Are cadmium, lead and mercury concentrations in mosses across Europe primarily determined by atmospheric deposition of these metals?

Purpose

This study aimed at investigating correlations between heavy metal concentrations in mosses and modelled deposition values as well as other site-specific and regional characteristics to determine which factors primarily affect cadmium, lead and mercury concentrations in mosses. The resulting relationships could potentially be used to enhance the spatial resolution of heavy metal deposition maps across Europe.

Materials and methods

Modelled heavy metal deposition data and data on the concentration of heavy metals in naturally growing mosses were integrated into a geographic information system and analysed by means of bivariate rank correlation analysis and multivariate decision trees. Modelled deposition data were validated annually with deposition measurements at up to 63 EMEP measurement stations within the European Monitoring and Evaluation Programme (EMEP), and mosses were collected at up to 7,000 sites at 5-year intervals between 1990 and 2005.

Results and discussion

Moderate to high correlations were found between cadmium and lead concentrations in mosses and modelled atmospheric deposition of these metals: Spearman rank correlation coefficients were between 0.62 and 0.67, and 0.67 and 0.73 for cadmium and lead, respectively (p?<?0.001). Multivariate decision tree analyses showed that cadmium and lead concentrations in mosses were primarily determined by the atmospheric deposition of these metals, followed by emissions of the metals. Low to very low correlations were observed between mercury concentrations in mosses and modelled atmospheric deposition of mercury. According to the multivariate analyses, spatial variations of the mercury concentration in mosses was primarily associated with the sampled moss species and not with the modelled deposition, but regional differences in the atmospheric chemistry of mercury and corresponding interactions with the moss may also be involved.

Conclusions

At least for cadmium and lead, concentrations in mosses are a valuable tool in determining and mapping the spatial variation in atmospheric deposition across Europe at a high spatial resolution. For mercury, more studies are needed to elucidate interactions of different chemical species with the moss.     

Forms of Cu,Ni, and Zn in soils of sudbury,ontario and the metal concentrations in plants

Forms of Cu, Ni, and Zn in the contaminated soils of the Sudbury mining/smelting district were studied to assess metal mobility and plant availability. Soil, tufted grass (Deschampsia caespitosa (L.) Beauv.), tickle grass (Agrostis scabra Willd.), dwarf birch (Betula pumila L. var. glandulifera Regel) and white birch (Betula paprifera Marsh.) leaf and twig samples were taken from 20 locations around three Cu-Ni smelters. The sampling sites were collected to cover a wide range of soil pH and soil Cu and Ni concentrations. The water-soluble, exchangeable, sodium acetate-soluble, and total concentrations of the metals in the soils were analyzed. The soils were contaminated with Cu and Ni up to 2000 µg g^?1. Zinc concentrations were also elevated in some samples above the normal soil level of 100 µg g^?1. The mobility of Cu and Zn, expressed as the proportion of metals in Fl and F2 forms, increased with soil pH decrease. A strong positive correlation was found between the soil exchangeable (F2) Ni and the soil pH. Concentrations of Cu and Ni in birch twigs showed a good linear relationship with exchangeable forms of the metals in soils. A highly significant correlation was also found between total Ni in soils and the metal content of the twigs. No significant correlation was found between Zn concentrations in the soils and plants. Birch twigs are a good indicator (better than leaves) of Cu and Ni contamination of the Sudbury soils. The mobile forms of Cu and Ni and low pH seem to be the main factors that will control the success of revegetation. Strong variability of the soil metal mobility requires any reclamation effort be site-specific.     

Accumulation of Cadmium,Chromium, and Zinc by the Moss Sphagnum Papillosum Lindle

In a series of laboratory experiments employing radiotracer methodology, the uptake of Cd,Cr, and Zn by Sphagnum papillosum Lindle moss from solutions of deionized water and bogwater was investigated. Bioaccumulation of the metals was a passive process, since living anddead moss accumulated metal equally. No significant differences were found in metal uptake ratesfrom single metal solutions and mixed metal solutions, suggesting insignificant competitionbetween the metals occurred at the low concentration range used (10-10 to 10-7 M). Metaluptake conformed with Freundlich adsorption isotherms. Concentration factors of metals inSphagnum papillosum in bog water (103 for Cd and Zn, 102 for Cr) were lower than in deionizedwater (104 for Cd and Zn, 103 for Cr), possibly due to metal complexation by dissolved organicmatter, competition by other major cations present in the bog water (Na+, K+, Mg2+, Ca2+) orcomplexation by chlorides in the bog water. While earlier studies have demonstrated the potentialof using sphagnum mosses for monitoring environmental metal contamination, these experimentsare the first to assess metal uptake in moss using low, environmentally realistic metalconcentrations. The results confirm that mosses would be very effective bioindicators ofenvironmental metal concentrations because the concentration of metal in the moss rapidly anddirectly reflects the metal concentrations in the ambient water.     

comparison of sulphur and heavy metal contents and their regional distribution in humus and moss samples from the vicinity of Nikel and Zapoljarnij,Kola Peninsula,Russia

Terrestrial moss and humus (the O-horizon) are often used separately for determining and monitoring airborne heavy metal pollution. Here, we directly compare the results of analyses of moss and humus samples taken at a density of one site per 300 km² in a 12 000 km² area (45 samples) around the nickel smelter in Nikel, the nickel ore roasting plant in Zapoljarnij, both in Russia, and the iron ore mine and mill near Kirkenes in Norway. The samples were air dried, digested in conc. HNO₃ and analysed for more than 30 elements by ICP-MS and ICP-AES at the laboratory of the Geological Survey of Finland (GTK). For most elements, observed levels and variations are considerably greater in soil than in moss. The main contaminants, Ni and Cu, reach equally high median levels in the moss and soil, but maximum values are far higher in soil. Both media show comparable regional distribution patterns for the heavy metals, but not for sulphur. Cu and Ni can be used to delineate the limits of contamination in the survey area. Both media show the same picture, with a generally very steep gradient from east to west and background levels being reached 30–50 km from the nickel smelter. When moss is used, Cu/Ni, Cu/S and Ni/S ratios can be used to separate input from the smelting and roasting proccesses in Russia. Both media are well suited to use separately to detect airborne pollution in this heavily contaminated area. The moss data are generally easier to interpret, but moss is not available at the most polluted sites. Levels for many elements other than Cu and Ni are close to the detection levels in moss samples, but not in humus samples. Information gathered from both media thus complement each other in a regional multi-element survey.     

Short-term changes of metal availability in soil. II: The influence of earthworm activity

This study aimed to evaluate short-term earthworm-induced changes in the availability of metals applied to soil directly (metal-spiked) or via an organic matrix (sludge-amended). A laboratory experiment was performed using destructive sampling of microcosms filled with agricultural soil. A concentration gradient of industrial sludge contaminated predominantly with Cr, Cu, Ni, and Zn, and a soil freshly spiked with the same metal concentrations were applied on top of the soil columns. Individuals of Dendrobaena veneta (mimicking a realistic density of 500 earthworms per m²) were introduced in half of the replicates of each treatment. Total and 0.01 M CaCl₂ extractable metal concentrations were measured in soil after 0, 3, 6 and 12 weeks and metal concentrations in earthworms and percolates were measured after 3, 6, and 12 weeks. Earthworm activity did not affect metal availability of any treatment over time, but Ni and Cu concentrations in D. veneta were higher at the highest treatment levels. Earthworm Zn concentrations were similar in all treatments while Cr concentrations increased with increasing soil total metal content only for sludge treatments. Existing relationships of earthworm metal concentrations with total metal content in soil, taken from the literature, were not able to predict the metal levels measured in D. veneta. Results demonstrated that although over 12 weeks earthworm activity did not affect metal availability in soil, their burrowing activities did influence the metal concentrations of percolates over time.     

Statistical models for the accumulation of PAH,chlorinated hydrocarbons and trace metals in epiphytic Hypnum cupressiforme

Concentrations of PAH (1.12-benzoperylene, 3.4-benzopyrene, fluoranthene), chlorinated hydrocarbons (α-BHC, lindane, PCB) and trace metals (Zn, Pb, Cu) in bulk precipitation, as well as PAH and trace metal concentrations in atmospheric dust samples from 14 sites in Bavaria, F.R.G. are presented for two vegetation periods (1979 and 1980). The same substances were also analyzed in epiphytic moss (Hypnum cupressiforme var. filiforme) sampled from tree trunks in October 1979 and 1980. Using mean immission values and the amount of precipitation as predictors and concentrations of pollutants in moss samples as criteria, a number of multiple regression models were computed in order to quantify the relationships between absolute air pollution data and accumulated trace substance values. Beta values of all variables help to determine whether bulk precipitation or atmospheric particulate matter has dominant influence on the uptake of trace substances by mosses. The study shows that epiphytic mosses can be used to monitor both heavy-metal, PAH and chlorinated hydrocarbons.     

Soil Factors Affecting Heavy Metal Solubility in Some New Zealand Soils

Heavy metal contamination of soils is usually quantified and guidelines set solely on the basis of total heavy metal content. However, it is recognised that water soluble heavy metal concentrations may provide a better indication of the potential risk that heavy metals may pose to the soil environment. The aim of this study was to use a semi-empirical model based on the competitive adsorption of metal and H⁺ ions [dependent on solution pH, total metal content, total carbon content and soil oxide content] to predict water soluble Cu, Cr, Cd, Pb, Ni and Zn concentrations in a range of field contaminated soils. The results of multiple linear regressions showed that basic soil properties could predict 85, 72, 66, 78, 50 and 75% of the variation in soluble Ni, Cu, Cr, Pb, Cd and Zn concentrations respectively. Water soluble metal concentrations were best predicted using empirical linear regressions which included total metal content, while the importance of other soil properties such as soil pH, total carbon and oxalate extractable Fe and Al oxides varied between metals. The models have the potential to provide valuable information on metal availability in contaminated soils and offer an indication of the potential risk a metal may pose to a given soil environment, along with providing a basis for developing soil quality guidelines for the prevention, investigation and clean-up of soil metal contamination.     

Estimation method of residual alkylating agents in water treated with chloring-containing oxidant

Concentrations of trace metals in mosses Hylocomium splendens (Hs) and Pleurozium schreberi (Ps) are compared along with wet deposition at 8 sites in Sweden. Cd, Mn, Zn and Cr concentrations were similar in both mosses, while Cu, Fe, Pb, Ni and V levels were 14 to 24% higher in Hs than in Ps. The comparison to wet deposition estimates indicates that concentrations in mosses are also influenced by other factors than the adsorption of precipitation. No correlation was observed between the wet deposition of Mn, Cr and Ni and moss concentrations.     

Mosses as bioindicators of heavy metal pollution in polish national parks

The concentrations of heavy metals (Cd, Co, Cr, Ni, Cu, Ph, Zn, Mn, Fe) and other elements (Mg, Na, K, Ca) were determined in the samples of Pleurozium schreberi and Hylocomium splendens from 12 Polish national parks. The significant differences in the concentrations of all heavy metals between particular parks were found. The lowest concentrations of these metals were recorded in the mosses from the national parks in northern Poland, the highest in southern Poland. Significant differences in the heavy metals contents of the mosses between central and peripheral park areas, between green and brown parts of mosses, as well as between moss species were also found.     

Improvement of phytoremediation effects with help of different fertilizer

Abstract

Phytoremediation is increasingly used to remediate metal contaminated soils. However, in order to provide technically efficient phytoremediation of contaminated sites the plant yield and metal uptake have to be enhanced dramatically. The aim of the study was to find appropriate combination of plant species and fertilizers capable of improving yields of the plants and stimulate a transfer of metals to more available to the plants forms. Wheat Triticum vulgare was used for the phytoremediation research. To increase yield of crops and enhance mobility of metals in the rhizosphere the soils were amended with three fertilizers (urea, horse manure, and “ispolin”). Short-term (36 d) vegetation test showed that concentrations of heavy metals in the plants grown in contaminated soil (from site 2) were significantly higher than those in the plants grown in clean soil (from site 1). Growth of wheat resulted in a decrease of Cd content in the soil. Amendment of the contaminated soil with urea enhanced the effect and the decrease of Cd concentration in the soil was more significant. The best effect was demonstrated after application of ispolin: concentrations of Cd, Cu, Pb, and Zn in the rhizosphere decreased 1.2–1.4 times as compared with those in the initial contaminated soil (the decrease was statistically significant).     

Aquatic mosses for the detection and follow-up of accidental discharges in surface waters

Aquatic mosses have been used to study four accidental discharges of the heavy metals Cd, Zn and Hg or the chlorinated hydrocarbons pentachlorophenol (PCP) and lindane in highly contrasting river types. Hg, PCP and lindane moss concentrations reached 880, 4500 and 350 ng g^?1, respectively. In the case of Cd and Zn, water samples and transferred bioindicators were taken simultaneously throughout an accidental discharge. The very high dissolved metal concentrations reached during this accident (9 mg L^?1 Zn, 90 μg L^?1 Cd) induced accumulation by the mosses of up to 28 mg g^?1 for Zn and 225 μg g^?1 for Cd. The increase in concentrations in the mosses was as rapid and substantial as in the water, the time lag due to accumulation kinetics being almost zero. On the other hand, the memory effect enabled mosses to retain marked evidence of Cd, Zn, Hg, PCP and lindane up to 13 days after the accident when difference from background levels can hardly be detected in the water. The four case studies, which killed fish, but not the mosses, show that the previously established scales of quality based on the analysis of aquatic mosses are well suited to estimating the potential damage to the aquatic ecosystem as a whole.     

Accumulation Capacities of Particulate Matter in an Acrocarpous and a Pleurocarpous Moss Exposed at Three Differently Polluted Sites (Industrial, Urban and Rural)

The aim of this study was to compare the capacity of two morphologically different moss species to accumulate elements when exposed to three different types of air pollution (rural, urban and industrial). Transplants of Pseudoscleropodium purum and Ceratodon purpureus were exposed for 6 months, and the concentrations of 18 elements (Al, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, As, Mo, Cd, Sn, Sb, Ba, La, Pb and Bi) in the mosses samples were analysed by inductively coupled plasma–mass spectrometry. On the whole, the metals were accumulated by mosses, and this accumulation was correlated with concentrations in the atmospheric particles. Whereas P. purum is to be preferred for Al, Cu, Zn and Fe monitoring, C. purpureus was most efficient at accumulating Mo, Ti, V, As, Sn, La and Pb. In both species, a phenomenon of saturation was observed during the exposure at the most contaminated site (industrial).     

Bioavailability as a Factor in Risk Assessment of Metal-Contaminated Soil

To accurately assess the risks of metal contaminants in soil, the bioavailability of the metals need to be considered. The bioavailable concentrations determined from homogenized, dried soils are not necessarily representative of in situ conditions of undisturbed field soils. In this study, we investigated the accumulation of metals in wheat (Triticum aestivum) grown in undisturbed contaminated (Pb, Zn, Cu, and Cd) soil cores, in relation to total soil, leachate, and diffusive gradients in thin films (DGT)-labile metal concentrations. Despite the fact that many of the samples contained metal concentrations above guideline values, no significant effects were observed on wheat growth. The bioavailability of metals in the most contaminated samples was estimated to be medium to low, possibly explaining why few effects were observed in the bioassay. For Cu, Zn, and especially for Pb, leachate and DGT-labile concentrations were better predictors of uptake by wheat than total concentrations based on correlations. It is suggested that DGT and leachate concentrations in combination with bioassays in undisturbed soil cores can be used to account for metal bioavailability in soil. These tests could be used during the ecological risk screening stage, in conjunction with total concentrations and guideline values to better estimate receptor exposure.     

Variability and relationships between Pb,Cu, and Zn concentrations in soil solutions and forest floor leachates at heavily polluted sites

Seasonal variability of Cu, Pb, and Zn concentrations in litter leachates and soil solutions was examined in an afforested zone surrounding a copper smelter in SW Poland. Litter leachates (with zero‐tension lysimeters) and soil solutions (with MacroRhizon suction‐cup samplers, installed at a depth of 25–30 cm) were collected monthly at three sites differing in contamination levels in the years 2009 and 2010 (total Cu: 2380, 439, and 200 mg kg^–1, respectively). Concentrations of Cu in the litter leachate were correlated with dissolved organic C (DOC), whereas Zn and Pb were mainly related to leachate pH. Metal concentrations in the soil solution were weakly influenced by their total content in soils and the monthly fluctuations reached 300, 600, and 700% for Cu, Pb, and Zn, respectively. Metal concentrations in soil solutions (Cu 110–460 μg L^–1; Zn 20–1190 μg L^–1; Pb 0.5–36 μg L^–1) were correlated with their contents in the litter leachates. Chemical speciation, using Visual Minteq 3.0, proved organically‐complexed forms even though the correlations between metal concentrations and soil solution pH and DOC were statistically insignificant. The flux of organically‐complexed metals from contaminated forest floors is believed to be a direct and crucial factor affecting the actual heavy metal concentrations and their forms in the soil solutions of the upper mineral soil horizons.     

Fraction Distributions of Lead,Cadmium, Copper,and Zinc in Metal‐Contaminated Soil before and after Extraction with Disodium Ethylenediaminetetraacetic Acid

Abstract: The fraction distributions of heavy metals have attracted more attention because of the relationship between the toxicity and their speciation. Heavy‐metal fraction distributions in soil contaminated with mine tailings (soil A) and in soil irrigated with mine wastewater (soil B), before and after treatment with disodium ethylenediaminetetraacetic acid (EDTA), were analyzed with Tessier's sequential extraction procedures. The total contents of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) exceeded the maximum permissible levels by 5.1, 33.3, 3.1, and 8.0 times in soil A and by 2.6, 12.0, 0.2, and 1.9 times in soil B, respectively. The results showed that both soils had high levels of heavy‐metal pollution. Although the fractions were found in different distribution before extraction, the residual fraction was found to be the predominant fraction of the four heavy metals. There was a small amount of exchangeable fraction of heavy metals in both contaminated soils. Furthermore, in this study, the extraction efficiencies of Pb, Cd, and Cu were higher than those of Zn. After extraction, the concentrations of exchangeable Pb, Cd, Cu, and Zn increased 84.7 mg·kg^?1, 0.3 mg·kg^?1, 4.1 mg·kg^?1, and 39.9 mg·kg^?1 in soil A and 48.7 mg·kg^?1, 0.6 mg·kg^?1, 2.7 mg·kg^?1, and 44.1 mg·kg^?1 in soil B, respectively. The concentrations of carbonate, iron and manganese oxides, organic matter, and residue of heavy metals decreased. This implies that EDTA increased metal mobility and bioavailability and may lead to groundwater contamination.     

Fate of heavy metals in a strongly acidic shooting‐range soil: small‐scale metal distribution and its relation to preferential water flow

To assess the mobility of Pb and associated metals in a highly contaminated shooting range soil (Losone, Ticino, Switzerland), we investigated the spatial distribution of the metals and their relation to preferential water flow paths. A 2.2 m² plot located 40 m behind the stop butt was irrigated with a solution containing bromide and Brilliant Blue, a slightly sorbing dye. A soil profile 50 cm in width was sampled down to 80 cm with a spatial resolution of 2.5 cm, resulting in 626 samples. Concentrations of elements (12 ≤ Z ≤ 92) were determined by energy‐dispersive Xray fluorescence spectrometry, and Brilliant Blue concentrations were determined with a chromameter. In the acidic (pH 3), organic matter‐rich, well drained Dystric Cambisol, maximum concentrations of 80.9 g kg^‐1 Pb, 4.0 g kg^‐1 Sb, and 0.55 g kg^‐1 Cu were measured in the topsoil. Within 40 cm soil depth, however, Pb, Sb, and Cu approached background concentrations of 23 mg kg^‐1, 0.4 mg kg^‐1, and 9.4 mg kg^‐1, respectively. The even horizontal distribution and the steep gradient along soil depth indicate tight metal binding in the topsoil, and a fairly homogeneous transport front. In contrast, water flow through the profile was highly heterogeneous. In the uppermost 20 cm, preferential flow was initiated by heterogeneous infiltration at the soil surface, but had no influence on metal distribution. Below 20 cm, however, preferential flow originated from larger tree roots, and metal concentrations were significantly elevated along these macropores. Spatial distributions of Pb, Sb, and Cu were similar, suggesting that all three metals are strongly retained in the topsoil and transported along preferential water flow paths in the subsoil.     

Respiration and priming effects after fructose and alanine additions in two copper- and zinc-contaminated Australian soils

The objective of the present study was to determine whether substrate-induced priming effects in soils are sensitive to increasing levels of Cu and Zn. Soils were collected from ten plots of two Australian field experiments (Spalding and Avon) where increasing amounts of Cu or Zn had been added 2?years prior to sampling, reaching maximum values of 5,880?mg?kg^?1 for Cu and 7,400?mg?kg^?1 for Zn. In a 21-day incubation experiment, the effect of uniformly ¹⁴C-labeled fructose and alanine on the mineralization of the soil organic carbon (SOC) was investigated. With increasing heavy metal content, the initial peak of soil respiration after substrate addition was retarded, indicating that the microorganisms utilizing these substrates were inhibited in soils highly contaminated with heavy metals. Both substrates strongly changed the mineralization of the soil organic matter (SOM), i.e., priming effects were induced. In the soil samples with high Cu concentrations from Spalding, fructose induced a stronger additional mineralization of the SOC than in the lower contaminated samples. In the samples with the highest Zn contamination level, negative priming effects, i.e., a reduced mineralization of SOM, were observed. In contrast, heavy metal effects in the Avon soil (pH?7.6) were less pronounced since substrate mineralization and priming effects were not directly related to the increasing heavy metal content. Apart from direct toxic heavy metal effects, the tested microbial activity parameters were also indirectly affected through the toxic heavy metal effects on plant growth. At the highest heavy metal contaminations, no fresh biomass inputs occurred during the past 2?years so that microorganisms in these soils were highly substrate-limited. As a consequence, complex interactions between different levels of heavy metal contamination, the microbial activity, and the input of SOC via plant biomass have to be considered.     

重金属污染土壤生态工程修复的试验研究

该文研究了细叶香薷(Moslem chinensis Maxim)和构树(Broussonetia papyrifera(Linn.) Vent.)对Cu、Zn污染土壤的修复及污染土壤对植物生理性状的影响。研究结果表明：随着盆栽土壤中重金属浓度的增高，植物体内吸收重金属的浓度相应增大。Cu在细叶香薷体内的含量是地上部＜地下部，Zn含量却是地上部＞地下部；重金属Cu、Zn在构树体内的浓度都是根部＞叶部＞茎部。细叶香薷的富集系数基本大于1，对Cu的最大富集系数是2.42；构树的富集系数都在0.5以下，但由于其地上部生物量很大，从土壤中移除的重金属量也很可观，而且构树能产生经济价值，建议把构树和细叶香薷组成一个立体的生态工程修复模式，既能修复污染土壤又能恢复污染地区的生态环境和土壤微生物环境，产生经济和环境效益。     

Heavy‐metal mobilization and uptake by mycorrhizal and nonmycorrhizal willows (Salix × dasyclados)

Ectomycorrhizal fungi have been shown to affect metal transfer from the soil to the host plant, but the use of these fungi for increased phytoextraction of heavy metals has been scarcely investigated. Therefore, a two‐factorial pot experiment was conducted with Salix × dasyclados and (1) two contaminated soils with different concentrations of NH₄NO₃‐extractable metals and (2) two strains of the ectomycorrhizal fungus Paxillus involutus (one strain originating from a noncontaminated site—Pax1, and another from a contaminated site—Pax2). The inoculation with Pax2 increased the phytoavailability of Cd in the soils. Inoculation with both fungal strains increased the stem and root biomass, but had no effect on metal concentrations in the stems. Decreased Cd and increased Cu concentrations were observed in the roots of inoculated willows. The inoculation with P. involutus increased Cd (up to 22%), Zn (up to 48%), and Cu content in the stems. Decreased Pb content (Cu and Pb content were always <1 mg per plant) occurred in the stems from plants at the soil with the higher concentration of NH₄NO₃‐extractable metals. Contrary to this, in the soil with lower concentrations of NH₄NO₃‐extractable metals, the inoculation had no significant effects on the total uptake of Zn and Cu and even caused decreased Cd (Pax2) and Pb (Pax1) contents in the stems. Strain Pax2 had higher colonization densities, but the plants had lower mycorrhizal dependencies in the contaminated soils than after inoculation with the strain Pax1. Generally, metal extractability in the soils substantially affected the mycorrhizal dependency and heavy‐metal uptake of the willows. We concluded, that the inoculation with P. involutus offers an opportunity to particularly increase the phytoextraction of Zn, but the metal extractability and fungal strain effects have to be tested.     

Competitivity,selectivity, and heavy metals-induced alkaline cation displacement in soils

Abstract

The simultaneous incorporation of heavy metals into the soil is still a matter of great concern. Interaction (competitive sorption) between these metals and the soil solid phase may result in a deterioration of soil quality which relies basically on amounts of alkaline cations saturating soils sorptive complex. Results of this study indicate that Pb, Cu, C d, and Zn have induced solution pH decreases which were more intensive at highest metal loading rates. Partition parameters (Kd)-based sequences showed that Pb and Cu were more competitive than Cd and Zn and the overall selectivity sequence followed: Pb > Cu > Cd > Zn. Metal loadings and their competitive sorption have led to a strengthened displacement of alkaline cations (i.e. Ca²⁺, Mg²⁺, K⁺, Na⁺), especially of Ca²⁺ as a factor “stabilizing” soil sorptive complex. Such metals impact jointly with soils acidification are of great environmental concern since tremendous amounts of alkaline cations (especially Ca²⁺) may be potentially leached out, irrespective of the degree of soil contamination, as evidenced in the current study. High and positive ΔG values implied that the studied soils were characterized by generally low concentrations of exchangeable potassium which required high energy to get displaced (desorbed). Further studies on heavy metal uncontaminated or contaminated areas should be undertaken to provide with data which should be used for predictions on changes related to soil buffering capacity as impacted by heavy metal inputs.