Zdzisław M. Migaszewski

Polynuclear aromatic hydrocarbons, phenols, and trace metals in selected soil profiles and plant bioindicators in the Holy Cross Mountains, South-Central Poland

This report presents the results of PAH, phenol, and selected trace element (Cd, Cu, Hg, Pb, S, and Zn) determinations on detailed soil profiles and associated plant bioindicators (including lichen Hypogymnia physodes, moss Hylocomium splendens, pine Pinus sylvetris) from the three most representative habitats in the Holy Cross Mts, south-central Poland. This study is only part of a larger ongoing environmental study that includes complex sulfur isotope and element determinations in three national parks in N, central and S parts of Poland. The highest concentrations of PAHs (1887 ppb) and numerous trace elements are found in the organic horizon-O and humic horizon-A of each soil type. Different plant species and their individual tissues reveal considerable variability in the concentration of PAHs, phenols and elements examined. Most of the H. physodes thalli also reveal higher concentrations of individual hydrocarbons and some elements (including S and Zn) than their host bark. The highest concentration levels of phenols (1217 ppb) are noted in the 1-year pine needles. Most of the PAHs and elements examined seem to be of anthropogenic origin. The only exception is the distribution pattern of elements in southwestern part of the study area, which is linked to the local bedrock geochemical anomaly. The results of this study indicate that the content of PAHs, Cd, Cu, Hg, Pb, S and Zn in the soils and plant bioindicators examined has not changed considerably since 1998.

The Characteristics, Occurrence, and Geochemical Behavior of Rare Earth Elements in the Environment: A Review

The increasing number of rare earth elements (REEs) studies in the past decade has been induced by their wider applications in industry, including electronics and high technology. This review presents the brief characteristics of REE, their occurrence in abiotic and biotic systems, and their possible detrimental effects on the environmental quality and human health. This also outlines the REE behavior in different geochemical interactions and the potential for tracing anthropogenic pollution sources.

Moving your laboratories to the field - Advantages and limitations of the use of field portable instruments in environmental sample analysis

The recent rapid progress in technology of field portable instruments has increased their applications in environmental sample analysis. These instruments offer a possibility of cost-effective, non-destructive, real-time, direct, on-site measurements of a wide range of both inorganic and organic analytes in gaseous, liquid and solid samples. Some of them do not require the use of reagents and do not produce any analytical waste. All these features contribute to the greenness of field portable techniques. Several stationary analytical instruments have their portable versions. The most popular ones include: gas chromatographs with different detectors (mass spectrometer (MS), flame ionization detector, photoionization detector), ultraviolet-visible and near-infrared spectrophotometers, X-ray fluorescence spectrometers, ion mobility spectrometers, electronic noses and electronic tongues. The use of portable instruments in environmental sample analysis gives a possibility of on-site screening and a subsequent selection of samples for routine laboratory analyses. They are also very useful in situations that require an emergency response and for process monitoring applications. However, quantification of results is still problematic in many cases. The other disadvantages include: higher detection limits and lower sensitivity than these obtained in laboratory conditions, a strong influence of environmental factors on the instrument performance and a high possibility of sample contamination in the field. This paper reviews recent applications of field portable instruments in environmental sample analysis and discusses their analytical capabilities.

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.

Determining organic compound ratios in soils and vegetation of the Holy Cross Mts, Poland

The objectives of this investigation in the Holy Cross Mountain region of Poland were (1) to establish organic-concentration baselines, and (2) (if possible) to determine spatial distribution pattern of polynuclear aromatic hydrocarbons in topsoil. These objections were accomplished using an unbalanced, nested analysis-of- variance (ANOVA) barbell sampling design. Samples of topsoil (horizon A), Scots pine (Pinus sylvestris L.) needles and lichen thalii Hypogymnia physodes (L.) Nyl. were collected for polynuclear aromatic hydrocarbons (PAHs), polychlorinatedbiphenyls (PCBs), organochlorine pesticides and phenols. Of these four organic groups, PAHs was detected in topsoil of nearly all investigation sites. Their total content ranged from 4.43 to 1905.83 μg kg- 1, exceeding at some places that assessed for unpolluted cultivated soils of Poland. The results of organic compound determinations performed on soils and vegetation from the Holy Cross Mountain region showed that some concentrations of compounds were elevated probably due to air pollution. Nonetheless, some portions of them, especially phenols, might have been products of metabolic activity. Topsoil, Scots pine and partly lichens of Łysica Mt. revealed the highest concentrations of PAHs, PCBs and organochlorine pesticides. The content of PCBs in lichens of the study region was somewhat higher than in Lapland.

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.

Antiphase hydrogen and oxygen isotope periodicity in chert nodules

Abstract Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ 18 O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976) ; the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ 18 O line with δD values that are almost 50‰ lower. The δD-δ 18 O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999) , and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990) . The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.

Assessing the Anthropocene with geochemical methods

Abstract Anthropogenic chemical contamination is one of the most evident signals of human influence on the environment. The large amounts of industrially produced pollutants that have been introduced, over decades, into air, soil and water have caused modifications to natural elemental cycling. Anthropogenic contamination usually leads to enrichment in many elements, particularly in industrial areas. Thus, certain elements and their isotopes can be used as geochemical tracers of anthropogenic impact. Some human-induced changes in the environment may be regarded as a secondary effect of pollution, such as acidification, which causes increased geochemical mobility of several trace elements in surficial deposits. Methods used by geochemists to assess the scale of anthropogenic influence on the environment include calculations of anthropogenic influence on the environment via enrichment and contamination factors, geoaccumulation index and pollution load index. The use of geochemical background levels for delineating between natural and anthropogenic pollution is important. A historical perspective of anthropogenic contamination, allied with isotopic and geochemical signatures in dated sediment cores, may be applied to help define the Anthropocene.

ELEMENT CONCENTRATIONS IN SOILS AND PLANT BIOINDICATORS IN SELECTED HABITATS OF THE HOLY CROSS MOUNTAINS, POLAND

The objectives of this investigation in the HolyCross Mountain region of Poland were (1) to determineconcentration ranges and (2) mobility of elements within fivedetailed soil profiles and their apparent impact on thechemistry of some plant bioindicators, i.e. lichen thalli ofthe species Hypogymnia physodes (L.) Nyl. and Scotspine (Pinus sylvestris L.) bark. The results ofelemental determinations performed on soils and vegetationfrom the Holy Cross Mts show that some concentrations ofelements are elevated primarily due to air pollution.However, since 1994 a steady decrease in the content of S andsome heavy metals has been recorded in all the mediaexamined. Concentrations of many elements in H.physodes thalli and P. sylvestris needles of the Holy Cross Mountains are generally similarto those in other areas of Europe.

The study of rare earth elements in farmer's well waters of the Podwiśniówka acid mine drainage area (south-central Poland).

The principal objective of the current study was to elucidate the potential influence of acid mine drainage (AMD) pond on neighboring farmers wells in the Podwiśniówka area (south-central Poland), using North American Shale Composite (NASC)-normalized rare earth element (REE) concentration profiles. The well waters generally displayed a distinctly positive Eu anomaly similar to that of parent rocks and AMD sediment. In contrast, the AMD pit pond water exhibited the typical roof-shaped NASC-normalized REE concentration pattern with a strong positive Gd anomaly. The low pH (mean of 2.9) of this pond water is induced by oxidation of pyrite that occurs in quartz veins and rocks exposed in the abandoned Podwiśniówka quarry. The principal source of REEs in turn is a crandallite series of aluminum–phosphate–sulfate (APS) minerals (gorceixite with florencite and Ce-bearing goyazite) that prevail in most clayey shales. These data indicate that the REE contents of the AMD pit pond and well waters are linked to bedrock mineralogy and lithology, but not to pyrite mineralization. The diverse REE patterns of NASC-normalized REE concentrations of the AMD and well waters may suggest complex sorption and desorption processes that occur at the rock–water interface influenced by different pH, Eh, temperature, and other factors. This is evidenced by a presence of strong positive Ce anomaly in the rocks, a lack of Ce anomaly in the AMD water and sediment, and the dominant negative anomaly of this element in the well waters. Variations in correlation coefficients (r2) of REE concentrations between the rocks and the well waters may also result from a different contribution of quartzites, clayey shales, or tuffites to the REE signal of well waters as well as from mixing of shallow groundwater with infiltrating rainwater or meltwater with different REE profiles.