Trace elements and stable sulfur isotopes in plants of acid mine drainage area: Implications for revegetation of degraded land.

The abundances of trace elements, a low pH of water and soil in areas impacted by the acid mine drainage (AMD) may cause an excessive uptake of potentially toxic elements and nutritional imbalances in plants. Metal-tolerant, native plants are used for revegetation of degraded mining areas. We established levels of selected trace elements and stable sulfur isotopes in the above-ground plant biomass collected in a mining area in south-central Poland. In 2016, 20 samples of the most common species were collected from sites with a different influence of acid mine drainage and analyzed for trace elements by the inductively coupled plasma mass spectrometry technique. On the basis of the results obtained in 2016, the most contaminated site was selected for a more detailed study, in which sulfur contents and stable sulfur isotope ratios were determined together with trace elements in 17 samples. The results confirmed that the plants native to the AMD area efficiently accumulated trace elements, especially As and rare earth elements. Mosses showed the highest content of trace elements, but exhibited the lowest concentrations of sulfur accompanied by the highest δ34S values. It has been shown for the first time that stable sulfur isotope composition of AMD plants in south-central Poland is significantly depleted in the 34S isotope showing an average δ34S value of -10.5‰ in comparison with positive δ34S values in local vegetation growing outside the AMD area and in local precipitation.

The use of a geostatistical model supported by multivariate analysis to assess the spatial distribution of mercury in soils from historical mining areas: Karczówka Mt., Miedzianka Mt., and Rudki (south-central Poland).

For the purpose of this study, 181 soil samples were collected from three post-mining areas (Miedzianka Mt. (62), Karczówka Mt. (61), and Rudki (58)) in the Holy Cross Mountains, south-central Poland. Collected samples were dried, disaggregated, and digested in a closed microwave system. All solutions were analyzed for Hg concentrations with cold vapor-atomic absorption spectroscopy (CV-AAS) technique using a continuous flow vapor accessory. The average Hg concentrations and the upper limits of geochemical background (UBG) were as follows: Miedzianka Mt. Hg 0.501 mg kg-1, UBG 0.312 mg kg-1; Karczówka Mt. Hg 0.150 mg kg-1, UBG 0.180 mg kg-1; Rudki area Hg 0.216 mg kg-1, UBG 0.193 mg kg-1. The use of a spatial distribution map of mercury concentrations integrated with computed geochemical factors and results of cluster analysis showed a direct relationship between mercury contents and mining activity conducted in these areas. Only in the case of Miedzianka Mt., this relationship was visible and probably resulted from the presence of tennantite (Cu,Fe)12As4S13 in soil samples, which was also confirmed with the factor analysis. Higher Hg concentrations in soil samples from Karczówka Mt. and Rudki resulted from the presence of clay and other secondary minerals that increase the mercury adsorption from atmospheric deposition. Fossil fuel and biomass combustion was classified as the main anthropogenic source of the metal, but the neighborhood of a cement factory may be taken under consideration. Our results showed that the use of integrated geostatistical models allows for better data visualization and interpretation.

Heterogeneous areas-identification of outliers and calculation of soil sampling uncertainty using the modified RANOVA method.

We modified the robust analysis of variance (RANOVA) method to calculate sampling uncertainty of selected trace elements determined in soil samples from two heterogeneous remote historic metal ore mining areas. Classical RANOVA is down-weighting the outlying values by replacing them during the calculation process with mean ± c·σ r . Because the arithmetic mean is greatly influenced by outliers, it cannot represent a robust statistic. The main novel contribution of this work is use of median value that is independent on outliers and replace all extreme values during the calculation process with median ± 2·σ r . In our work, 18 duplicate, composite soil samples were collected, digested with aqua regia in a closed microwave system, and analyzed twice for selected trace elements. To extract homogenous groups within sampling areas and make the results more accessible for interpretation, a cluster analysis was done. Subsequently, histograms of each element were prepared and statistical tests were applied to determine the normal distribution of datasets. For abnormally distributed elements, the outlying values were identified by four different methods: boxplot, mean ± c·σ r , mean ± c·σ, and median ± 2·σ r . For five elements, the amount of outliers identified by the median ± 2·σ r procedure was less than 10 %, and for these elements, the sampling uncertainty was computed using a modified RANOVA method. The sampling uncertainty computed with this method was 28.9 % for Cd, 15.2 % for Co, 14.5 % for Mn, 12.7 % for Ni, and 16.3 % for Zn, whereas that computed with a traditional model was 16.7 % for Cd, 9.2 % for Co, 20.5 % for Mn, 17.9 % for Ni, and 16.3 % for Zn.

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. Czekanowski's 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.

Abundance and fate of glass microspheres in river sediments and roadside soils: Lessons from the Swietokrzyskie region case study (south-central Poland).

Traffic-related glass microspheres in fluvial and roadside soil settings were used as an indicator for the occurrence and extent of road dust as a source of emissions. Microspheres were found in sediments of two rivers, at a distance of approximately 25 km of the city of Kielce (south-central Poland). Their highest contents in sediments were recorded near street stormwater drains into the Silnica River flowing through the city. The study also showed no influence of local bridges on the spatial distribution of glass microspheres in the river deposits. In contrast, soils adjacent to a two-lane highway revealed the presence of microspheres as far as 60 m of the roadway. As opposed to other road dust components, which have commonly been applied in traffic contamination studies, glass microspheres were a good indicator for road dust contamination. Most microspheres showed diverse concentrations of all minor and trace metal(loid)s. The mean contents of As, Pb and Sb (n = 601) were: 0.003 wt%, 0.014 wt% and 0.010 wt%, respectively, and only in some microspherules these elements exceeded EU current/expected regulatory standard levels (0.02%/0.015% for each). Although generally considered to be non-toxic, silica rich microbeads might be the best proxy for non-exhaust particle matter discharged from the road traffic into the environment.

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

Forty eight samples of mosses Hylocomium splendens and Pleurozium schreberi from the Kielce area (south-central Poland) were analyzed for seventeen polycyclic aromatic hydrocarbons. The PAH concentrations varied from 558.00 µg/kg (ppb) to 4457.00 µg/kg in H. splendens and from 643.00 to 3086.00 µg/kg in P. schreberi. In both moss species phenanthrene (75.00-732.00 µg/kg), fluoranthene (101.00-577.00 µg/kg) and pyrene (68.00-568.00 µg/kg) predominated, but H. splendens accumulated more PAHs than P. schreberi at eighteen different sites. The highest PAH concentrations were noted at sites located close to the housing estates (sites 1-10) and potential emission sources (e.g. heat and power generating plant "Kielce S.A.") (sites 19-21). The moss samples displayed the diverse ring sequence, but the most prevalent was four>five>three>six. The diagnostic ratios (three+four ring/total PAHs, Flu/Py, Phen/Ant, Phen/Phen+Ant, Flu/Flu+Py, IndPy/IndPy+BghiPe and BaA/BaA+Chr) indicated that coal and petroleum combustion was a principal PAH source in the study area.

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(+), Ca(2+), Mg(2+), 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.

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.

Glass microspheres in road dust of the city of Kielce (south-central Poland) as markers of traffic-related pollution.

Glass microspheres are widely used as reflective components in road and pavement marking materials. They commonly occur in road dust mixed with different particles of anthropogenic and geogenic origin. This paper describes different methods that enable discrimination of glass microspheres from other morphologically similar particles that occur in road dust of Kielce. The individual glass microspheres vary from 30 to 1350 µm in diameter and consist of recycled Ca-, Na-, Mg-silica glass with a minor admixture of Al, Fe, K and S. Because of their stability and chemical composition, glass microspheres are good markers of traffic-related pollution in different environmental archives. Of different elements present in Kielce road dust, the fraction < 0.125 mm was distinctly abundant in zirconium, the main constituent of disk brakes or brake pads and a potential marker of road traffic pollution. However, the statistically significant positive correlation of the Si-Zr pair (R = 0.54) in the 1.0-2.0 mm fraction is linked to the presence of some detritic quartz grains with zircon inclusions. The other metals determined provide ambiguous traffic-related signatures and may be derived from different pollution sources.

Mercury in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from Poland and Alaska: understanding the origin of pollution sources.

This report shows baseline concentrations of mercury in the moss species Hylocomium splendens and Pleurozium schreberi from the Kielce area and the remaining Holy Cross Mountains (HCM) region (south-central Poland), and Wrangell-Saint Elias National Park and Preserve (Alaska) and Denali National Park and Preserve (Alaska). Like mosses from many European countries, Polish mosses were distinctly elevated in Hg, bearing a signature of cross-border atmospheric transport combined with local point sources. In contrast, Alaskan mosses showed lower Hg levels, reflecting mostly the underlying geology. Compared to HCM, Alaskan and Kielce mosses exhibited more uneven spatial distribution patterns of Hg. This variation is linked to topography and location of local point sources (Kielce) and underlying geology (Alaska). Both H. splendens and P. schreberi showed similar bioaccumulative capabilities of Hg in all four study areas.

A first insight into the estimation of uncertainty associated with storage and physical preparation of forest moss samples for trace element analysis.

To assess the level of uncertainty related to storage and physical preparation, 27 combined samples of moss species Pleurozium schreberi (Brid.) Mitt and their duplicates were collected within three forest areas. Each sample was divided into three sub-samples subjected to further treatment: D - drying (20-25 °C), F - freezing (-20 °C), and A - acclimatization (4 °C). After 7 days, all the samples were split into two sub-samples for physical preparation, dry (P1) and wet (P2) cleaning, respectively. Subsequently, the samples were milled, digested in a closed microwave system and analysed for Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn using the flame (FAAS) and graphite furnace (GFAAS) atomic absorption spectrometry. In four out of eight metals (Cu, Fe, Mn, Ni), the lowest mean values were in the samples stored at -20 °C, however, in two cases (Cd, Pb), the acclimatization procedure also led to lower concentrations. Except for Mn and Zn, the higher contents of elements were found in samples that were dry cleaned after storage. The level of sample storage uncertainty (srstor) varied from 4.8% to 24.0%. The uncertainty related to preparation was in the range of 3.0-21.0%. Only for Co, the contribution of srstor uncertainty to the budget of uncertainty was lower than that from physical preparation. For the other elements, this contribution was at a similar level (Ni, Zn) or higher (Cd, Cu, Fe, Mn, Pb). In most cases, the lower srprep values were obtained when the samples were dry cleaned after storage, regardless of the storage conditions.

Extreme enrichment of arsenic and rare earth elements in acid mine drainage: Case study of Wisniówka mining area (south-central Poland).

The Wisniówka rock strip mining area (south-central Poland) with quartzite quarries, acid water bodies and tailings piles is one of the most unique acid mine drainage (AMD) sites throughout the world. This is due to the occurrence of enormous amounts of pyrite unknown in sedimentary formations worldwide. Of the two mineralization zones, one that is the most abundant in arsenical pyrite occurs in the lowermost Upper Cambrian formation of the Podwisniówka quarry. The As-rich pyritiferous clastic rocks are exposed as a result of deep quartzite extraction during 2013-2014. In addition, the clayey-silty shale interbeds are enriched in rare earth element (REE) minerals. The mining operation left an acidic lake with a pH of about 2.4-2.6 and increased contents of sulfates, metal(loid)s and REE. The Podwisniówka pyrite-rich waste material was stacked up in many places of the mining area giving rise to strongly acidic spills that jeopardized the neighboring environment. One of these unexplored tailings piles was a source of extremely sulfate- and metal(loid)-rich pools with unusual enrichments in As (up to 1548 mg L-1) and REE (up to 24.84 mg L-1). These distinctly exceeded those previously reported in the Wisniówka area. A broad scope of geochemical, mineralogical and petrographic methods was used to document these specific textural and mineralogical properties of pyrite facilitating its rapid oxidation. The pyrite oxidation products reacted with REE-bearing minerals releasing these elements into acid water bodies. Statistical methods were employed to connect the obtained tailings pool hydrogeochemical data with those derived from this and the previous studies of the Podwisniówka and Wisniówka Duza acid pit lakes. In contrast to metal(loid) profiles, the characteristic shale-normalized REE concentration patterns turned out to be more suitable for solving different AMD issues including provenance of mine waste material in the tailings pile examined.

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.

Estimation of plant sampling uncertainty: an example based on chemical analysis of moss samples.

In order to estimate the level of uncertainty arising from sampling, 54 samples (primary and duplicate) of the moss species Pleurozium schreberi (Brid.) Mitt. were collected within three forested areas (Wierna Rzeka, Piaski, Poslowice Range) in the Holy Cross Mountains (south-central Poland). During the fieldwork, each primary sample composed of 8 to 10 increments (subsamples) was taken over an area of 10 m2 whereas duplicate samples were collected in the same way at a distance of 1-2 m. Subsequently, all samples were triple rinsed with deionized water, dried, milled, and digested (8 mL HNO3 (1:1) + 1 mL 30 % H2O2) in a closed microwave system Multiwave 3000. The prepared solutions were analyzed twice for Cu, Fe, Mn, and Zn using FAAS and GFAAS techniques. All datasets were checked for normality and for normally distributed elements (Cu from Piaski, Zn from Poslowice, Fe, Zn from Wierna Rzeka). The sampling uncertainty was computed with (i) classical ANOVA, (ii) classical RANOVA, (iii) modified RANOVA, and (iv) range statistics. For the remaining elements, the sampling uncertainty was calculated with traditional and/or modified RANOVA (if the amount of outliers did not exceed 10 %) or classical ANOVA after Box-Cox transformation (if the amount of outliers exceeded 10 %). The highest concentrations of all elements were found in moss samples from Piaski, whereas the sampling uncertainty calculated with different statistical methods ranged from 4.1 to 22 %.

Rare earth and trace element signatures for assessing an impact of rock mining and processing on the environment: Wisniówka case study, south-central Poland.

A detailed hydrogeochemical study was performed in the Wisniówka mining area (south-central Poland). This covered three acid pit bodies, historic tailings acid ponds, acid pools, and additionally two neighboring rivers. All these acid mine drainage (AMD) waters are characterized by the pH in the range of 1.7 (pools) to 3.5 (tailings ponds). The most interesting is the Podwisniówka acid pit lake that shows a very low pH (2.2-2.5) and very high concentrations of SO42- (2720-5460 mg/L), Fe (545-1140 mg/L), Al (86.2 mg/L), As (9603-24,883 µg/L), Co (1317-3458 µg/L), Cr (753-2047 µg/L), Cu (6307-18,879 µg/L), Ni (1168-3127 µg/L), and rare earth element (REE) (589-1341 µg/L). In addition, seeps that drain the Podwisniówka mine tailings and partly aggregate piles form strong acid pools in the mining area. Along with these pools, in which As and REE contents reach 369,726 and 6288 µg/L, respectively, these waters are among the most distinctive As- and REE-rich AMD surface waters across the world. It is noteworthy that the Podwisniówka acid pit lake and Wisniówka Duza acid pit sump exhibit different element signatures and REE concentration patterns normalized to North American Composite Shale (NASC): the Podwisniówka acid pit lake always shows a characteristic roof-shaped medium REE (MREE) profile with distinct enrichments in Gd, Eu, and Tb whereas the other one displays a step-shaped heavy REE (HREE) profile with positive Tb and Gd anomalies. The REE undergo fractionation during weathering and the subsequent leaching of dissolved and suspended fractions from rocks to acid water bodies where these and other elements are further fractionated by geochemical processes. This study shows that the individual REE have greater affinities for Mn, HREE for Fe and SO42-, and only La and Ce for Al. This specific water geochemistry has enabled us to (i) pinpoint the location of AMD "hot spots" originated from quartzite mining and processing operations conducted by current and previous mining companies, (ii) predict the directions and effects of future strip mining for quartzites in the Wisniówka Duza and Podwisniówka open pits, and (iii) evaluate the potential impact of mining and processing effluents on the quality of rivers.

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.

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 delta(34)S of Hylocomium splendens varied from 4.4 to 7.1 per thousand, whereas the delta(34)S of Pleurozium schreberi was in the range of 3.7-9.1 per thousand. The Holy Cross Mountains mosses display a positive delta(34)S signature of airborne SO(2) and sulphates of anthropogenic origin, which is characteristic for this part of Europe. Some spatial variations in the delta(34)S 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.