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Article

Assessment of Air Quality in the South-Western Part of the Świętokrzyskie Mountains Based on Selected Indicators

by
Mirosław Szwed
1,*,
Rafał Kozłowski
1 and
Witold Żukowski
2
1
Institute of Geography and Environmental Sciences, Jan Kochanowski University, 25-406 Kielce, Poland
2
Faculty of Chemical Engineering and Technology, Cracow University of Technology, 31-155 Cracow, Poland
*
Author to whom correspondence should be addressed.
Forests 2020, 11(5), 499; https://doi.org/10.3390/f11050499
Submission received: 12 March 2020 / Revised: 27 April 2020 / Accepted: 27 April 2020 / Published: 29 April 2020
(This article belongs to the Section Forest Ecology and Management)
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Abstract

:
This article presents the results of research on the air quality which was under the anthropogenic impact of the cement and lime industry in the Świętokrzyskie Mountains for many years. Research using geo- and bio-indicators was carried out at fixed measuring points in the years 2016–2018. Hypogymnia physodes (L.) Nyl. and two-year old Scots pine needles Pinus sylvestris L. were used for bioindication research. Physico-chemical properties of precipitation were developed on the basis of research conducted at the Jan Kochanowski University’s field research station located on the Malik Mt. Increased pH and specific electrolytic conductivity (EC) of precipitation, as well as variable concentrations of heavy metals throughout a year were found. Analysis of the chemical properties of transplanted lichens and pine needles confirmed the presence of elements from the cement and lime industry sector located in the Białe Zagłębie. Scanning electron microscope (SEM) image of the needles’ surface revealed morphologic changes resulting from pollution of stoma opening and closing by small solid particles of anthropogenic origins, disturbing gas exchange.

1. Introduction

Gas and dust emissions from specialized industrial centers are the largest sources of anthropogenic pollutants to the atmosphere, soil and surface waters. It has a negative effect on the natural environment [1,2,3,4,5,6,7,8,9] and human health [10]. The smallest dust particles may easily enter living organisms and disturb their metabolism. In this aspect, long-term deposition of trace elements contained in cement-lime dust, including heavy metals that are toxic to the environment (lead, chromium, nickel, cadmium), is particularly important. Poland is one of the leading producers of cement in Europe (17.3 million tons in 2017—data from the Central Statistical Office of Poland 2017), taking the third place behind Germany and Italy. Lime production amounting to 1904 thousand tons (2017) gives Poland the fifth place. A significant part of these products is produced in plants located within the Białe Zagłębie in the Świętokrzyskie Mountains. The Białe Zagłębie consists of cement plants in Nowiny and Małogoszcz as well as lime plants in Bukowa and Trzuskawica. Almost fifty years of the functioning of the Białe Zagłębie have caused changes in the natural environment [11,12,13,14]. This article determines the amount of metal deposition using the accumulation capacity of selected living organisms and atmospheric precipitation over the study area. The biologic material used in the research (pine needles and lichen), which are commonly found and react to stress caused by anthropogenic pressure and accumulate air pollution well. Before, the issue of bioindication in industrialized areas was undertaken by Alaimo et al. [15], Sawicka-Kapusta et al. [16], Ots and Mandre [17], Parzych et al. [18] and—when it comes to the Świętokrzyskie Region—by Migaszewskiet al. [19], Jóźwiak [20], Barga-Więcławska and Świercz [21], as well as Kozłowski et al. [22], among others. The authors of the above works have demonstrated the impact of alkaline pressure on soils, some animals, changes in vegetation species and the functioning of ecosystems. The properties of atmospheric precipitation in areas exposed to anthropogenic impact were determined, among others, by Baciak et al. [23], Kasina [24], Sporek [25], Polkowska et al. [26], Stachnik et al. [27], Kozłowski et al. [28], as well as Jóźwiak [29] when it comes to the Białe Zagłębie. The combination of geo- and bio-indicators was used to develop a multi-factorial assessment of the natural environment and its transformation within the Białe Zagłębie. The interdisciplinary approach to research, combining geographical, biologic and chemical research methods, allows for monitoring industrial impact on plants along with their technical infrastructure, roads, spoil tips and mining areas.
Currently, industrial scale operations concentrated within the Białe Zagłębie cover an area of about 180 km2 in the south-western part of the Świętokrzyskie Mountains [30], forming an irregular triangle (Figure 1). The largest plants producing cement and lime products are located in Bukowa, Małogoszcz, Trzuskawica and Nowiny. Mass production and significant fuel consumption in the technological process result in increased emissions of harmful gases and dust into the atmosphere (Figure 2). Despite modernization and innovation activities over the last decades [31,32], their presence is a basic factor reducing the quality of air in this part of the region [33]. Monitoring carried out in 2016–2018 was aimed at determining the range of impact of cement and lime plants as well as a multi-factorial assessment of the state of natural environment under the influence of such kind of emission.

2. Materials and Methods

The measuring system included tests conducted on permanent control surfaces where gas and dust amounts in the air were analyzed, as well as precipitation sampling and lichen transplantation and pine needle collection were carried out (Figure 1).
The analysis of dust emissions from cement and lime plants was based on annual permits for the emission of substances issued by the Provincial Inspectorate for Environmental Protection. PM10 (particulate matter less than 10 microns), SO2 and NO2 emissions were analyzed on the basis of daily data from the stations in Nowiny and Małogoszcz.
Precipitation sampling was carried out at the point no. 10 (Malik Mt.) at the Geo-ecological Station of the Jan Kochanowski University in Kielce. Samples were taken using a Hellmann rain gauge mounted on a steel tower at a height of 27 m, i.e., 1 m above the tree crowns, thus excluding the influence of trees on the precipitation amount and quality. The sampling was conducted at weekly intervals. The pH and electrolytic conductivity (EC) of the collected water were tested in each case using a multi-parameter water quality sensor Hach HQ 40d equipped with an Intellical electrode (calibrated on Hamilton standards with pH 4.0, 7.0, 9.21). The samples were immediately transported to the Environmental Research Laboratory of the Jan Kochanowski University, where they were subjected to chemical analysis according to the Inductively Coupled Plasma-Mass Spectrometer-Time-of-Flight (ICP-MS-TOF) OptiMass 9500 mass spectrometer.
Due to good bioindication properties, two-year-old needles of Scots pine Pinus sylvestris L., forming dense complexes of upland and lowland forests with rich undergrowth and lower fir floors, were selected for monitoring analyses. The sample of fresh organic matter, weighing about 200 g, was an average sample taken from three trees of similar height and DBH (diameter at breast height 1.3 m)—Figure 1. The average age of trees ranged from 30 to 40 years. The height of the trees was measured with a Nikon Forestry Pro II laser rangefinder.
Within the calciphilic Białe Zagłębie, there is no presence of Hypogymnia physodes (L.) Nyl. used in bioindication [34,35,36,37,38] and that is why, it was transplanted from the Borecka Primeval Forest (north-eastern Poland) where it occurs widely. The Borecka Primeval Forest belongs to the most valuable forest complexes in Europe due to the natural preservation of Central European deciduous forest habitats and the low anthropogenic impact characterized by a negligible share of heavy metal concentrations in atmospheric precipitation [39]. The Hypogymnia physodes (L.) Nyl. lichens were taken on approximately 30-cm twigs and then placed in 22 control points at a height of approximately 2 m above ground level, using plastic self-locking bands. At a distance of about 50 km north-east of the study area (in the Suchedniowsko–Oblęgorski Landscape Park), the background area was located. The duration of lichen exposure in the area of anthropogenic pressure lasted for six months in four measuring series, two for each half year (warm, cool). Each time, lichens (after the transplantation time) and pine needles (after the growing season) were transported to the Environmental Research Laboratory of the Jan Kochanowski University, where they were subjected to further tests. All samples were washed with deionized water three times. After having been dried at 65 °C for 24 h, the air-dried samples were ground in an IKA A-11 Basic organic matter mill. In the ground samples, pH was analyzed in solutions obtained by mixing the samples with water or a 1-N KCl purum p.a. solution in a ratio of 1:2.5. After 24 h, the pH value was measured using a HACH HQ-40d multiparameter with an INTELLICAL electrode. A mixture of nitric acid (V) (Suprapur Merck 65%) and hydrogen peroxide purum p.a. in a ratio of 2.5:1 was used for distributing wet samples of amounts weighing 0.1 g in polytetrafluoroethylene (PTFE) vessels. Material prepared in that way was subjected to microwave waves of 1400 W power and temperature of 200 °C for 40 min using the Multiwave 3000 Anton Paar mineralizer. The mineralized material and monthly collected samples of precipitation were subjected to chemical analysis for the content of selected metals (Al, Cd, Cr, Co, Cu, Fe, Ni, Pb, Zn), using the ICP-MS-TOF ICP MS TOF (Coupled Plasma MassSpectrometer Time-of-Flight) spectrometer (OptiMass 9500, GBC Scientific Equipment, Melbourne, Australia). Results consisted of an average value of three measurements. In order to control the quality of obtained results, such certified reference materials as ERM-CA713 made by the Institute for Reference Materials and Measurements in Belgium were used. The obtained data were statistically elaborated using the Statistica 13.1 program. Microscopic research was performed using scanning electron microscope (SEM) model TM3000 (under full vacuum and with 15kV accelerating voltage, Hitachi, Tokio, Japan) at the Institute of Inorganic Chemistry and Technology at the Cracow University of Technology. This analysis was supplemented with energy-dispersive X-ray spectroscopy (EDS). The EDS analysis allowed for obtaining the spectrum of X radiation arising after excitation of the surface layer of the sample being tested under the electron stream used during scanning in the SEM microscope. The spectra obtained after scanning the sample being tested allowed for identifying the elements on its surface or inside it to a depth of several micrometers. This approach allowed for performing a good assessment of the types of pollutants adsorbed on the surface or absorbed by biologic material from the surrounding gaseous environment.

3. Results

The largest share of dust emissions to the atmosphere belonged to the Trzuskawica Lime Industry Plant located in the central part of the Białe Zagłębie, which emitted annually 131.7 tons of dust, on average and the Lafarge Cement Plant in Małogoszcz, which emitted annually 129.75 tons, on average in the years 2002–2018 (Figure 2).
During the analyzed period, only the cement plant in Bukowa decreased its volume of emissions. In total, 263.3 tons of dust from the plants monitored by the Provincial Inspectorate of Environmental Protection got into the atmosphere in 2016, 302.2 tons in 2017 and 293.0 tons in 2018. According to the regulation of the Minister of Environment (Journal of Laws of 2018, item 799), the permissible level of dust with a fraction of 10 microns—PM10 in the air is 50 µg m−3(daily average) and the limit of permissible exceedances during the year amounts to 35 days. The permissible annual PM10 level amounts to 40 µg m−3.
The analysis of suspended PM10 concentrations from the Provincial Inspectorate of Environmental Protection’s station in the Białe Zagłębie, meteorological data and the NOAA Hysplit model showed that:
  • the highest average annual PM10 concentrations were recorded in 2017, i.e., 85.3 µg m−3 for Nowiny and 35.8 µg m−3 for Małogoszcz
  • the biggest number of days with exceedances of the permissible level was recorded in 2017 in Nowiny, i.e., 108 days, in total
  • the values above the permissible level and the highest values were recorded for the cool half-year periods
  • the maximum value of PM10 concentrations at both stations (274.6 µg m−3 in Nowiny and 175.7 µg m−3 in Małogoszcz) fell on 8th and 9th January 2017, with such minimum temperatures on those days as: −25.2 °C and −26.3 °C, respectively
  • the maximum values of concentrations were recorded during the period of air inflow from the south-west direction, along with the lowest air temperature during the year.
Chemical analysis of dust samples from the Dyckerhoff Nowiny and Lafarge Małogoszcz cement plants showed a significant share of heavy metals in their composition (Table 1). The largest share was reported for iron and aluminum, lead and zinc (Table 1). The pH of both samples was alkaline, its value in H2O and KCl was pHH2O = 13.21 and pHKCl = 13.02 for the sample from Małogoszcz and pHH2O = 12.61 and pHKCl = 12.38 for the sample from Nowiny.
Analysis of PM10 showed variable values throughout the year. Dust concentrations in the air correlated with the increase in cement and lime production (Figure 3a). Increased values in winter periods could be related to the release of pollutants from domestic heating installations and the inflow of air from local and remote sources of industrial emissions [40], (Figure 3b).
The hourly values of sulfur dioxide and nitrogen dioxide concentrations in the whole analyzed period did not exceed the permissible values at both Provincial Inspectorate of Environmental Protection’s measuring stations. In the case of sulfur dioxide and PM10, there was an increase in pollution during the cold half-year and a decrease during the warm half-year with lower concentration values.
The relationship between SO2 and PM10 concentrations and air temperature was noticeable (Figure 4).
Based on the conducted research, it was found that the weighted average pH value of precipitation in 2016 was 5.91 (normal precipitation according to the classification by Jansen et al. [41]) with fluctuations from 5.30 (January 2016) to 6.57 (May 2016). Electrolytic conductivity (EC) was 4.50 mS m−1 (significantly elevated). In 2017, the average pH value was 6.47 (slightly elevated) and conductivity—7.12 mS m−1 (extremely elevated). The lowest pH for precipitation was recorded in December 2017. In 2018, the slightly elevated pH (6.15) and extremely elevated electrolytic conductivity (9.95 mS m−1) were found. The lowest pH values were recorded in the winter months (January—pH 5.77, December—pH 5.39).
The analysis of heavy metal content showed the highest concentrations of iron, copper, aluminum and nickel in precipitation. Concentrations of other heavy metals did not exceed 100 µg dm−3 in average monthly precipitation samples. The highest concentrations of iron in the monthly sample was found in January 2016 (580 µg dm−3). The highest concentrations for copper (180 µg dm−3) and aluminum (57.5 µg dm−3) were found, in turn, in September 2018. To compare to the entire study period, two months (January and September 2018) were distinguished due to elevated concentrations of all tested heavy metals. Such a situation could have been affected by the weather conditions. Low temperatures in January and February 2016 and the extremely dry summer of 2018 were favoring high concentrations of heavy metals in the air and their deposition and after precipitation—due to leaching—were increasing their values in the analyzed water samples. Conducted statistical testing procedure using the non-parametric U Mann–Whitney test showed a statistical significance level of “p” (p < 0.05) for cadmium in dust as well as cobalt and nickel in precipitation. A strong correlation (r > 0.8) of metals in dust and precipitation was found in the following pairs: Al-Pb; Cr-Pb; Cd-Cd; Al-Cr; Cr-Cr; Cd-Co; Al-Al; and Cd-Fe.
Transplantation of lichens in the south-western part of the Świętokrzyskie Mountains indicated the accumulation of trace elements of anthropogenic origins. The amount of accumulated metals was calculated for each control point based on the difference between the concentrations of metals in the biota of lichens transplanted into the Białe Zagłębie and the concentrations of metals in the blank sample tested immediately after taking it from the Borecka Primeval Forest. The average content of accumulated heavy metals was the highest for aluminum (about 900 mg kg−1 d.m.) and iron over 400 mg kg−1 d.m.; and, both elements reached the highest concentrations during the third series of transplantation. Meteorological conditions may have had an impact on such concentration dynamics. Longer periods without precipitation favored the presence of dust in the air (third series) and enabled their absorption by lichens. This is confirmed by the results of the statistical analysis using the non-parametric U Mann–Whitney test. There are statistically significant differences (p < 0.05) between the third and the first exposure series for the following metals: Pb, Cr, Cu, Ni, Al, Fe; between the third and the second exposure series for such metals as: Pb, Cr, Cu, Ni, Al; and between the third and the fourth exposure series for Pb, Cd, Cu, Al and Fe.
The lowest concentrations of aluminum in the lichen thallus were recorded during the fourth series of transplantation (325.6 mg kg−1 d.m.), while for iron—during the first series (222.6 mg kg−1 d.m.).
The highest concentrations of these metals were observed in Bolechowice (11), Bukowa (13) and Lipowica (21), located in the immediate vicinity of the cement plant [22]. The increased content of iron and aluminum in the air, apart from the emission from cement plants, was also associated with the weathering process of rocks and minerals [42]. The next largest element in the six-month series was zinc. Its values were the highest during the second series of transplantation, with an average of 41.7 mg kg−1 d.m. The highest concentrations were recorded in thalli exposed in Bolechowice (11) and Lipowica (21) and the lowest ones were found in Chorężów (7) (in three series below 5 mg kg−1 d.m.). Copper and lead concentrations in lichens were similar to each other in all analyzed periods. Visible differences occurred during the fourth series in which an average of 12.7 mg kg−1 d.m. was recorded for lead and 19.6 mg kg−1 d.m.—for copper (Figure 5.). The highest concentrations of lead (up to 64 mg kg−1 d.m.) were recorded for the lichen samples from Bolechowice (11) and Lipowica (21), while the highest ones of copper (up to 56 mg kg−1 d.m.) were found in the samples collected from Jaworznia (1), Wymysłów (22), Brzeziny (17) and Milechowy (6). Increased lead concentrations were found in the vicinity of the cement plant in Nowiny (11, 21). In turn, the highest copper concentrations were detected at the points located along the International Road E77 (1, 22) and National Road No. 763 connecting Chęciny and Morawica (6, 17).
Chromium, cobalt, cadmium and nickel concentrations in all exposure series did not exceed 1 mg kg−1 d.m. During the first year of research, there was a noticeable increase in the accumulation of the analyzed elements for the cold half-year in comparison with their accumulation in the warm half-year. It was the largest for zinc—by 50%, lead and copper by 23%, aluminum by 17% and iron and nickel by 10%. Only concentrations of cobalt, chromium and cadmium slightly decreased. During the second year of lichen transplantation, the concentrations of accumulated elements were higher in the samples exposed in the cold half-year in comparison with the elements accumulated in the warm half-year for: copper (by 83%), cadmium (by 64%), lead (by 57%), cobalt (by 54%) and chromium (by 51%). A decrease in concentrations was noted for other heavy metals. It was the highest for aluminum (by 174%), zinc (by 97%), iron (by 50%) and nickel (by 9%).
Correlation analysis showed a strong relationship (r > 0.8) between the content of metals in dust and lichens for the following pair Cd-Cu; and a moderate one (0.8 < r > 0.6) for such pairs as Pb-Cd, Cd-Cd and Ni-Zn, respectively.
Needle pH determinations showed the average values of pHH2O 5.62 and pHKCl 5.28 (in the background area pHH2O 5.21 and pHKCl 4.98.) The highest values of pHH2O 6.38 and pHKCl 5.81 were recorded in the central part of the study area, i.e., in Polichno (15). The obtained results were not statistically significant.
Average content of the analyzed metals in the samples of needles was the highest in the case of aluminum (over 400 mg kg−1 d.m.), iron (270 mg kg−1 d.m.) and zinc (65 mg kg−1 d.m.). The content of lead, copper, nickel and strontium did not exceed 10 mg kg−1 d.m. In 2018, pine needle samples for physico-chemical and chemical tests were collected again. The analysis of results showed a significant increase in heavy metal concentrations, especially for chromium (3.3-fold), aluminum (3-fold), manganese (2-fold) and nickel (1.4-fold), compared to the samples from 2016. Other heavy metals (lead, copper, cobalt, zinc, strontium and iron) had a similar level as that in the previous study period. Regarding the background area (Pb: 0.12 mg kg−1 d.m.; Cu: 0.74 mg kg−1 d.m.; Zn: 21 mg kg−1 d.m.; Al: 34 mg kg−1 d.m.; Fe: 132 mg kg−1 d.m.; nickel, cobalt, cadmium and chromium below detection level), a much lower concentration level of all metals were found compared to both measurement series.
Considering the small changes in the volume of emissions, the fact of increased concentrations should be associated with favorable conditions for deposition of dust on pine needles (high air temperature, low annual precipitation). Depending on the location, and above all, the distance from the emitter, the volume of accumulated elements by the pine needles varied considerably; while the highest concentrations of lead, zinc, chrome, iron, aluminum and copper were recorded in the control points located within 5 km from the industrial plants and nearby quarries (Figure 6).
There was a spatial pattern of concentrations of selected trace elements (Pb, Cu, Ni) observed in a latitudinal system, i.e., higher in the area of lime and cement plants within 2 km from the emission source, and lower east of them, located in the vicinity of forest complexes within more than 2 km from rock processing plants. Correlation analysis showed a strong relationship (r > 0.8) between metals concentrations in dust and pine needles in the following pairs: Cu-Fe; Ni-Al; Zn-Al; Co-Al; Cr-Al; Ni-Cu; Co-Cu; Pb-Cu; Cd-Co; and Cd-Cd. In addition, there were statistically significant differences (p < 0.05) between the first and the second series for chromium, copper, zinc and aluminum.
A source of heavy metals in the vicinity of lime plants in Bukowa may be the co-combustion of car tires in a process of lime production. The SEM/EDS analysis of the chemical composition confirmed the presence of metals (Pb, Fe and Al) as well as Ca, K and Mg (Figure 7). The most important elements included in the cement-lime dust comprise of Pb, Fe, Al and Ca. It may therefore be concluded that the direct source of emissions of elements found on the surface of the needles were the cement and lime plants operating in the study area.
Using the principal component analysis (PCA) method, three main components were distinguished, i.e., PC1–PC3 (Table 2. In total, they generated 64% of cumulative total variance of trace elements in the samples from the analyzed area of the Białe Zagłębie, regardless of bio-indicator’s location. They take into account the conditions associated with the cement and lime industry operating in this area (PC1–PC3) and transportation resulting from the course of the S7 express way at a distance of about 1 km from the study area (PC3).
The first component (PC1) generated 34% of total variance and showed high weight (≤−0.87) for Fe and Pb (Table 2). The second component (PC2), in turn, formed 17% of total variance with the highest weight for Zn and Cr. Also important is the PC3 analysis (13% of variance) which indicated high weight for Cu (Figure 8).

4. Discussion

The quality of atmospheric air in the Białe Zagłębie is primarily determined by the type of economy carried out in its area. The rock raw material mining and processing industry and, additionally, communal and living sector and road transportation are the largest sources of emissions there. Moreover, air masses from the Upper Silesian Industrial District and even the Czech Moravia, periodically occurring in the Białe Zagłębie and identified on the basis of NOAA Hysplit backward trajectories, may be an additional environmental burden (Figure 9).
As a result of local emissions, the chemical composition mainly showed the impact of dust pollution, confirmed by the presence of heavy metals, especially lead, chromium, nickel and copper. The results of the chemical composition of precipitation on the Malik Mountain were similar to the concentrations of nickel, cadmium, cobalt and chromium obtained on the basis of atmospheric precipitation in the region of Upper Silesia [43]. In all years of research, the average annual concentrations of iron and copper in the precipitation water from the Białe Zagłębie were several times higher (Fe—6 times; Cu—7 times) than those obtained in the most industrialized and urbanized part of the Central Europe. Much lower concentrations of the analyzed metals were found in atmospheric precipitation studied in 2007–2008 in the Tibetan Highland at Nam Co [44]. In samples of the melted mountain glacier from Mount Everest [45] and in snow samples taken in the Himalayas [46] and the Pamir Mountains [47], lower concentrations of aluminum, chromium, iron and cobalt were found than in the Świętokrzyskie Mountains. Only concentrations of lead, aluminum and cobalt in the urban part of Mersin in Turkey [48] were several times higher than in the south-western part of the Świętokrzyskie Mountains. Research conducted in Singapore [49], Virginia [50], Nakanoto [51] and the Aegean Sea [52] showed similar concentrations of lead, cadmium and chromium to those found in the Świętokrzyskie Mountains. Monthly average copper concentrations on the Malik Mountain, only in the case of research in 2017, especially for February and March, were comparable with the results obtained in precipitation water in Singapore [49]. In other regions of the world, lower copper concentrations were recorded than in the Świętokrzyskie Mountains (the lowest ones in the Himalayas and Virginia).
Research using the same lichen species is carried out in many regions of the world. Due to their high accumulation capacity, they are widely used in areas exposed to high industrial pressure. In Poland, studies on the same species were carried out by Białońska and Dayan [53] in the same transplant periods. Lead and zinc concentrations were two times higher (except for Bukowno), cadmium concentrations was 10 times higher; nickel, copper and iron concentrations were at a similar level; and chromium concentration was lower by half (except for Alwernia) than the metal concentrations recorded for the lichens. Studies conducted by Sawicka-Kapusta et al. [16] as part of the Integrated Environmental Monitoring (IEM) in Poland in 2010, had conducted lichen-indication studies of Hypogymnia physodes occurring in its natural environment (in situ) in the IEM study base stations. The obtained metal concentrations were close to the values found in the lichen thalli in “Białe Zagłębie” in the case of iron and copper, and several times higher in the case of cadmium and zinc. In the Kaliningrad Oblast (Russia), Koroleva and Revunkov [54] who were studying metals in the Hypogymnia physodes (L.) Nyl. found similar concentrations of copper, lead, nickel and strontium, as well as twice as high zinc concentrations and three times higher iron concentrations than those recorded for the control points. Studies conducted by Poličnik et al. [37] in Slovenia and Mikhailova et al. [36] in Russia, with the annual exposure period of the same species of transplanted lichens, had indicated varying accumulation of Fe, Pb, Cu, Cd and Zn throughout the year. Lichen transplantation carried out by Asplund et al. [55] proves that it may be used to estimate the dependence of the impact of selected tree species on the local chemical environment. After one year from transplantation onto beech trunks, lichens had significantly higher concentrations of base cations (Ca, Mg, K); lower Mn and Zn concentrations; as well as similar Al and Fe concentrations.
Studies carried out on pine needles taken from the forests of the north-western part of Poland [56], characterized by the lack of significant impact of industrial pressure on air quality, showed significantly lower concentrations of iron (34 mg kg−1 d.m.), zinc (48 mg kg−1 d.m.), copper (3 mg kg−1 d.m.) and chromium (1 mg kg−1 d.m.). Studies conducted in Słupsk in the northern part of Poland [18] showed similar concentrations of zinc in washed needles to those in the study area, with an average value of 66.8 mg kg−1 d.m., and significantly higher concentrations in the case of lead, amounting to 13.3 mg kg−1 d.m. In Olsztyn, in turn, located in the north-eastern part of Poland, considered as the area with the lowest anthropopression [57], concentrations of lead in pine needles were almost 9 times lower (0.13 mg kg−1 d.m.) and—in the case of chromium—8 times lower (0.03 mg kg−1 d.m.) than in the study area. Concentrations of lead and zinc found in pine needles in the Upper Silesian conurbation, being the most industrialized part of Poland, reached a few hundred higher level [58] than in the study area. Studies conducted on the Kola Peninsula (Russia), in its industrialized part [59], showed comparable concentrations of chromium and zinc and much higher concentrations of lead (7.4 times), strontium (2 times), copper (8.6 times), nickel (63.4 times) and iron (3 times) than in the study area. In the northern part of Estonia, being exposed to alkalization by the cement plant [17,60], concentrations of chromium, lead, iron, zinc and copper were found to be about half as high as in the study area, but it should be noted that the authors did research on one-year-old needles. Particles deposited inside the inter-cellular structure of needle may penetrate it and thus cause its capping which disturbs gas exchange [61,62,63]. Studies conducted by Juranović-Cindrićet al. [64] confirm the physiological changes of needles by demonstrating the relationship between mineral deficiency in soils and advanced alkalization. Studies carried out by Barga-Wiecławska et al. [21] in the Białe Zagłębie confirm the changes in the soil profile towards alkalization resulting from more than forty-year-old emission of cement-lime dust.
The conducted principal component analysis indicated the conditions associated with the cement and lime industry operating in this area (PC1–PC3) and transportation resulting from the course of the S7 express way at a distance of about 1 km from the study area (PC3). The Kozłowski’s research (2013) showed that the cement and lime dust emitted by the industry operating in this area is characterized by an increased content of Fe, Pb, Cr, Zn and Cu resulting from the technological process used. For the production of clinker and lime, coal, coal dust, coke and car tires are commonly used.
The average concentrations for individual measuring series in the analyzed components (precipitation, needles, lichens) did not exceed the natural concentrations determined by Kabata and Kabata-Pendias [42]. However, significant exceedances of the concentrations of some trace elements (Ni, Pb, Zn) were found in relation to the results of lichen transplantation in the vicinity of the cement plant in Nowiny (11).

5. Conclusions

The aim to assess the extent of the impact of air pollution sources on the environment is a difficult task, especially if there are many emitters located in a small area. Such a case is in the south-western part of the Świętokrzyskie Mountains, where several plants extracting rock raw materials and producing cement and lime were located in close proximity to each other. This area already in the 1970’s was classified as the area of the so-called ecological disaster.
Based on the conducted research, significant changes in the natural environment were found in the Białe Zagłębie. They mainly concern the air quality and atmospheric precipitation properties which in turn affect the entire natural environment and people. The analysis of air research showed significant dynamics of the amount of air pollution in individual years. A large number of days with exceedances of the permissible PM10 concentrations at both measuring stations in Nowiny and Małogoszcz should be noted, as well. A relationship between air temperature and dust concentrations during the periods of severe frosts was found. Such a situation causes an additional reduction in the air quality in connection with emissions from the communal sector (low emission).
The research carried out on the geo-indicators has confirmed the impact of existing plants in the Białe Zagłębie on the quality of atmospheric precipitation. It was discovered that both the physico-chemical properties and chemical composition of precipitation are subject to transformation. An increase in the natural pH, electrolytic conductivity and the presence of heavy metals of anthropogenic origins, i.e., lead, zinc, cadmium and chromium were found. Increased pH and mineralization values indicate anthropogenic pressure related to the cement and lime industry branch dominating in the region and remote sources of emissions. The concentrations of heavy metals, especially iron, aluminum, manganese and zinc occurring in all measuring points indicate a significant dispersion of pollutants in the atmosphere and the possibility of further movement.
Lichens transplanted to the study area accumulated the largest amount of heavy metals among the analyzed indicators. Four measurement series conducted in the half-year periods showed a variable accumulation of elements, higher in the cool half-year and lower in the warm half-year. The most important factor affecting the volume of accumulated metals was the distance from the source of emissions (industrial plant, fast highways), i.e., the closer the distance, the higher the heavy metal content was in the bio-indicator. Local orographic barriers in the form of hills and dense forest complexes were disturbing the dispersion of pollutants in the atmosphere and caused variable accumulation in the thalli of bio-indicators. The lichens exposed in the Białe Zagłębie accumulated significant volumes of the analyzed trace elements, exceeding the concentrations occurring in the Borecka Primeval Forest several times (Cu—4.2 times, Pb—2.9 times, Cr—2.8 times, Ni—2.1 times, Fe—1.8 times).
The collected pine needle samples indicated physico-chemical and chemical properties conditioned by the deposition of cement and lime dust. The highest concentrations of heavy metals were found in those samples which were collected up to two kilometers from the cement plants in Nowiny and Małogoszcz (Cr, Co, Cu, Ni) and the lime plants in Trzuskawica and Bukowa (Zn, Sr, Pb).
Analyses, including SEM photomicrographs, confirmed the effectiveness of capturing cement and lime dust, along with heavy metals, by coniferous forest complexes within the area of Białe Zagłębie. In addition, it may be noted that fine dusts, regardless of their chemical composition, adversely affect the stomata, which may lead to gas exchange reduction. As a consequence, the reduction of gas exchange may lead to a decrease in the efficiency of photosynthesis and thus limit the development of the analyzed forest stand. Considering the slight changes in the volume of emissions from the cement and lime plants being monitored, the fact that the concentrations of heavy metals in the pine needles from 2018 increased in comparison with the samples from 2016 should be associated with a significant change in meteorological conditions. The year 2018 was extremely dry and warm, and that certainly enabled dust deposition and was effectively making it difficult to flush it from the surface of needles.
The statistical method used for the main components of PCA showed a significant impact of the industry functioning in the analyzed area.
The geo- and bio-indicators used in the research are used to assess the state of the natural environment under the influence of anthropogenic pressure in a given study area. High sensitivity to pollution and accumulation capacity allowed for delimitation of the zone most exposed to the impact of the cement and lime plants. Chemical composition of precipitation, pine needles and transplanted lichens were conditioned by deposition of cement and lime dust from the industrial plants and quarries located in the study area.
The conducted research clearly indicates the need for further interdisciplinary studies aimed at determining the impact of cement and lime industry pressure on organisms living in its immediate vicinity.

Author Contributions

M.S. was involved in the sampling, experiments, made chemical analysis and wrote the manuscript. R.K. designed the study, made chemical analysis and wrote the manuscript. W.Ż. made SEM/EDS analysis. All authors have read and agreed to the published version of the manuscript.

Funding

This study was funded by the Jan Kochanowski University.

Conflicts of Interest

The authors declare that they have no competing interests.

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Figure 1. Location of study area (elaborated by M. Szwed on the basis of BDOT and CORINE L and Cover v.2012), 1—sampling points, 2—cement and limestone plants, 3—rivers, 4—quarries, 5—buildings, 6—forests.
Figure 1. Location of study area (elaborated by M. Szwed on the basis of BDOT and CORINE L and Cover v.2012), 1—sampling points, 2—cement and limestone plants, 3—rivers, 4—quarries, 5—buildings, 6—forests.
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Figure 2. Volume of cement and lime dust emissions in the Białe Zagłębie in the years 2002–2018 (data by Provincial Inspectorate of Environmental Protection in Kielce).
Figure 2. Volume of cement and lime dust emissions in the Białe Zagłębie in the years 2002–2018 (data by Provincial Inspectorate of Environmental Protection in Kielce).
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Figure 3. PM10 concentrations in Nowiny, (a)—for a year, (b)—for a winter period—as a function of the air temperature.
Figure 3. PM10 concentrations in Nowiny, (a)—for a year, (b)—for a winter period—as a function of the air temperature.
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Figure 4. Relationship between SO2 and PM10 concentrations and air temperature (January 2018).
Figure 4. Relationship between SO2 and PM10 concentrations and air temperature (January 2018).
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Figure 5. Copper concentrations in transplanted lichen—fourth series. (Legend: 1—sampling points, 2—cement and limestone plants, 3—rivers, 4—quarries, 5—buildings, 6—forests).
Figure 5. Copper concentrations in transplanted lichen—fourth series. (Legend: 1—sampling points, 2—cement and limestone plants, 3—rivers, 4—quarries, 5—buildings, 6—forests).
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Figure 6. Copper concentrations in pine needles—second series. (Legend: 1—sampling points, 2—cement and limestone plants, 3—rivers, 4—quarries, 5—buildings, 6—forests).
Figure 6. Copper concentrations in pine needles—second series. (Legend: 1—sampling points, 2—cement and limestone plants, 3—rivers, 4—quarries, 5—buildings, 6—forests).
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Figure 7. Scanning electron microscope image and energy-dispersive X-ray spectroscopy analysis of the needles’ surface—collected in the near vicinity of the Trzuskawica Lime Industry Plant in Kowala.
Figure 7. Scanning electron microscope image and energy-dispersive X-ray spectroscopy analysis of the needles’ surface—collected in the near vicinity of the Trzuskawica Lime Industry Plant in Kowala.
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Figure 8. Graphic image of relationships among PC1, PC2 and PC3 components.
Figure 8. Graphic image of relationships among PC1, PC2 and PC3 components.
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Figure 9. Backward trajectory graph for Nowiny determined on days of highest PM10 concentrations in the atmospheric air, using the Hysplit model.
Figure 9. Backward trajectory graph for Nowiny determined on days of highest PM10 concentrations in the atmospheric air, using the Hysplit model.
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Table
Table 1. Chemical analysis of selected dust components from cement plant in Białe Zagłebie [14].
Table 1. Chemical analysis of selected dust components from cement plant in Białe Zagłebie [14].
Cement PlantPbCdCrCoCuNiZnAlFeCaMg
mg kg−1 d.m. (Dry Mass)
Małogoszcz38.00.40.70.41.43.719.81760.0365.0131,5708340
Nowiny3139.041.44.21.26.88.51373.14280.0588.0131,2002070
Table
Table 2. Principal component analysis (PCA) analyses of heavy metals.
Table 2. Principal component analysis (PCA) analyses of heavy metals.
VariableComponent
PC1PC2PC3
Pb−0.824 *−0.2100.115
Cd−0.5140.563−0.254
Cr0.079−0.776 *−0.350
Co−0.590−0.1460.384
Cu−0.2400.341−0.746
Ni−0.6410.015−0.077
Zn−0.451−0.662 *−0.292
Al−0.5890.0590.415
Fe−0.870 *0.093−0.117
% of variance341713
% in total345164
* PC1 ≤ −0.9; PC2–PC3 ≥ 0.6.

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Szwed, M.; Kozłowski, R.; Żukowski, W. Assessment of Air Quality in the South-Western Part of the Świętokrzyskie Mountains Based on Selected Indicators. Forests 2020, 11, 499. https://doi.org/10.3390/f11050499

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Szwed M, Kozłowski R, Żukowski W. Assessment of Air Quality in the South-Western Part of the Świętokrzyskie Mountains Based on Selected Indicators. Forests. 2020; 11(5):499. https://doi.org/10.3390/f11050499

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Szwed, Mirosław, Rafał Kozłowski, and Witold Żukowski. 2020. "Assessment of Air Quality in the South-Western Part of the Świętokrzyskie Mountains Based on Selected Indicators" Forests 11, no. 5: 499. https://doi.org/10.3390/f11050499

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