The significance of heterophasic ion exchange in active biomonitoring of heavy metal pollution of surface waters.

We have carried out studies to examine the possibility of using biosorbents: the epigeic mosses Pleurozium schreberi (Willd. ex Brid.) Mitt., and the epiphytic lichens Hypogymnia physodes (L.) Nyl. in active biomonitoring of heavy metal pollution of surface waters. The dried sea algae Palmaria palmata (L.) Weber & Mohr were used as the third biosorbent. The studies were conducted in the waters of the Turawa Reservoir, a dam reservoir with a significant level of eutrophication in south-western Poland. Incremental concentrations of Mn, Ni, Zn, Cu, Cd, and Pb were determined in the exposed samples. It was shown that a 2-h exposure period increases the concentration of some metals in the exposed samples, even by as much as several hundred percent. High increments of nickel concentrations in the algae Palmaria palmata (mean: 0.0040 mg/g, with the initial concentration of c0 < 0.0016 in the algae) were noted, with negligible increments in concentrations of this metal in mosses and lichens. In contrast, mosses and lichens accumulated relatively high amounts of Cd (mean: 0.0033 mg/g, c0 = 0.00043 mg/g) and Pb (mean: 0.0243 mg/g, c0 = 0.0103 mg/g), respectively.

Role of calcium carbonate in the process of heavy metal biosorption from solutions: synergy of metal removal mechanisms.

The effect of calcium carbonate on the removal efficiency of cations of the selected heavy metals Cu, Zn and Pb from aqueous solutions using various biosorbents (BS) was investigated under laboratory static conditions. The main mechanism of biosorption of heavy metal cations is ion exchange, whereas the reaction with calcium carbonate results in precipitation of poorly soluble carbonates and hydroxides of the examined heavy metals. Studies conducted under static conditions have shown that the effect of Cu and Zn cations removal from solutions is better when using a mixture of BS and CaCO3 as compared to the effect of process, in which these two components were used separately. Removal efficiency for Cu and Zn has been shown to increase from 20 to 50% depending on the BS used. For the removal of lead cations, a measurable effect is found only for biosorbents whose active centers are saturated with protons (improvement in removal efficiency by about 20%). A synergy effect in the flow system was also investigated. It was found that under the conditions of the experiment, the addition of powdered CaCO3, in a weight ratio of 1 g CaCO3: 15 g BS, increases the removal efficiency of all the metals studied by 20-30%. It has been shown that an important role in the process of heterophasic ion exchange is played by neutralization of protons-desorbed from the biosorbents-with hydroxide ions released into the solution by partial dissolution of CaCO3 and subsequent hydrolysis reaction.

Using moss and lichens in biomonitoring of heavy-metal contamination of forest areas in southern and north-eastern Poland.

In the years 2014-2016 biomonitoring studies were conducted in the forest areas of south and north-eastern Poland: the Karkonosze Mountains, the Beskidy Mountains, the Borecka Forest, the Knyszynska Forest and the Bialowieska Forest. This study used epigeic moss Pleurozium schreberi and epiphytic lichens Hypogymnia physodes. Samples were collected in spring, summer and autumn. Approximately 500 samples of moss and lichens were collected for the study. In the samples, Mn, Ni, Cu, Zn, Cd, Hg and Pb concentrations were determined. Based on the obtained results, the studied areas were ranked by extent of heavy-metal deposition: Beskidy > Karkonosze Mountains > forests of north-eastern Poland. Some seasonal changes in concentrations of metals accumulated in moss and lichens were also indicated. There was observed, i.a., an increase in Cd concentration at the beginning of the growing season, which may be related to low emissions during the heating season. Analysis of the surface distribution of deposition of metals in the studied areas showed a significant contribution of nearby territorial emissions and unidentified local emission sources. The contribution of distant emission to Zn, Hg and Pb deposition levels in the Karkonosze and Beskidy region was also indicated.

The activity concentration of post-Chernobyl ¹³7Cs in the area of the Opole Anomaly (southern Poland).

During the years 2007 and 2010, the activity concentration of (137)Cs accumulated in soil, mosses Pleurozium schreberi and lichens Hypogymnia physodes was measured. The studies covered the areas of the so-called Opole Anomaly. In consequence of the Chernobyl nuclear power plant breakdown in 1986, relatively large amounts of this radionuclide were deposited in this area. In some areas of the Anomaly, over 100 times higher surface activity of (137)Cs was detected, compared to the lowest values registered in Poland. Currently, (137)Cs is still present in woodlands and wastelands. As at 2 April 2013, the surface activity concentration of (137)Cs in soil on the tested area was from 0.34 to 67.5 kBq m(-2). In comparison, the surface activity concentration of (137)Cs as at 1 June 1986, soon after deposition, was from 2.08 to over 125 kBq m(-2). The maximum specific activity concentrations of (137)Cs in mosses and lichens sampled for testing in 2010 were respectively 1234 and 959 Bq kg(-1). It was also proven that the changes in activity concentration of (137)Cs in the area of the Anomaly are mainly the consequence of the radioactive decay of this radionuclide.

Sorption of cadmium and zinc in selected species of epigeic mosses.

The sorption abilities of seven moss species growing on the area of Bory Stobrawskie forest (southern Poland) were tested in laboratory. Sorption was carried out in solutions of Zn and Cd chlorides. It has been shown that the sorption properties depend on the moss species and increases in the series as follows: Polytrichum commune < Leucobryum glaucum < Eurhynchium praelongum < Thuidium tamtariscifolium ≤ Dicranum scoparium ≤ Pleurozium schreberi < Sphagnum sp. With help of microscope images, it was also demonstrated that one of the factors affecting the sorption properties of mosses was the level of their surface development. The determined sorption capacity of Zn varies according to species of mosses from 0.0491 to 0.1287 mmol g(-1), and in relation to Cd from 0.0319 to 0.1335 mmol g(-1). The described results may be important in the process of biomonitoring research design and in the test results interpretation.

Sorption of heavy metals in the biomass of alga Palmaria palmata.

Sorption of heavy metals by the sea alga Palmaria palmata was investigated in laboratory conditions. The sorption process of the analytes was carried out with constant flow of the solutions through the algae samples. The Langmuir isotherm model was used to describe equilibria. The experiments confirmed that 50 min of exposure of algae with little heavy metal contamination in contaminated waters results in the increase of concentration of these analytes, proportional to their concentration in the tested waters. On the basis of the Langmuir isotherm direction factor, a = (c(a,max) × K)(-1), affinity of heavy metals and algae increases in the following sequence: Mn(2+) < Zn(2+) ≈ Cd(2+) < Cu(2+), and the competitiveness of sorption of cations naturally present in the algae environment versus Zn(2+) ions changes according to following sequence: Na(+) < Ca(2+) < H(+), defined for the concentrations referring to the ion unit charge. It was also confirmed, that the presence of sodium and calcium ions in the solutions, within the conductivity range from 200 to 1,000 µS/cm, is not statistically significant for the sorption of heavy metals from these solutions.

Influence of hydrogen cations on kinetics and equilibria of heavy-metal sorption by algae-sorption of copper cations by the alga Palmaria palmata (Linnaeus) Weber & Mohr (Rhodophyta).

The influence of hydrogen cations on kinetics and equilibria of sorption of copper cations by the marine alga Palmaria palmata (Linnaeus) Weber & Mohr was studied under static conditions. The competitive effect of the H+ cations is described, which influenced the uncertainty of evaluation of the alga sorption capacity. Under static conditions, the variation of the Cu2+/H+ concentration ratio during sorption was found nonmonotonic. The Langmuir isotherm model was used to determine the sorption capacity of the alga, namely 12.4 mg g-1 of dry algae mass. A similar value was determined from the kinetic parameters of the ionic exchange which is considered a pseudo-second-order chemical reaction. The consistent results indicated that the mathematical models used correctly described the equilibria and kinetics of the ionic exchange between algae and solutions.

The impact of candle burning during All Saints' Day ceremonies on ambient alkyl-substituted benzene concentrations.

Research findings concerning benzene, toluene, ethylobenzene, meta-, para- and ortho-xylene as well as styrene (BTEXS) emission at public cemeteries during All Saints' Day are presented here. Tests were carried out at town-located cemeteries in Opole and Grodków (southern Poland) and, as a benchmark, at the centres of those same towns. The purpose of the study was to estimate BTEXS emissions caused by the candle burning and, equally important to examine, whether emissions generated by the tested sources were similar to the BTEXS emissions generated by road transport. During the festive period, significant increases in benzene concentrations, by 200 % and 144 %, were noted at the cemeteries in Opole and Grodków, as well as in toluene, by 366 % and 342 %, respectively. Styrene concentrations also increased. It was demonstrated that the ratio of toluene to benzene concentrations from emissions caused by the burning candles are comparable to the ratio established for transportation emissions.

Mechanisms for Translocation of Heavy Metals from Soil to Epigeal Mosses.

The mechanisms for translocation of heavy metals from soil to epigeal mosses were investigated. The first mechanism was demonstrated for (137)Cs and involved the uplifting of the pollutant-containing dust from the soil, followed by the local secondary deposition on surfaces of epigeal mosses and epiphytic lichens. The second mechanism involved the diffusion of metal cations from the soil through water wetting the moss into the gametophyte. The mechanism was demonstrated by measuring the electric conductance of wetted gametophytes with single ends immersed in solutions of Cu and Na salts. In addition, the concentrations of Cu and Cd were compared in moss samples exposed to the natural soil and to the soil contaminated with the metals. The exposition to the contaminated soil resulted in the statistically significant increase of metal concentrations in the gametophytes.

Sorption of copper(II) ions in the biomass of alga Spirogyra sp.

Sorption of copper ions by the alga Spirogyra sp. was investigated to determine the influence of experimental conditions and the methods of sample preparation on the process. The experiments were carried out both under the static and the dynamic conditions. Kinetics and equilibrium parameters of the sorption were evaluated. In addition, the influence was studied of the algae preparation methods on the conductivity of demineralized water in which the algae samples were immersed. The static experiments showed that the sorption of Cu(2+) ions reached equilibrium in about 30 min, with approximately 90% of the ions adsorbed in the initial 15 min. The sorption capacity determined from the Langmuir isotherms appeared highly uncertain (SD=±0.027 mg/g dry mass or ±11%, for the live algae). Under static conditions, the slopes of the Langmuir isotherms depended on the ratio of the alga mass to the volume of solution. The conductometric measurements were proven to be a simple and fast way to evaluate the quality of algae used for the experiments.

Mercury concentration in lichen, moss and soil samples collected from the forest areas of Praded and Glacensis Euroregions (Poland and Czech Republic).

The concentration of mercury was determined in samples of the lichen Hypogymnia physodes, the moss Pleurozium schreberi, and the soil humus collected in Polish and Czech Euroregions Praded and Glacensis. The sampling sites were located in Bory Stobrawskie, Bory Niemodlinskie and Kotlina Klodzka in Poland, and in Jeseniki and Gory Orlickie in the Czech Republic. The mean concentrations of mercury accumulated in the lichen (0.129 mg g(-1)), in the moss (0.094 mg g(-1)) and in soil (0.286 mg g(-1)) were fairly close to the corresponding concentrations in other low-industrialized regions. The highest concentrations of mercury were observed in the lichen and the moss samples from Kotlina Klodzka. The primary deposition of mercury was evaluated using the comparison factor, defined as the ratio of a difference between the concentrations of a bioavailable analyte in lichens and in mosses, to the arithmetic mean of these concentrations.

Use of Lichen and Moss in Assessment of Forest Contamination with Heavy Metals in Praded and Glacensis Euroregions (Poland and Czech Republic).

The concentrations of selected metals-Cr, Ni, Cu, Zn, Cd, and Pb-were determined in the samples of Hypogymnia physodes lichen and Pleurozium schreberi moss collected in Polish and Czech Euroregions Praded and Glacensis. More specifically, the samples were collected in Bory Stobrawskie, Bory Niemodlinskie, and Kotlina Klodzka (Poland) and in Jeseniki (Czech Republic). The concentration of metals in the samples was measured using the atomic absorption spectrometry (flame AAS technique and electrothermal atomization AAS technique). The results were used to calculate the comparison factor (CF) that quantifies the difference in concentration of a given bioavailable analyte × accumulated in lichens and mosses: CF = 2 (c(x,lichen) - c(x,moss)) (c(x,lichen) + c(x,moss))(-1). The values of CF greater than 0.62 indicate the most probable location of heavy metals deposited in the considered area. In this work, the method was used to show a significant contribution of urban emissions to the deposition of heavy metals in the area of Bory Stobrawskie and in the vicinity of Klodzko City.

Algae utilization in assessment of the large Turawa Lake (Poland) pollution with heavy metals.

This investigation was undertaken to determine the applicability of algae for the assessment of contamination level of water reservoirs with heavy metals. The alga Spirogyra sp. collected in the littoral zone of the Large Turawa Lake (artificial lake in Southern Poland) was used for the study. The concentrations of heavy metals accumulated in the alga inhabiting a flow-through water basin of the Large Turawa Lake were found to correlate with sources of these metals, such as benthic sediments and contaminated watercourses. The highest concentrations of metals were found in alga samples collected at the outlet of the lake: c (Mn) = 12330 mg/kg dry mass, c (Fe) = 15059 mg/kg d.m., c (Cu) = 47.5 mg/kg d.m., c (Zn) = 1411 mg/kg d.m., c (Cd) = 108.8 mg/kg d.m., and c (Pb) = 684 mg/kg d.m. The metals originated from benthic sediments (sapropelic mud) deposited close to the outlet of the lake. Statistically significant differences in the concentrations of cadmium accumulated in the alga were found between samples from the sites, where cadmium occurred in sandy sediments (max. 27.6 mg/kg d.m.), and samples from the sites located far from the contaminated sediments (max. 12.8 mg/kg d.m.).

Sorption properties of algae Spirogyra sp. and their use for determination of heavy metal ions concentrations in surface water.

Kinetics of heavy-metal ions sorption by alga Spirogyra sp. was evaluated experimentally in the laboratory, using both the static and the dynamic approach. The metal ions--Mn(2+), Cu(2+), Zn(2+) and Cd(2+)--were sorbed from aqueous solutions of their salts. The static experiments showed that the sorption equilibria were attained in 30 min, with 90-95% of metal ions sorbed in first 10 min of each process. The sorption equilibria were approximated with the Langmuir isotherm model. The algae sorbed each heavy metal ions proportionally to the amount of this metal ions in solution. The experiments confirmed that after 30 min of exposition to contaminated water, the concentration of heavy metal ions in the algae, which initially contained small amounts of these metal ions, increased proportionally to the concentration of metal ions in solution. The presented results can be used for elaboration of a method for classification of surface waters that complies with the legal regulations.

Ion equilibrium in lichen surrounding.

In laboratory conditions, the ionic equilibriums between a solution and a cation-active layer of epiphytic lichens Hypogymnia physodes immersed in the solution were examined. It was found that such equilibriums, due to exchange of mobile cations: H, Na, K, Ca, and Mg, are established in natural conditions between a lichen and atmospheric water.