Various techniques of determination of properties of physicochemical processes of heavy metal sorption in biosorbents were analysed. The methods of preparing and storing samples, conditions of experiment performance, as well as the methods of data interpretation were discussed. Two procedures of study were analysed: (1) in the static system of biosorbent-solution contact and (2) in the system of dynamic flow of solution. Copper cation sorption was studied. The effect of consecutive stages of the study on the quality of final results was shown. A high degree of uncertainty of the sorption capacity assessment was reported, which was dependent on the manner of conducting the study. The application of the pseudo-second order reaction model was substantiated to describe kinetics of cation-exchange sorption and the model of Langmuir isotherm to describe equilibria. The study conducted reveals that in order to perform comparative analyses, it is necessary to establish a joint concept of conducting studies and the interpretation of results.
Biomonitoring studies have been carried out in three retention reservoirs located in the Opole Province (southern Poland): Turawa reservoir, Nysa reservoir and Otmuchow reservoir. The increases of concentrations of Mn, Fe, Cu, Zn, Cd and Pb in fresh water algae Spirogyra sp. and sea water Palmaria palmata (Linnaeus) Weber & Mohr, exposed in the analysed waters, were determined by the atomic absorption spectrometry method (AAS). Also the waters pH, conductivity and Mn and Fe concentrations were determined. The concentrations of Cu, Zn, Cd and Pb in the analysed waters were lower than the method limit of determination. The analyses were carried out during the period from June to July 2014. The differences between the increases of heavy metal concentrations in the samples of algae found along the coastline were indicated; they result from different distances from the pollution sources, such as sediments or drainage from the areas adjacent to the reservoirs. Better sorption characteristics of Palmaria palmata in comparison to Spirogyra sp. were indicated. An empirical interrelation was also tested, the application of which after modification may enable the quantitative assessment of waters pollution with heavy metals, based on the analysis of the concentration of the element in the algae thallus.
Kinetics of the sorption of copper cations in Spirogyra sp. algae was analysed, together with the accompanying processes of hydrogen cations sorption and releasing to the solution the cations bonded in the algae: Na+, Mg2+, K+ and Ca2+. It was established that, in a static system, at the fixed proportion of algae mass to the solution volume, these processes occur simultaneously, however presumably the quantity of the released salts influences the parameters of heterophase equilibrium of ion exchange. In the experiment conditions, the quantity of the released cations was nearly 10 times larger than the quantity of the sorbed cations. The equilibrium parameters, determined from the model of pseudo second order reaction, were compared with the parameters obtained after 30 min of the process duration, ie at relatively stable indications of measuring equipment. On the example of the sorbed copper, the difference is approximately 8%. It was confirmed that the solution conductivity is a good parameter for the estimation of the state close to equilibrium.
Agnieszka Dołhańczuk-Śródka, Łukasz Wróbel, Andrzej Kłos and Maria Wacławek
Exploitation of coal deposits in Upper Silesia is associated with production of large quantities of waste deposited at dumps. The tested samples from five dumps showed different radioactivity from each other. Radioactivity measurements made it possible to analyze the degree of risk with the factors specified by UNSCEAR such as radium equivalent activity Raeq, internal Ein and external Eex occupancy factor. There is a raised level of radiation in dumps as compared with outside dump areas. In the study area, however, there is no risk associated with elevated levels of radiation in relation to standards established by the Council of Ministers of the ionizing radiation dose limits.
Małgorzata Rajfur, Małgorzata Anna Jóźwiak and Andrzej Kłos
Due to their occurrence in very different conditions and high resistance to physical and chemical factors, algae are pioneers colonising new environments and their sorption properties are used in biomonitoring and water remediation. The efficiency of the process of heavy metal sorption in algae used for in situ tests depends on abiotic factors, such as the chemical composition of water. Freshwater algae Spirogyra sp. were used in tests. Algae were exposed in the laboratory in manganese chloride solutions with various contents of other cations, including heavy metals and macronutrients. It has been shown that some heavy metals may desorb manganese bound to the surface of algae as a result of ion exchange in the following sequence: Cd2+ < Mn2+ ≈ Zn2+ < Cu2+. It has been also found that the competitiveness of sorption of cations naturally present in the alga environment versus Mn2+ cations changes in the sequence Na+ < Ca2+ < H+, defined for the concentrations referring to the cation unit charge. The results of tests were compared to the results of dried sea algae Palmaria palmata analyses.
Paweł Krems, Małgorzata Rajfur, Maria Wacławek and Andrzej Kłos
The publication is a synthetic review of many years of research on the possibility of using water plants (macrophytes) to assess pollution of surface waters and the possibility of using the biomass in phytoremediation processes. The results of the research of kinetics and equilibria of heavy metals sorption and desorption conditions were presented in order to repeatedly use the biomass, as well as the research on the influence of abiotic factors on sorption processes. Defence mechanisms of macrophytes, which enable them to vegetate in considerably polluted waters, have been discussed. The results presented herein and carried out in many countries demonstrate that macrophytes can be successfully used in the biomonitoring of water environments and phytoremediation of waters and sewage; however, validation of these procedures requires more detailed research of the mechanisms, which accompany them.
Małgorzata Rajfur, Paweł Krems, Andrzej Kłos, Rafał Kozłowski, Małgorzata A. Jóźwiak, Jan Kříž and Maria Wacławek
During the years 2014-2015, biomonitoring studies were carried out at three holding reservoirs located in Swietokrzyskie Province (central Poland): Kielce artificial lake, Chancza reservoir and Sielpia reservoir. In sea water algae Palmaria palmata (Linnaeus) Weber & Mohr, exposed in the analysed waters, the increases of concentrations were determined by the atomic absorption spectrometry method (AAS), of the following: Mn, Fe, Cu, Zn, Cd and Pb. Conductivity and pH were also determined in the reservoirs waters. The differences between the increases of heavy metal concentrations in the samples of algae found along the coastline were indicated; they result from different distances from the pollution sources, such as resorts, communication routes and industrial plants.
Jan Kříž, Jan Loskot, Vladimír Štěpánek, Lidmila Hyšplerová, Daniel Jezbera, Lucie Trnková, Agnieszka Dołhańczuk-Śródka, Zbigniew Ziembik, Małgorzata Rajfur, Andrzej Kłos and Maria Wacławek
Tightening of norms for air protection leads to a development of new and significantly more effective techniques for removing particulate matter, SOx and NOx from flue gas which originates from large solid fuel combustion. Recently, it has been found that combinations of these environmental technologies can also lead to the reduction of mercury emissions from coal power plants. Now the greatest attention is paid especially to the coal power plant in Opatovice nad Labem, close to Hradec Kralove. Its system for flue gas dedusting was replaced by a modern type of cloth fabric filter with the highest particle separation efficiency which belongs to the category of BAT. Using this technology, together with modernization of the desulphurisation device and increasing of nitrogen oxides removal efficiency, leads also to a reduction of mercury emissions from this power plant. The University of Hradec Kralove, the Opole University and EMPLA Hradec Kralove successfully cooperate in the field of toxic metals biomonitoring almost 20 years. In the Czech-Polish border region, comprehensive biomonitoring of mercury in bioindicators Xerocomus badius in 9 long-term monitored reference points is done. The values of mercury concentration measured in 2012 and 2016 were compared with values computed by a dispersion model SYMOS′97 (updated 2014). Thanks to modern methods of dedusting and desulphurisation, emissions of mercury from this large coal power plant are now smaller than before and that the downward trends continues. The results indicate that Xerocomus badius is a suitable bioindicator for a long-term monitoring of changes in mercury imissions in this forested border region. This finding is significant because it shows that this region is suitable for leisure, recreation, and rehabilitation.
Tomasz Ciesielczuk, Tomasz Olszowski, Marcin Prokop and Andrzej Kłos
The moss Pleurozium schreberi was used to evaluate the emission of polycyclic aromatic hydrocarbons (PAHs) at Polish cemeteries on the All Saints' Day, when Poles traditionally light candles and candle lamps in memory of the deceased. Moss samples were exposed for 7 days at 4 cemeteries and, for comparison, in a city centre and in a rural area. During exposition, the mean content of 16 monitored PAHs in the samples increased by 455 ng/g at the cemeteries and by 689 ng g-1 in the city centre. In the rural area, the samples showed no statistically significant changes. PAHs whose content increased only in the moss samples exposed at the cemeteries included naphthalene, pyrene, benzo[b]fluoranthene together with benzo[k]fluoranthene, benzo[g,h,i]perylene, indeno[1,2,3-cd]pyrene and dibenzo[a,h]anthracene. The concentrations of other PAHs increased in samples exposed in the city centre and at two cemeteries located in the suburban areas. The results presented confirm the possibility of using mosses in biomonitoring of PAHs.
Andrzej Kłos, Yulia A. Aleksiayenak, Zbigniew Ziembik, Małgorzata Rajfur, Dominik Jerz, Maria Wacławek and Marina V. Frontasyeva
The neutron activation analysis procedure was used to determine the concentration of 42 elements: Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Co, Zn, As, Se, Br, Rb, Sr, Zr, Nb, Mo, I, Ag, Cd, Sb, Ba, Cs, La, Ce, Nd, Sm, Eu, Tb, Yb, Hf, Ta, W, Au, Hg, Th, and U accumulated in mosses sampled for testing in September and October 2011 in the Opole Province (Southern Poland). Samples of different moss species were collected near the intersections of the grid lines marked on the map of the province. The distance between the points was approximately 20 km. The analysis of the results made it possible to identify the places of increased deposition of element-pollutants and to indicate the potential sources of emission. Factor analysis revealed four components, two of which are of definite anthropogenic origin. The possible sources of elements are local industry and farming, and distant heavy industry complexes. The results have demonstrated the increased content of Cr, Cd, Hg, and U in moss samples collected in agricultural areas located in the southern part of the province. It has been concluded that the industrial areas of Rybnik and Ostrava and Karvina Coal Basin may be the potential source of emission of these elements.