Sabina Dołęgowska

Anomalous concentrations of rare earth elements in the moss–soil system from south-central Poland

Fourteen rare earth elements were determined in mosses (Pleurozium schreberi) and soils (subhorizon-Ofh and -Ol, mixed horizon-AE and AEB) from south-central Poland. The results were normalized against North American Shale Composite (NASC) and Post-Archean Australian Shales (PAAS). The distribution of REEs in the moss-soil system differed considerably, but all the samples showed the average percent of increase of medium rare earth elements. The shale-normalized concentration ratios calculated for selected elements (LaN/YbN, GdN/YbN, LaN/SmN) were in the range of 1.22-2.43, 1.74-3.10 and 0.86-1.09. Both subhorizon-Ofh (-Ol) and horizon-AE (-AEB) showed a weak enrichment of Gd. The shale-normalized patterns of soils showed a somewhat negative Eu anomaly in the horizon-AE (-AEB), and a slightly negative Ce anomaly in the subhorizon-Ofh (-Ol). A strongly positive Eu anomaly and a somewhat negative Nd anomaly were found in the moss samples.

The influence of chloride deicers on mineral nutrition and the health status of roadside trees in the city of Kielce, Poland

Application of chemical road deicers has a negative impact on roadside vegetation. Every year, the trees in cities suffer from direct and indirect effects of salt application for winter road maintenance. To elucidate this problem in the city of Kielce, the chemistry of snow, soil, tree bark, and leaf samples has been investigated together with an assessment of the health status of the trees. Twelve investigation sites were selected along the roads with different traffic intensity. Snow samples were collected twice during the winter and analyzed for pH, EC, Na + , Ca2 + , Mg2 + , and Cl − . In soil (collected from two depth intervals), tree bark, and leaf samples, the concentrations of B, Ca, Fe, K, Mg, Mn, N, Na, P, S, and Zn were determined. The contents of total organic carbon (TOC) in soils, as well as the pH of soil and tree bark samples were also measured. Negative symptoms revealed by roadside trees included the loss of assimilative apparatus and decreased vitality. The results of chemical analyses indicated that the snowmelt might be a substantial source of chloride ions and alkalizing substances that influenced higher pH of soils. The soil samples displayed elevated concentrations of S and Zn and lower than typical for soil contents of B, Mg, and TOC. The pH of alkaline soils favored greater bioavailability of B and reduced bioavailability of Na and Zn by the trees examined.

Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. as trace element bioindicators: statistical comparison of bioaccumulative properties.

The principal objective of this study was to compare bioaccumulative properties of two terrestrial moss species Hylocomium splendens and Pleurozium schreberi from the Kielce area (south-central Poland), using various statistical techniques. Forty-six moss samples from 23 sampling sites located within the city limits were analyzed for 33 trace elements. The results indicated that 17 elements (Ba, Ce, Co, Cu, Eu, Fe, Gd, Hg, La, Mo, Nd, Ni, Pb, Pr, Sm, V, Y) dominated in H. splendens, whereas only three elements (Mn, Sr, Zn) occurred in excessive amounts in P. schreberi. No differences in the distribution pattern of Dy, Er, Ho, Sn, Tb, Th and Yb were observed. The element concentration ratio (PI/Hy) varied from 0.50 to 1.19. For 14 elements (Ce, Co, Cu, Fe, Gd, Hg, La, Mo, Nd, Ni, Pb, Sm, Th, V), PI/Hy < 1; for 4 elements (Cd, Mn, Sr, Zn), PI/Hy > 1; for 7 elements (Ba, Dy, Er, Eu, Pr, Y, Yb), PI/Hy = equalled 1. Czekanowskis method showed similarities in rare earth element concentrations for both moss species. The cluster analysis exhibited three significant clusters at D(link)/D(max) x 100 < 50 for both moss species. Strong positive Spearman correlations between both moss species were recorded for the following pairs: Ba-Ba, Co-Co, Er-Er, Eu-Eu, Gd Gd, Mn-Mn, Ni-Ni, Pb-Pb, Pr-Pr, Sm-Sm, Th-Th, Y-Y, and Yb-Yb. Nonparametric tests (Sign test, Wilcoxon tests) showed statistically significant differences only for Cd, Ce, Co, Cu, Hg, Mo, Ni, Pb and Sr. The scanning electron microscope study of H. splendens and P. schreberi revealed a different morphology of these species with no injuries.

Stable sulphur isotope ratios in the moss species Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from the Kielce area (south-central Poland)

Stable sulphur isotope determinations were performed on 18 moss samples collected at nine sites in forested areas of the city of Kielce. The δ34S of Hylocomium splendens varied from 4.4 to 7.1 ‰, whereas the δ34S of Pleurozium schreberi was in the range of 3.7–9.1 ‰. The Holy Cross Mountains mosses display a positive δ34S signature of airborne SO2 and sulphates of anthropogenic origin, which is characteristic for this part of Europe. Some spatial variations in the δ34S of mosses are due to the interactions that occur between coal combustion emissions with diverse isotopic imprints, variations in wind direction and topographic features combined with biological fractionation.

Geochemical anomalies of trace elements in unremediated soils of Mt. Karczówka, a historic lead mining area in the city of Kielce, Poland

Concentrations of selected trace elements (Ag, As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Zn) and rare earth elements were determined in 61 samples of surface soils collected from Mt. Karczówka, a historic Pb ore mining area located in the city of Kielce, south-central Poland. Some of these samples were subjected to XRD analyses and Pb stable isotope measurements. The mineral and chemical composition of rock samples were also examined. Mining activity in the study area was conducted mostly during 15th-17th centuries using technologically primitive methods, and was finally ceased in the first half of the 19th century. More than three thousand old shafts, pits and adits occur in the study area and its vicinity. The soils of the study area have not been remediated since the end of the mining operations. The trace elements of the examined surface soils are heterogeneously distributed with lead concentrations in the range of 41-9114 mg/kg and Pb isotopic signatures similar to those of local galena. The results of trace element measurements allowed us to discriminate geochemical anomalies from background levels and to link mineralogy of the host rocks to the origin of anomalous element concentrations. This study shows that elevated levels of elements of geogenic origin have remained in surface soil for two centuries after cessation of mining operations.

An impact of moss sample cleaning on uncertainty of analytical measurement and pattern profiles of rare earth elements

The main source of rare earth elements (REE) in mosses is atmospheric deposition of particles. Sample treatment operations including shaking, rinsing or washing, which are made in a standard way on moss samples prior to chemical analysis, may lead to removing particles adsorbed onto their tissues. This in turn causes differences in REE concentrations in treated and untreated samples. For the present study, 27 combined moss samples were collected within three wooded areas and prepared for REE determinations by ICP-MS using both manual cleaning by shaking and triple rinsing with deionized water. Higher concentrations of REE were found in manually cleaned samples. The comparison of REE signatures and shale-normalized REE concentration patterns showed that the treatment procedure did not lead to fractionation of REE. All the samples were enriched in medium rare earth elements, and the δMREE factor remained practically unchanged after rinsing. Positive anomalies of Nd, Sm, Eu, Gd, Er and Yb were observed in both, manually cleaned and rinsed samples. For all the elements examined, analytical uncertainty was below 3.0% whereas sample preparation uncertainty computed with ANOVA, RANOVA, modified RANOVA and range statistics methods varied from 3.5 to 29.7%. In most cases the lowest srprep values were obtained with the modified RANOVA method.