australis (common reed) seedlings collected from different locations, differing in the scale of anthropogenic interference. The analysis includes the reference samples of sediments in uncontaminated lake Garczonki and contaminated roadside ditch in Cieplewo. The concentrations of Zn, Cu, Pb, Cd, Ni, and Cr were analyzed in plant tissues and sediments using the atomic absorption spectrometry and inductively coupled plasma mass spectrometry. The general assessment of sediments collected in the Garczonki lake showed a good environmental status; while in the roadside ditch in Cieplewo, the sediments were considerably polluted with HM. In the first stage of plant growth, all of the analyzed HMs are mainly inhibited by BLG system. The decreasing trend of elements was as follows: BLG > ST > LF. The organs followed different decreasing trends of HM concentration; the trend Zn > Cu > Ni > Cr > Pb > Cd was found in ST and LF for the Garczonki lake seedlings and for BLG and LF for the roadside ditch in Cieplewo seedlings. Zn showed the highest concentration, while Cd the lowest concentration in each of the examined organs. The bioaccumulation factor indicated the higher mobility of HM in seedlings in the Garczonki lake than in the roadside ditch in Cieplewo. The morphological studies suggest the good state and health of seedling from both sites; however, the reduction of root hair surface was observed for the roadside ditch seedlings. The anatomical studies present changes in the size of the nucleus and count of chloroplasts in LF. No reaction on HM contamination sediments in the seedlings from the roadside ditch in Cieplewo in the aerenchyma was noted. Potentially, both types of seedlings can be used to decontaminate environments rich in HM. However, the level of HM absorbed by seedlings (in the first stage of growth) should be considered due to the behavior in the target phytoremediation site.

     

Dust-particle migration around flotation tailings ponds: pine needles as passive samplers

The potential use of dust particles trapped on Scots pine needles for tracking dust migration around flotation tailings ponds in the Silesian-Krakowian ore district, Southern Poland was tested. 1-, 2- and 3-years old needles were studied using a scanning electron microscope and energy dispersive X-ray microanalysis. Particle sizes and morphologies, and the nature of the compounds hosting metals ions, were examined. A large majority of the particles examined are <10 microm in size. Almost 80% of particles represent respirable dust. All the components in the flotation wastes appear among the chemical compounds identified in particles on the pine needles. The quantity of the waste particles decreases with distance from the flotation tailings ponds. The analysis of dust particles on pine needles could be a useful method for estimating vectors and travel distances of suspended dust migrating around open flotation tailings ponds and around other point sources emitting dust particles with chemical compositions differing from the environmental background.     

Adaptive alterations in the fatty acids composition under induced oxidative stress in heavy metal-tolerant filamentous fungus Paecilomyces marquandii cultured in ascorbic acid presence

The ability of the heavy metal-tolerant fungus Paecilomyces marquandii to modulate whole cells fatty acid composition and saturation in response to IC₅₀ of Cd, Pb, Zn, Ni, and Cu was studied. Cadmium and nickel caused the most significant growth reduction. In the mycelia cultured with all tested metals, with the exception of nickel, a rise in the fatty acid unsaturation was noted. The fungus exposure to Pb, Cu, and Ni led to significantly higher lipid peroxidation. P. marquandii incubated in the presence of the tested metals responded with an increase in the level of linoleic acid and escalation of electrolyte leakage. The highest efflux of electrolytes was caused by lead. In these conditions, the fungus was able to bind up to 100 mg?g^?1 of lead, whereas the content of the other metals in the mycelium was significantly lower and reached from 3.18 mg?g^?1 (Cu) to 15.21 mg?g^?1 (Zn). Additionally, it was shown that ascorbic acid at the concentration of 1 mM protected fungal growth and prevented the changes in the fatty acid composition and saturation but did not alleviate lipid peroxidation or affect the increased permeability of membranes after lead exposure. Pro-oxidant properties of ascorbic acid in the copper-stressed cells manifested strong growth inhibition and enhanced metal accumulation as a result of membrane damage. Toxic metals action caused cellular modulations, which might contributed to P. marquandii tolerance to the studied metals. Moreover, these changes can enhance metal removal from contaminated environment.     

Genotoxicological effects of some phenoxyherbicides and their metabolites on Bacillus subtilis M45 Rec- and H17 Rec+ strains

Because they are used in a number of commercial preparations phenoxyacetic acids and their salts can occur in wastewater. During their degradation genotoxic substances may be created. The results of investigations of biodegradability and genotoxicity of some phenoxyherbicides are presented. Commercial formulations of 2,4-D (Aminopielik 720) and MCPA (Chwastox Extra) were the substrates studied. Biodegradation tests were conducted according to OECD guidelines for testing of chemicals--confirmatory test (OECD Method 303 A). Genotoxicity tests were conducted with Bacillus subtilis strains according to the method of [Chemical Mutagens, vol. 6, Plenum Press. New York, 1980, p. 149]. Genotoxicity of biodegradation products was also studied. Both commercial formulations were biodegradable. Aminopielik 720 was potentially genotoxic but only at great concentrations while Chwastox Extra was not genotoxic. Biodegradation products of neither compound were genotoxic.