Effect of Cross-Linking Waste Protein with Dialdehydes on Its Biodegradation Under Anaerobic Conditions

Most native polymers used in processing and application technologies are admittedly disposable from the environment in a biologic manner, but products possess low mechanical strength. One of the paths to increasing this attribute (if feasible) is their cross-linking, which may, however, affect their readiness to biodegradation. In the presented work this condition was observed on the example of waste protein (Hykol B) cross-linking by means of glutardialdehyde and glyoxal. Degree and course of cross-linking were determined through impedance spectroscopy. The objective of this work also was to obtain data for constructing a sensor capable of following the cross-linking course in real time, for potential industrial application of Hykol in continuous production. Impedance spectroscopy proved to be applicable even to this kind of material marked by considerable water content and exhibiting relatively high electric conductivity; so far it had been used only for materials of low conductivity. An aqueous environment inoculated with digested anaerobic sludge from a municipal wastewater treatment plant was selected for modeling anaerobic conditions. The relation was studied between cross-linking degree given by content of cross-linking agent (determined by impedance spectroscopy) and biodegradation degree under anaerobic conditions. It was confirmed that network density as given by quantity of added agent not only reduced breakdown degree but also slowed the course of the process. This fact is particularly obvious with cross-linking by means of glyoxal; network density is thus dependent on type of employed substance, which affect type and structure of created network. That not merely forms an obstacle during polymer swelling and dissolution but also prevents access of bacteria to source of metabolized organic carbon.     

Effect of Cross-Linking Waste Protein with Diepoxides on its Biodegradation under Anaerobic Conditions

Biodegradability testing was performed in an aqueous environment under anaerobic conditions after inoculation with digested sludge from municipal wastewater treatment plant. In cross-linking with 1,2:3,4-diepoxybutane in limits 0.8–9.1% weight, biodegradability degree decreased from 76.8 to 62.2%; when 1,2:7,8 diepoxyoctane in quantities 1.1–13.2% weight was used, biodegradability degree dropped more prominently – from 72.3 to 22.8%. There is obviously a direct connection between growing cross-link degree (assessed by so-called fixation index) and decreasing readiness to biodegradation, apparently owing to build-up of a network forming an obstacle to access of micro-organisms and enzymes.     

Deposition and Fate of Lead in a Forested Catchment, Lesni Potok, Central Czech Republic

The deposition of trace elements and their fate in a forest ecosystemhas been monitored at the experimental site, Lesni Potok catchment (LP), with granite bedrock. The catchment is located 30 km ESE from Prague. Annual bulk Pb-deposition flux F_Pb was 3.41 kg km^-2 a^-1 in 1994 and gradually decreased to 0.49 kg km^-2 a^-1 in 2001. The decrease is comparable with those observed in Germany and in the U.S.A. in the 1970s and 1980s. The total sales ban of leaded gasoline in the Czech Republic since January 2001 was accompanied by a pronounced decrease of F_Pb in a single year. The residual Pb-deposition flux is assigned to both the long-range transport of fine-grained vehicular lead aerosol (with a long residence time in the atmosphere) and to theemissions from power plant boilers burning lignite mined in the Czech northwest coal basin. The F_Pb of lead correlates stronglywith those of As, Cd, Cu, Zn and Be, the typical metals in coal fly ash, at two monitored sites. Topsoil horizons contain elevated concentrations of Pb (53–67 mg kg^-1), which are of anthropogenicorigin. Soils in the riparian areas contain increased concentrations of Pb when compared to soils on the hillslope areas. Significant amounts of Pb were found on a stream substrate and Fe-precipitate sampled from the stream. Low concentrations of Pb in bark and bole wood suggest that the uptake of Pb by vegetation is negligible. The very small surface water outputs (average of 0.002 kg km^-2 a^-1) compared to inputs (average of 1.890 kg km^-2 a^-1) from the LP catchment indicate an ongoing accumulation of Pb in a forested landscape.     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Effects of synthetic pyrethroids and methidation on activities of some digestive enzymes in carp (Cyprinus carpio L.)

Abstract

The effects of pyrethroid pesticides (deltamethrin, permethrin and cypermethrin) and an organophosphate ester (methidation) on the activities of carp trypsin, α‐chymotrypsin, carboxypeptidase A and lipase were studied. The enzymes were isolated from the gastrointestinal tract and the effects of the pesticides were investigated during incubation for 5 min. The activity of trypsin was influenced only slightly by the presence of deltamethrin and methidation, whereas permethrin and cypermethrin caused significant inhibition. The pyrethroid pesticides at lower concentrations resulted in a slight activation of α‐chymotrypsin. Methidation inhibited the α‐chymotrypsin activity by about 20%. These pesticides modified the lipase activity to a lesser extent; the highest inhibition was measured with cypermethrin. The carboxypeptidase A activity was inhibited by both pyrethroid pesticides and methidation. The results suggest that these pesticides might interact with the active conformation of the studied hydrolytic enzymes, resulting in changes in their activities.     

Evaluation of the use of bioaccumulation and biological effects tools in caged mussels,within the European Water Framework Directive

Bioaccumulation and biological effects of pollution were assessed in mussels (Mytilus galloprovincialis) caged for one month at three sites in the Oiartzun estuary (south-eastern Bay of Biscay, Spain) with the aim of evaluating their usefulness within the investigative monitoring defined in the European Union Water Framework Directive (WFD). The highest concentrations of organic contaminants determined in mussels' tissue were detected towards the inner part of the estuary but no gradient pattern was found for metal bioaccumulation. Population fitness responses measured as condition index, stress on stress and gonad index were similar in all caged mussels and did not follow the organic pollution gradient. However, biomarkers determined at tissue, cell and protein level (histopathology, micronuclei frequency, malondialdehyde levels and vitellogenin-like protein levels) revealed a higher stress syndrome at the inner part of the estuary showing signs of genotoxicity, oxidative stress and endocrine disruption. Overall, the integrated chemical–biological approach in connection with mussel caging technique proved to be a useful tool to assess environmental pollution, allowing a better understanding of the cause–effect relationship within the investigative monitoring defined in the WFD.     

Trace element concentrations in soils along urbanization gradients in the city of Wien, Austria

Urban soil is an important component of urban ecosystems. This study focuses on heavy metal contamination in soils of Wien (Austria) and results are compared to those for a few large European cities. We analysed the elemental contents of 96 samples of topsoil from urban, suburban and rural areas in Wien along a dynamic (floodplain forest) and a stable (oak–hornbeam forest) urbanization gradient. The following elements were quantified using ICP-OES technique: Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Pb, P, S and Zn. For heavy metals PI (pollution index) values were used to assess the level of pollution. The PI values indicated high level of pollution by Pb in the suburban and rural area of stable gradient and in the urban area of dynamic gradient; moderate level of pollution was indicated for Cd in the urban area of stable gradient. The level of pollution was moderate for Co in the suburban and rural area of the stable gradient, and for Cu in suburban area of stable gradient, and urban area of dynamic gradient. The pollution level of Zn was moderate in all areas. Urban soils, especially in urban parks and green areas may have a direct influence on human health. Thus, the elemental analysis of soil samples is one of the best ways to study the effects of urbanization. Our results indicated that the heavy metal contamination was higher in Wien than in a few large European cities.     

Effects of heavy metals and nitroaromatic compounds on horseradish glutathione S-transferase and peroxidase

Glutathione S-transferase (GST) and peroxidase (POX) activities have a direct relation to the effect of stress on plant metabolism. Changes in the activities of the enzymes were therefore studied. Horseradish hairy roots were treated by selected bivalent ions of heavy metals (HMs) and nitroaromatic compounds (NACs). We have shown differences in GST activity when assayed with substrates 1-chloro-2,4-dinitrobenzene (CDNB) and 1,2-dichloro-4-nitrobenzene (DCNB). The conjugation of DCNB catalysed by GST was inhibited in all roots treated with HMs as compared to non-treated roots, whereas NACs caused induction of the activity in dependence on the exposition time and concentration of compounds. The conjugation of CDNB by GST was not affected to the same extent. The increase of GST activity was determined in cultures treated by nickel (0.1 mM) and diaminonitrotoluenes (DANTs, 0.1 mM) for 6 h, whereas the roots treated by 2,4,6-trinitrotoluene (TNT), 4-amino-2,6-dinitrotoluene (ADNT) and dinitrotoluene (DNT, 1.0 mM) needed 27 h treatment to induce the activity. The POX activity of cultures treated by HMs was inhibited to 17-35% in comparison to non-treated cultures. The POX activity of roots treated by TNT (0.1 and 1.0 mM) for 6 and 27 h and by ADNT (0.1 and 1.0 mM) for 6 h was inhibited. A partial increase of POX activity was measured in roots treated by all NACs for 27 h. The content of oxidized glutathione (GSSG) and reduced glutathione (GSH) in the roots differed significantly. It was followed as a symptom of the stress reaction of the plant metabolism to the effect of NACs and HMs.     

A real-time,dynamic early-warning model based on uncertainty analysis and risk assessment for sudden water pollution accidents

A real-time, dynamic, early-warning model (EP-risk model) is proposed to cope with sudden water quality pollution accidents affecting downstream areas with raw-water intakes (denoted as EPs). The EP-risk model outputs the risk level of water pollution at the EP by calculating the likelihood of pollution and evaluating the impact of pollution. A generalized form of the EP-risk model for river pollution accidents based on Monte Carlo simulation, the analytic hierarchy process (AHP) method, and the risk matrix method is proposed. The likelihood of water pollution at the EP is calculated by the Monte Carlo method, which is used for uncertainty analysis of pollutants’ transport in rivers. The impact of water pollution at the EP is evaluated by expert knowledge and the results of Monte Carlo simulation based on the analytic hierarchy process. The final risk level of water pollution at the EP is determined by the risk matrix method. A case study of the proposed method is illustrated with a phenol spill accident in China.     

Evaluation of boron removal from water by hydrotalcite-like compounds

Layered double hydroxides (LDHs) or hydrotalcite (HT)-like compounds with different kinds of metal ions (Mg-Al and Mg-Fe) in the brucite-like sheets were prepared and their adsorption properties were studied in the boron removal from aqueous solution under laboratory conditions. The hydrotalcites were synthesized by the coprecipitation method and were characterized by chemical analyses, X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and specific surface area measurements (BET). The affinity of these materials with a mixture of B(OH)(3) and B(OH)(4)(-) was studied as a function of contact time, initial pH of the solutions, HT quantity and B concentration (adsorption isotherms). It was found that 120 min is enough time for the equilibrium state to be reached in boron adsorption. Boron removal was independent of the initial pH of the solutions because of the high buffering capacity of the LDHs. On the other hand, the adsorption capacity increases with increasing the adsorbent quantity. The adsorption isotherms, described by the Langmuir model, are of L-type, suggesting that B(OH)(4)(-) is adsorbed preferentially on HT-like materials. Besides, Mg-Al hydrotalcites showed higher adsorption capacity than Mg-Fe. We proposed that in Mg-Al hydrotalcites, the boron removal occurs by both adsorption on external surface and ion exchange, whereas for Mg-Fe it occurs only by surface adsorption. After treatment of a solution containing 5.2 mgBl(-1) with Mg-Al hydrotalcites the final boron concentration reached the recommended limit by WHO for drinking water (0.5 mgl(-1)).