Interspecies and interregional comparisons of the chemistry of PAHs and trace elements in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from Poland and Alaska

Comparative biogeochemical studies performed on the same plant species in remote areas enable pinpointing interspecies and interregional differences of chemical composition. This report presents baseline concentrations of PAHs and trace elements in moss species Hylocomium splendens and Pleurozium schreberi from the Holy Cross Mountains (south-central Poland) (HCM) and Wrangell–Saint Elias National Park and Preserve (Alaska) and Denali National Park and Preserve (Alaska). Total PAH concentrations in the mosses of HCM were in the range of 473–2970 μg kg^?1 (dry weight basis; DW), whereas those in the same species of Alaska were 80–3390 μg kg^?1 DW. Nearly all the moss samples displayed the similar ring sequence: 3 > 4 > 5 > 6 for the PAHs. The 3 + 4 ring/total PAH ratios show statistically significant differences between HCM (0.73) and Alaska (0.91). The elevated concentrations of PAHs observed in some sampling locations of the Alaskan parks were linked to local combustion of wood, with a component of vehicle particle- and vapor-phase emissions. In HCM, the principal source of PAH emissions has been linked to residential and industrial combustion of coal and vehicle traffic. In contrast to HCM, the Alaskan mosses were distinctly elevated in most of the trace elements, bearing a signature of the underlying geology. H. splendens and P. schreberi showed diverse bioaccumulative capabilities of PAHs in all three study areas.     

Pesticide burial grounds in Poland: a review

Obsolete pesticides were stored in Poland from the middle sixties until the late eighties of the 20th century mostly in underground disposal sites, called "pesticide burial grounds" or "pesticide tombs". The total amount of pesticide waste and packaging materials disposed of in these landfills exceeded 20000 Mg. Typically, the content of a pesticide tomb was dominated by organochlorine pesticides (comprising 10-100% of the total waste volume) with DDT as the prevailing compound. Other pesticide types, such as phosphoroorganic, carbamate insecticides, dinitrophenols, phenoxyacids, and inorganic compounds were stored in smaller quantities, usually not exceeding 10-20% of the total waste volume. With the growing awareness of the threats that these landfills posed to the environment, the first inventory for the whole country was made in 1993 and remediation was initiated in 1999. The total amount of waste, which had to be removed from the known pesticide tombs (hazardous substances, contaminated soils, construction materials etc.) was about 100000 Mg. According to the National Waste Management Plan, the reclamation of pesticide tombs was assumed to have been finished by the end of 2010, however, this goal has not been achieved. The aim of this review is to present a historical perspective of pesticide burial grounds in Poland with an emphasis on their creation, function, inventory, and remediation. Based on unpublished reports, and other published materials of limited availability written in Polish, this review may serve as a source of information for representatives of other countries, where remediation of pesticide burial grounds is still in progress. The experience gained over a ten-year period, when restoration of pesticide tombs was implemented in Poland, reveals that there are many obstacles to this action arising not only from technical, but also from economic and social issues.     

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 use of the barbell cluster ANOVA design for the assessment of environmental pollution: a case study, Wigierski National Park, NE Poland

This report presents an assessment of chemical variability in natural ecosystems of Wigierski National Park (NE Poland) derived from the calculation of geochemical baselines using a barbell cluster ANOVA design. This method enabled us to obtain statistically valid information with a minimum number of samples collected. Results of summary statistics are presented for elemental concentrations in the soil horizons-O (Ol + Ofh), -A and -B, 1- and 2-year old Pinus sylvestris L. (Scots pine) needles, pine bark and Hypogymnia physodes (L.) Nyl. (lichen) thalli, as well as pH and TOC. The scope of this study also encompassed S and C stable isotope determinations and SEM examinations on Scots pine needles. The variability for S and trace metals in soils and plant bioindicators is primarily governed by parent material lithology and to a lesser extent by anthropogenic factors. This fact enabled us to study concentrations that are close to regional background levels.     

The role of sample preparation in interpretation of trace element concentration variability in moss bioindication studies

Trace element concentrations in plant bioindicators are often determined to assess the quality of the environment. Instrumental methods used for trace element determination require digestion of samples. There are different methods of sample preparation for trace element analysis, and the selection of the best method should be fitted for the purpose of a study. Our hypothesis is that the method of sample preparation is important for interpretation of the results. Here we compare the results of 36 element determinations performed by ICP-MS on ashed and on acid-digested (HNO₃, H₂O₂) samples of two moss species (Hylocomium splendens and Pleurozium schreberi) collected in Alaska and in south-central Poland. We found that dry ashing of the moss samples prior to analysis resulted in considerably lower detection limits of all the elements examined. We also show that this sample preparation technique facilitated the determination of interregional and interspecies differences in the chemistry of trace elements. Compared to the Polish mosses, the Alaskan mosses displayed more positive correlations of the major rock-forming elements with ash content, reflecting those elements’ geogenic origin. Of the two moss species, P. schreberi from both Alaska and Poland was also highlighted by a larger number of positive element pair correlations. The cluster analysis suggests that the more uniform element distribution pattern of the Polish mosses primarily reflects regional air pollution sources. Our study has shown that the method of sample preparation is an important factor in statistical interpretation of the results of trace element determinations.     

Significance of the long-term biomonitoring studies for understanding the impact of pollutants on the environment based on a synthesis of 25-year biomonitoring in the Holy Cross Mountains,Poland

This review presents compiled results of complex biomonitoring studies that have been conducted in the Holy Cross Mountains, south-central part of Poland, since the 1990s. The significance of these studies results from several aspects: (i) a number and a variety of plant organisms used, e.g., mosses, lichens, coniferous and deciduous trees, and their tissues (wood, bark, needles, leaves, the aboveground parts of several vascular plants); (ii) applications of a broad scope of instrumental methods aiming at determining major and trace elements (including rare earth elements), organic compounds (PAHs, PCBs, phenols), and stable sulfur isotopes (δ³⁴S); and (iii) different methodological and environmental issues addressed. The comparison and interpretation of results derived from seventeen sampling campaigns carried out between 1994 and 2017 are a valuable source of information on the following: (i) bioaccumulative properties of organisms used in air quality monitoring, (ii) identification and variations of local and regional pollution sources and geochemical landscape patterns and processes over years, and (iii) establishing environmental factors that variously affected chemical composition of plants growing under physiological stress, including roadside vegetation and plants from acid mine drainage areas.

     

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 farmer's wells in the Podwi?niówka 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 Podwi?niówka 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 (r ²) 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.