Oribatid mite communities and metal bioaccumulation in oribatid species (Acari, Oribatida) along the heavy metal gradient in forest ecosystems

The responses of oribatid communities to heavy metal contamination were studied. Concentration of cadmium, copper and zinc in nine oribatid species along a gradient of heavy metal pollution was measured. Oribatid mites were sampled seasonally during two years in five forests located at different distances from the zinc smelter in the Olkusz District, southern Poland. The most numerous and diverse oribatid communities were found in the forest with moderate concentrations of heavy metals. Analysis by atomic absorption spectrophotometry revealed large differences in metal body burdens among species. All studied oribatid species appeared to be accumulators of copper with Oppiella nova, Nothrus silvestris and Adoristes ovatus characterized by the highest bioaccumulation factors. Most species poorly accumulate cadmium and zinc. The accumulation of heavy metals in the body of oribatids was not strictly determined by their body size or the trophic level at which they operate.     

Ionic liquids as lubricants or lubrication additives: An ecotoxicity and biodegradability assessment

This paper reports on the (eco)toxicity and biodegradability of ionic liquids considered for application as lubricants or lubrication additives. Ammonium- and pyrrolidinium-based cations combined with methylsulphate, methylsulphonate and/or (CF₃SO₂)₂N⁻ anions were investigated in tests to determine their aquatic toxicity using water fleas Daphnia magna, green algae Selenastrum capricornutum and marine bacteria (Vibrio fischeri). Additional test systems with an isolated enzyme (acetylcholinesterase) and isolated leukaemia cells from rats (IPC-81) were used to assess the biological activity of the ionic liquids. These compounds generally exhibit low acute toxicity and biological activity. Their biodegradability was screened according to OECD test procedures 301 B and 301 F. For choline and methoxy-choline ionic liquids ready biodegradability was observed within 5 or 10 d, respectively. Some of the compounds selected have a considerable potential to contribute to the development of more sustainable products and processes.     

Detection and identification of baculovirus pesticides by multitemperature single-strand conformational polymorphism

The method of single-strand conformational polymorphism (SSCP) was modified in our laboratories for the characterization of baculoviruses, insect viruses with great potential for use as bioinsecticides in biological protection programs. A series of primers were synthesized after the comparison of the polyhedrin gene sequences of over 20 baculoviruses. Polyhedrin is a highly conserved protein which is responsible for the persistence of the virus in the environment. Universal primers were designed which could be used in polymerase chain reactions (PCR) containing genomic DNA from an array of nucleopolyhedrosis viruses (NPVs) including these which are used as biopesticides against important pests of forests and crops, such as Anticarsia gemmatalis, Spodoptera frugiperda, Lymantria dispar, Lymantria monacha and many others. PCR products were denatured and subjected to single-strand DNA electrophoresis at variable temperatures (MSSCP) where, after silver staining, they gave ssDNA band patterns characteristic for each baculovirus species. This technique can be potentially applied to detect baculoviruses in insects collected in the field, as well as to plant tissues and the excrements or bodies of predators without need for sequencing the PCR products. Sometimes MSSCP can be used not only for species determination but also as an indication of genomic variability which can be related to infectivity.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Assessment of soils contamination with veterinary antibiotic residues in Northern Poland using developed MAE-SPE-LC/MS/MS methods

Among the wide range of compounds reaching the soil are the veterinary antimicrobials. Since no regulations regarding acceptable levels of drug concentrations in the environment exist, monitoring tests, particularly concerning soils, are carried out very rarely. This study presents a preliminary assessment of the contamination of agricultural soils in Northern Poland with seven antimicrobial veterinary medicines which has never been carried out before. Veterinary drugs were detected in 54% of the examined soil samples; the most commonly detected drugs were sulfonamides and trimethoprim. The highest indicated concentrations refer to enrofloxacin (57.0 μg kg^?1) and trimethoprim (47.8 μg kg^?1). The presence of these target drugs in the soil environment confirms the need for further monitoring studies. The analytical methods developed in this study are an excellent tool to achieve this goal and allow an estimation of the risk connected with the presence of veterinary antimicrobials in soils.

     

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     

Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).     

Profiles of enzymatic activity in earthworms from zinc, lead and cadmium polluted areas near Olkusz (Poland)

The aim of the study was to determine whether there are signs of adaptation of soil fauna to a gradient of heavy metal contamination. Earthworms Aporrectodea caliginosa, Lumbricus terrestris and Eisenia fetida were collected during the spring and summer of 2000 and 2001 from meadow sites situated between 2 and 32 km from the Bukowno-Olkusz complex of zinc-lead ore mines and smelters. The heavy metal content in the soil near smelters reaches 10,500 mg/kg (d.w.) for Zn, 2600 mg/kg for Pb and 81.9 mg/kg for Cd. The sites differ with respect to species composition of earthworm community, with A. caliginosa being dominant. Complete data was obtained only for A. caliginosa, since other species were not abundant at all investigated sites during the whole period of investigation. The body burdens of Zn, Pb, Cd and Cu in A. caliginosa reached 1500, 100, 220 and 10 microg/g, respectively, in the vicinity of the smelter (2-4 km), and decreased to 400, 2, 36 and 6 microg/g at the most distant site (32 km). Cadmium and lead content was significantly elevated in the whole body of L. terrestris collected at the site 2.5 km distant from the smelters when compared to more distant sites, while in E. fetida only the body burden of cadmium was elevated at the nearest site compared to the next site of transect. Activities of glutathione peroxidase (GPX; EC 1.11.1.9) against hydrogen peroxide (H2O2) or cumene hydroperoxide (cumOOH), glutathione reductase (GR; EC 1.6.4.2), glutathione S-transferase (GST; EC 2.5.1.18) and catalase (CAT; EC 1.11.1.6) were assayed in postmitochondrial supernatant obtained from whole body homogenates. Seasonal and annual variations of enzyme activity were reflected by higher GPX activity in the late summer of 2001 in comparison with the spring and summer of 2000. This may reflect severe drought in the spring and summer of 2000. The activity of both GPX isozymes, GR and GST in A. caliginosa and L. terrestris increased with increasing distance from the smelters and reached maximum at sites III and IV (4 and 8 km from the smelters, respectively) and then it decreased in the animals from site V (32 km). These may be the effects of antagonism between the enzyme inducing and enzyme inhibiting action of smelter emissions, a phenomenon known as a hormetic effect. It is postulated here that this effect is of diagnostic value for metal pollution biomonitoring.     

Impact assessment of climate policy on Poland's power sector

This article addresses the impact of the European Union Emissions Trading System (EU ETS) on Poland’s conventional energy sector in 2008–2020 and further till 2050. Poland is a country with over 80% dependence on coal in the power sector being under political pressure of the European Union’s (EU) ambitious climate policy. The impact of the increase of the European Emission Allowance (EUA) price on fossil fuel power sector has been modelled for different scenarios. The innovation of this article consists in proposing a methodology of estimation actual costs and benefits of power stations in a country with a heavily coal-dependent power sector in the process of transition to a low-carbon economy. Strong political and economic interdependence of coal and power sector has been demonstrated as well as the impact caused by the EU ETS participation in different technology groups of power plants. It has been shown that gas-fuelled combined heat and power units are less vulnerable to the EU ETS-related costs, whereas the hard coal-fired plants may lose their profitability soon after 2020. Lignite power plants, despite their high emissivity, may longer remain in operation owing to low operational costs. Additionally, the results of long-term, up to 2050, modelling of Poland’s energy sector supported an unavoidable need of deep decarbonisation of the power sector to meet the post-Paris climate objectives. It has been concluded that investing in coal-based power capacity may lead to a carbon lock-in of the power sector. Finally, the overall costs of such a transformation have been discussed and confronted with the financial support offered by the EU. The whole consideration has been made in a wide context of changes ongoing globally in energy markets and compared with some other countries seeking transformation paths from coal. Poland’s case can serve as a lesson for all countries trying to reduce coal dependence in power generation. Reforms in the energy sector shall from the very beginning be an essential part of a sustainable transition of the whole nation’s economy. They must scale the power capacity to the future demand avoiding stranded costs. The reforms must be wide-ranging, based on a wide political consensus and not biased against the coal sector. Future energy mix and corresponding technologies shall be carefully designed, matched and should remain stable in the long-term perspective. Coal-based power capacity being near the end of its lifetime provides an economically viable option to commence a fuel switch and the following technology replacement. Real benefits and costs of the energy transition shall be fairly allocated to all stakeholders and communicated to the society. The social costs and implications in coal-dependent regions may be high, especially in the short-term perspective, but then the transformation will bring profits to the whole society.