The Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactide) Prepared by Different Synthesis Procedure

Different synthesis methods were applied to determine optimal conditions for polymerization of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (l-lactide), in order to obtain poly(l-lactide) (PLLA). Bulk polymerizations (in vacuum sealed vessel, high pressure reactor and in microwave field) were performed with tin(II) 2-ethylhexanoate as the initiator. Synthesis in the vacuum sealed vessel was carried out at the temperature of 150 °C. To reduce the reaction time second polymerization process was carried out in the high pressure reactor at 100 °C and at the pressure of 138 kPa. The third type of rapid synthesis was done in the microwave reactor at 100 °C, using frequency of 2.45 GHz and power of 150 W at the temperature of 100 °C. The temperature in this method was controlled via infrared system for in-bulk measuring. The solution polymerization (with trifluoromethanesulfonic acid as initiator) was possible even at the temperature of 40 °C, yielding PLLA with narrow molecular weight distribution in a very short period of time (less than 6 h). The obtained polymers had the number-average molecular weights ranging from 43,000 to 178,000 g mol⁻¹ (polydispersity index ranging from 1 to 3) according to the gel permeation chromatography measurements. The polymer structure was characterized by Fourier transform infrared and NMR spectroscopy. Thermal properties of the obtained polymers were investigated using thermogravimetry and differential scanning calorimetry.     

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g⁻¹. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C_org) concentrations.     

Bioremediation of soil contaminated with pentachlorophenol (PCP) using humic acids bound on zeolite

We determined the toxicity of various chlorophenols, especially pentachlorophenol (PCP), on five bacterial strains and studied PCP biodegradation in soils amended with an organomineral complex (OMC) prepared from humic acids (organic part) bound on zeolite (inorganic part). Both components of OMC have excellent sorption properties and are of natural origin and therefore suitable to be used in the environment. Toxicity of chlorophenols depends not only on the number of chlorine atoms but also on their position on aromatic ring, and is thus regiospecific. Biodegradation of PCP was studied in three real completely characterized soil samples, Chernozem, Fluvisol, and Regosol, with and without the addition of OMC. The soils were sterilized and bioaugmented with the bacterial isolate Comamonas testosteroni CCM 7530. The immobilization effect of OMC in relation to PCP depends on the concentration of humic acids (HAs), the PCP concentration, and the content of organic carbon in soil. The microbial activity and the simulated action of acid rains led to the gradual release and biodegradation of the reversibly bound PCP without no initial toxic effect on indigenous or bioaugmented microorganisms. OMC appeared to be a good trap for PCP with potential applications in remediation technology because it reduces the potential toxicity of PCP to microbial community by lowering its bioavailability and thus facilitates its biodegradation.     

Synthesis and Characterisation of Polyester Based on Isosorbide and Butanedioic Acid

Copolyesters based on isosorbide and butanedioic acid in combination with monomers such as adipic acid and dimethyl terephthalate, poly(isosorbide-co-butanedioic acid) (and -co-adipic acid) and poly(isosorbide-co-butanedioic acid-co-dimethyl terephthalate), were synthesized and characterized. Linear OH-functionalized polyesters were obtained via melt polyesterification of dicarboxylic acids with OH-functional monomers. The type of end-group was controlled by the monomer stoichiometry and hydroxyl functional group is formed in time. Average molecular masses of synthesised polyesters were measured by gel permeation chromatography. The glass transition temperatures and thermal stability of the obtained polyesters were effectively adjusted by varying polymer composition and molar mass. Addition of adipic acid or dimethyl terephthalate increased glass transition temperatures of obtained polyesters. Thermal stability of obtained polyester slightly increases by the increasing of dimethyl terephthalate content. Molecular structures of obtained polyester were assessed by Fourier transform infrared spectra and ¹H NMR spectroscopy.     

Biomass of Speckled Alder on an Air-Polluted Mountain Site and its Response to Fertilization

The article summarizes outcomes of a biomass study conducted in a young speckled alder plantation on a cold mountain site. At this location, the previously existing old forest was clear felled because of damage from air pollution, and present-day surface humus is in need of restoration. The intention of this study was to quantify the biomass and nutrients accumulated by alders and their components and assess whether the initial fertilization resulted in increased biomass production and nutrient accumulation in the biomass. Besides the control, two fertilized treatments were installed. In the surface treatment (SUT), the amendment was applied as a base dressing in small circles around trees. In the planting-hole treatment (PHT), the amendment was incorporated into soil inside the planting holes. Five growth seasons after planting and fertilization, six alders from each treatment were harvested including roots. Their biomass was quantified and analyzed for macroelements. The greatest pool of dry mass (DM) was branches in the control and stem wood in the fertilized treatments. The greatest pools of macroelements were leaves and branches. The most pronounced effects of fertilization were recorded in the DM and consequently in the absolute quantities of nutrients. The DM of an average tree in the control, SUT, and PHT was 85, 226, and 231 g, respectively. The absolute contents of nutrients per tree in the fertilized treatments showed the following increases, as compared with the control: (N) 2.5–2.6 times; (P) 1.6–2.4 times; (K) 1.8–2.1 times; and (Mg) 1.8–2.0 times, respectively. Speckled alder responded positively to fertilization.     

Structural Differences Between Lignin Model Polymers Synthesized from Various Monomers

In a plant cell wall, lignin is synthesized from several monomeric precursors, combined in various ratios. The variation in monomer type and quantity enables multifunctional role of lignin in plants. Thus, it is important to know how different combinations of lignin monomers impact variability of bond types and local structural changes in the polymer. Lignin model polymers are a good model system for studies of relation between variations of the starting monomers and structural variations within the polymer. We synthesized lignin model polymers from three monomers, CF??based on coniferyl alcohol and ferulic acid in monomer proportions 5:1 and 10:1 (w/w), CP??based on coniferyl alcohol and p-coumaric acid in proportion 10:1 (w/w) and CA??based on pure coniferyl alcohol. We studied structural modifications in the obtained polymers, by combining fluorescence microscopy and spectroscopy, FT-IR and Raman spectroscopy, in parallel with determination of polymers?? molecular mass distribution. The differences in the low M _w region of the distribution curves of the 10:1 polymers in comparison with the CA polymer may be connected with the increased content of C=C bonds and decreased content of condensed structures, as observed in FT-IR spectra and indicated by the analysis of fluorescence spectra. The 5:1 CF polymer contains a different type of structure in comparison with the 10:1 CF polymers, reflected in its simpler M _w distribution, higher homogeneity of the fluorescence emitting structures and in the appearance of a new high-wavelength emission component. We propose that this component may originate from ??-conjugated chains, which are longer in this polymer. The results are a contribution to the understanding of the involvement of structural variations of lignin polymers in the cell wall structural plasticity.     

Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) in urban soils of Bratislava, Slovakia: patterns, relation to PAHs and vertical distribution

We determined concentrations, sources, and vertical distribution of OPAHs and PAHs in soils of Bratislava. The ∑14 OPAHs concentrations in surface soil horizons ranged 88-2692 ng g⁻¹ and those of ∑34 PAHs 842-244,870 ng g⁻¹. The concentrations of the ∑9 carbonyl-OPAHs (r = 0.92, p = 0.0001) and the ∑5 hydroxyl-OPAHs (r = 0.73, p = 0.01) correlated significantly with ∑34 PAHs concentrations indicating the close association of OPAHs with parent-PAHs. OPAHs were quantitatively dominated by 9-fluorenone, 9,10-anthraquinone, 1-indanone and benzo[a]anthracene-7,12-dione. At several sites, individual carbonyl-OPAHs had higher concentrations than parent PAHs. The concentration ratios of several OPAHs to their parent-PAHs and contribution of the more soluble OPAHs (1-indanone and 9-fluorenone) to ∑14 OPAHs concentrations increased with soil depth suggesting that OPAHs were faster vertically transported in the study soils by leaching than PAHs which was supported by the correlation of subsoil:surface soil ratios of OPAH concentrations at several sites with K_OW.     

Photodegradation of fluoroquinolones in aqueous solution under light conditions relevant to surface waters,toxicity assessment of photoproduct mixtures

Environmental Science and Pollution Research - Photochemical degradation of fluoroquinolones ciprofloxacin, enrofloxacin and norfloxacin in aqueous solution under light conditions relevant to...