Download - Soil contamination with heavy metals as a potential and real risk to the environment

Journal of Geochemical Exploration xxx (2014) xxx–xxx

GEXPLO-05303; No of Pages 6

Contents lists available at ScienceDirect

Journal of Geochemical Exploration

j ourna l homepage: www.e lsev ie r .com/ locate / jgeoexp

Soil contamination with heavy metals as a potential and real risk to the environment

G.V. Motuzova a, T.M. Minkina b,⁎, E.A. Karpova a, N.U. Barsova a, S.S. Mandzhieva b

a Moscow State University, Department of Soil Science, Moscow, Russiab Southern Federal University, Rostov-on-Don 344090, Russia

⁎ Corresponding author at: 344090, prosp. Stachki, 194E-mail address: [email protected] (T.M. Minkina).

http://dx.doi.org/10.1016/j.gexplo.2014.01.0260375-6742/© 2014 Elsevier B.V. All rights reserved.

Please cite this article as: Motuzova, G.V., et aExplor. (2014), http://dx.doi.org/10.1016/j.g

a b s t r a c t
a r t i c l e i n f o
Article history:Received 4 October 2013Accepted 28 January 2014Available online xxxx

Keywords:ChernozemCompoundsExtractionPodzolsPollutionRemediation

The heavy metal content (Cu, Zn, Pb, Cd and Ni) in soils of natural landscapes and soils contaminated by thesemetals under technogenic and artificial conditions was investigated. Ecological hazards caused by heavy metalcompounds in soils were evaluated. The concept of a real and potential risk to the ecosystem in addition to soilcontaminationwith heavymetalswas formulated. The ratio of weekly boundheavymetal content to the stronglybound content ofmetalswas very informative parameter for the assessment of the ecological state of the pollutedsoils and evaluation of ameliorant effect to metal fixation in the soil.

© 2014 Elsevier B.V. All rights reserved.

1. Introduction

The environment contamination poses a serious hazard at present soputting in jeopardy the very basis of human existence at the planet. Thereal danger of environmental pollution is obvious (Bowen, 1979). Butthe doctrine about the potential threat of pollution for soils, about therelationship between actual and potential dangers of the pollutants forsoils is weakly developed.

The present paper is aimed at discussing the concept of ecologicalhazard to the biosphere through its pollution by different substances.Special attention is paid to approaches for evaluating the soil contami-nation with heavy metals and for describing informative indices,methods and results of their practical application under different condi-tions, thus answering the question about soil contaminationwith heavymetals as a potential and real risk to the environment.

1.1. Approaches for solving the above objectives

Contaminants are substances released into the environment fromman-made sources in amounts exceeding the natural level of theircontent (Motuzova, 1999). Heavy metals are referred to the mostdangerous group of contaminants and their chemical criteria (atomicweight, density) have proved far from sufficient in environmental re-search because the effect exerted by them on the behavior of chemicalelements reveals no manifestation in landscape. Nevertheless, the ef-fects of interaction between heavy metals and living organisms and

/1, Rostov-on-Don, Russia.

l., Soil contaminationwith heexplo.2014.01.026

the processes of their biogenic migration are of great importance(Weber and Karczewska, 2004). Essentially, heavy metals are micro-elements that are released into the environment from technogenicsources. In biochemistry, agrochemistry and soil science the heavymetals represent chemical elements, the small quantities of which(10−3–10−6%) in natural habitats contribute to the most importantbiochemical processes in living organisms.

In heterogenous natural landscapes the heavymetals are distributedcreating diverse biogeochemical provinces. They are intrazonal by char-acter and confined to areas with different distribution degrees of chem-ical elements (and their compounds) to be specifically interacted withliving organisms. The concept of biogeochemical provinces has beenfirst formulated by Vinogradov (1957). Kovalsky (1982) studied in de-tail the interaction between different organisms (crops, animals,human) and biogeochemical indices of their habitat. As a result of bio-geochemical zonation at the territory of the former USSR, 14 biogeo-chemical provinces have been distinguished according to surplus ordeficit of microelements in natural habitats (Kovalsky, 1982). Havingused the data about the living organisms in natural habitats, Kovalsky(1982)was the first to determine an optimal (threshold) level of micro-element content in the environment (prototype of the currently usedmaximum allowable concentration or critical load). The areas havebeen distinguished by him to show insufficient or abundant content ofmicroelements caused harm to living organisms including higher andlower plants, zoocoenoses, and microbiocoenoses. At present, thereare provinces that provide a breeding ground for endemic diseasesdue to deficiency or abundance of chemical elements in rocks andsoils (Avtsin et al., 1991). Among them are provinces characterized byabundance of molybdenum (endemic podagra), fluorine (fluorosis),strontium, barium and the other elements.

avymetals as a potential and real risk to the environment, J. Geochem.

http://dx.doi.org/10.1016/j.gexplo.2014.01.026

mailto:[email protected]


http://www.sciencedirect.com/science/journal/03756742


2 G.V. Motuzova et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

Apart from natural biogeochemical provinces, technogenic land-scapes are developed with a higher concentration of heavy metals(Meers et al., 2006). Only a comprehensive analysis of soils and theirstate makes possible to evaluate the hazard of these elements for livingorganisms. Just the soil plays a decisive role in the formation of sub-stance flows in landscape directly combined with plants, surface andground waters.

Soil compounds of microelements have a system organization beingrepresented by a great diversity of strongly bound solid phases (organic,mineral, organo-mineral, primary, secondary formations), mobile com-pounds, soluble and gaseous forms, and soil biota. It is formed under theinfluence of hierarchically organized soil-chemical and landscape-geochemical processes of migration, accumulation and transformationof these compounds.

The following objectives of this study were to:

- investigate the heavy metal content (Cu, Zn, Pb, Cd, Ni) in soils ofnatural landscapes and contaminated by these metals undertechnogenic and artificial conditions;

- evaluate ecological hazards caused by heavy metal compounds insoils;

- formulate the concept of a real and potential risk to the ecosystem inaddition to soil contamination with heavy metals.

2. Materials and methods

2.1. Study area

The study area presents the landscapes of the most significant terri-tories of Russia. These are forest landscapes of Murmansk surroundingarea (Kola Peninsula, North-Western Federal District of Russia) andRostov surrounding area (Southern Federal District of Russia).

The first group presents the forest landscapes that characterize thehighest share of the European part of Russia. Soils of this group are pre-sented by podzols, derived on the moraine deposits. Soils of the naturaland technogenic landscapes of this region were analyzed.

The second group of the investigated objects is the steppe land-scapes that are the most actively used in agriculture of Russia. Soils ofthis group are presented by chernozem, derived on the loess sediments.On the steppe soils two series of experiments were carried out. In thefirst series soils of the natural and technogenic landscapes were investi-gated. The other part of workwith chernozem is consisted of vegetationexperiments with artificial contamination of soils by heavy metals andtheir subsequent remediation by using some ameliorants.

We can compare the ecological situation that takes place in these re-gions under the influence of pollution by heavy metals.

2.2. Field experiment

To evaluate a real and potential risk of contaminated soils to the en-vironment, а long-term (2006–2011) field experiment was establishedon a clay loamy ordinary chernozem on loess-like loam (Haplic Cherno-zem, FAO).

The soil was contaminated with salts Zn2+ and Pb2+ acetate. Themetals were applied separately as dry acetate salts to the plow (0 to20-cm) horizon in fall. The application rates were 300 mg kg−1 for Znand 100 mg kg−1 for Pb, which corresponded to 3 maximum permissi-ble concentration (MPC) for thesemetals in the soil and to the real levelof soil contamination of Zn and Pb in the Rostov region (Russia).

Threemonths later the chalk (5mgm−2) and semidecomposed cat-tle manure (5 mg m−2) were applied as ameliorants according to thefollowing experimental design:

(1) Without metal addition;(2) Metal (Me);(3) Me + chalk, 5 mg m−2 + manure.

Please cite this article as: Motuzova, G.V., et al., Soil contaminationwith heExplor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.01.026

Experiments were conducted in triplicate. The previous results ofthepot experience has shown that themost significant effect of decreas-ing metal mobility in soil was at the simultaneous application of chalkand manure (Minkina et al., 2008, 2010).

Spring barley (Hordeum sativum distichum), cultivar Odesskii-100,was planted in experimental plots. The crop management practice rec-ommended for this zone was used. Samples of soil (0–20 cm layer) andplants were taken at the complete maturity stage of barley after 1 yearfrom the beginning of the experiment.

The establishment of experiments, observations, and recordings, andsampling of soils and plants were performed in accordance with proce-dures of field experiments (Dospekhov, 1968).

2.3. Methods of soil investigations

Soil properties were analyzed using Russian traditional methods(Arinushkina, 1970). Soil organic carbon was measured using 0.4 N po-tassium bichromate (the Tyurin method modified by Simakov). Soilparticle size distribution (silt and clay content) was determined by thepipettemethod after the pyrophosphate treatment. Cation exchange ca-pacity (CEC) of the soil was determined using 1 M ammonium chloride(the Bobko–Askinazi method). The exchangeable potassiumwas deter-mined by the Machigin (molybdenum blue) method. Adsorbed Na wasanalyzed by flame atomic adsorption spectrophotometry (FAAS). SoilpH was measured with a pH electrode using a 1:5 suspension of a soilto water ratio. Exchangeable calcium and magnesium were measuredby the titration at pH 12.5–13 and 10 respectively. Carbonates weremeasured by the Kudrin method using 0.005 NH2SO4 and then an ex-cess of the acid was titrated with alkali.

2.4. Analytical procedure

Soil samples for determining metal total concentrations wereground to pass through a 0.25 mm sieve. The total content of heavymetals was determined by heating with HF + H2SO4 and analyzedwith themetals in groundwater samples by atomic absorption spectro-photometry (Scientific Buck 200 A).

To detect the metal content that weakly bound with soil compo-nents (mobile compounds) was used following the protocol of Mineev(1989):

1) extraction for 1 h shaking, using a 1:10 suspension of a soil to H2Oratio — extract of water soluble metal form.

2) extraction for 18 h, using a 1:10 suspension of a soil to 1 N NH4OAc,pH4.8, ratio— extract of exchangeablewater solublemetals form in-cluding water soluble form.

The content of metals in strongly bound compounds was deter-mined as the difference between the total amount of metals in soilsand their weakly bound compound forms.

The extract from each stepwere filtered through paper (pore size 2–3 μm)and analyzed by atomic absorption spectrophotometry (ScientificBuck 200 A).

Heavy metals in plants were prepared for analyzing by dry combus-tion at 450 °C, the rest was dissolved by an acid mixture (HNO3 + HCl)(Methodological Guidelines on the Determination of Heavy Metals inAgricultural Soils and Crops, 1992). The content of heavy metals in ex-tracts from plants was determined by atomic absorption spectropho-tometry (Scientific Buck 200 A). The nitrogen content in grain ofbarley was analyzed by the optical method with indophenol greens(Mineev, 1989).

2.5. Ecological situation in Murmansky District under the influence of thepollution by heavy metals

TheMonchegorsk place (Murmansky region) is represented by nat-ural and technogenically transformed landscapes. Its sufficient part is



3G.V. Motuzova et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

under the influence of the gaseous wastes of Severonickel metallurgicalsmelter. It is one of the largest non-ferrous metallurgy smelter in theworld. The deposits of copper–nickel ores are predominantly concen-trated at a depth of 1–15 m of the Kola Peninsula. A number of greatmanufactories of nickel, copper, cobalt, and sulfuric acid productionhave grown in this region during more than 75 years (Dauwalter,1999; Environmetal Atlas of the Murmansk region, 1999).

The territory under consideration suffers from intensive technogenicloads (Kelley et al., 1995; Norseth, 1994; Paton et al., 2006). The majorpart of waste products enriched with copper and nickel pollutes the at-mosphere (Gregurek et al., 1998; Jaffe et al., 1995). For example, at theend of XX century the atmospheric pollution by harmful industrial dis-charges and car exhaust gasesmade up 800000–1000000 t (Chekushinet al., 1996).

The objects of this studywere the soils, located at different distancesfrom Severonickel smelter: in the background territory (80–90 km fromthe plant), in the technogenic zone (40–50 km from the plant), and inthe technogenic wasteland (7–15 km from the plant). Soil sampleswere selected through the soil profile. The soil samples were homoge-nized, air dried, and passed through 1 mm sieve.

2.6. Ecological situation in Rostov District under the influence of the pollu-tion by heavy metals

The soils, surrounding the Novocherkassk power station, were in-vestigated. This power station is the largest source of atmospheric aero-sol emissions in the South of Russia. The main components of theNovocherkassk power station emissions are ash, sulfur dioxide, andnitrogen oxides. The atmospheric emissions contain soot (more than30 t/year), vanadium pentoxide (about 8 t/year), iron oxides (morethan 5 t/year), chromic anhydride (about 0.1 t/year), Mn dioxide

Table 1The properties (рН, Corg (mg l−1)), Cu and Ni (mkg l−1) inwater extract, total content of Cu andof natural (background) and technogenic territories of natural (background) and technogenPeninsula).

Horizon, cm рН Corg Cu in water extract,mkg l−1

Background territoryА0

0–74.28 107 10.8

А2

7–154.64 52 13

Bhfa15–23

5.17 38 2.0

BС23–38

5.50 Not determined 1.6

C38–55


LSD0.95 1.1

Technogenic territoryА00–2

3.67 154 243.2

А2

2–44.28 20 19.6

Bhfa14–8

4.52 23 16.2

Bhfa28–22


BC22–40


C40–58


LSD0.95 7.2


(about 0.15 t/year), Ni oxide (1.5 kg/year), and hydrogen fluoride(7 kg/year). (Minkina et al., 2009).

The soil of ten monitoring plots located from 1.0 to 20.0 km aroundthe Novocherkassk power station was prepared. A relatively greaternumber of plots were arranged in the “main direction” from the stationaccording to the prevailing wind direction to the northwest of the pol-lution source through the residential areas of the city of Novocherkassk(Minkina et al., 2013).

3. Results and discussion

3.1. The state of soils of Murmansky District (Monchegorsk)

The studied podzols of background landscapes of Kola Peninsula,developed under the spruce and pine forests, have pH 3.6–4.2, or-ganic C content of 32–42%, and cation exchange capacity (CEC) of25–37 mg-eq 100 g−1. They have a relatively high content of Cu(30–89 mg kg−1) and Ni (50–120 mg kg−1). Table 1 is one of suchexamples. These levels exceed the average content of these elementsin soils (Vinogradov, 1957). They characterize the study area as bio-geochemical province. The high level of Cu and Ni concentration inthe investigated soils takes place due to the mineralogical composi-tion of soil-forming rocks. The last ones are presented by moraine de-posits. They are characterized with high content of Cu and Ni — 70–80and 100–150 mg kg−1 respectively (Dobrovolsky and Aleschukin,1964). These values significantly exceed Clarke levels of Cu and Ni forthe lithosphere, respectively equal to 47 and 58 mg kg−1 (Vinogradov,1957). High content of metals in soils is not dangerous for the ecosystemof the region because of low metal mobility.

This is evidenced by the ratio of the concentrations of the weaklybound (WB) and strongly bound (SB) compounds of these metals. In

Ni, their weakly bound (WB) compounds and strongly bound (SB) compounds in podzolsic landscapes in the surrounding area of Severonickel smelter (Murmansk District, Kola

Ni in water extract,mkg l−1

Total content,mg kg−1

WB/SB, % from totalcontent

Cu Ni Cu Ni

2.5 30 137 8/92 2/88

1.2 6 19 17/83 6/94

2.7 7 30 13/77 4/96

1.2 10 32 10/90 3/97

1.5 9 35 9/91 3/97

0.7 4 10

78.8 806 1922 57/43 12/88

20.4 16 124 54/46 6/94

41.3 28 137 75/25 14/86

29.4 35 149 21/79 7/93

3.2 19 139 9/91 6/94

4.2 31 121 2/98 2/98

3.9 16 23



Table 3Composition of ground waters and water of spring (mkg l−1) in the surrounding area ofSeveronickel smelter (Murmansk District, Kola Peninsula).

No. HCO3− SO4

2− Cu2+ Ni2+

Wells1 50/82 15/20 50/190 30/1604 58/67 37/43 110/240 80/1606 18/19 12/17 70/150 30/70

Springs3 14/27 17/20 3/16 9/504 9/11 10/12 6/13 30/130

in the numerator— the average content, in the denominator— the maximum content


organic horizons of the background soils this ratio consists of 8/92(Table 1). In this circumstances forest biogeocenosis of the region arecharacterized by high biological productivity.

The supply of phytomass of spruce and pine forests makes up 60–120 t/ha, the mass ratio of above-ground and under-ground parts oftrees is measured by 3:1, and the share of trunks have 60–64% of themass of trees. Annual production is measured 2.8–6.6 t/ha per year(Lukina and Nikonov, 1996).

Within the technogenic zone the soils suffer from adverse effects ofdust and gas emission of industrial enterprises. They reveal a higherconcentration of heavy metals. In the soils of the technogenic territoryof Severonickel metallurgical smelter (30–50 km from the plant) thetotal content of Cu and Ni increased in 2–5 times in comparison withbackground territory, while in the technogenic wasteland (5–10 kmfrom the plant) it increased in 26–40 times (Table 2). It is very impor-tant to take a note, that the content of metal mobile compounds in-creased, what is especially harm to biogeocenosis (Kryutchkov andMakarova, 1989; Minkina et al., 2009, 2013).

The content of weakly bound forms of Cu and Ni in soils of thetechnogenic zone increased till 30–50 times and in the technogenicwasteland — till 2 orders of magnitude (Table 2). Coefficients of varia-tion of metal content in soils of each zone consist of 20–30% and differ-ence in the content of metal compounds in soils of the investigatedzones is significant. The levels of metal content in technogenic soilspresent a real danger for ecosystem.

The total stock of biomass of spruce and pine trees decreases to 30times, overground phytomass of the trees reduces till 50 times theshare of the mass of the tree trunks decreases more than 13 times. An-nual production of spruce and pine reduced on orders, phytomass of aground part of trees decreases in 50 times.

Such a concentration of thesemetals in soils together with the otheraccompanying factors should be considered as a real hazard to pine andspruce forests. The latter are degraded, the wood stand, zoocoenosis,and microbiocoenosis show adverse changes. The content of organicsubstances in the wood phytomass and a share of photosynthesis or-gans reveal decreasing, the litter structure is changing as well (a highercontent of assimilative organs, perennial plants and mortmass). All thisserves as evidence of soil contamination as a real risk to biogeocenosis.

The podzolic soils under pine and spruce forests in the KolaPeninsula are capable to control the transfer of heavy metals and sul-fates to ground waters. These soils in particular easily absorb theheavy metals. The major part of elements absorbed by the litter is rep-resented by potentially mobile compounds of their solid phase.

In the technogenic zone the majority of copper and nickel com-pounds penetrate into soil mineral horizons, thus increasing their totalcontent by 2–3 times as compared to the background zone. The soilproves to be contaminated by heavy metals at a depth of more than50 cm. The soils reveal a higher concentration of soluble compounds.The contaminated soils exert an adverse effect on groundwaters aswell.

The composition of water extracts was also changed. Parallel withdecreasing pH in them, the content of Cu and Ni increased to a greaterextent (Table 1). As a result, soil waters (lysimeter water and water ex-tracts) of the impact zone become a danger.

Table 2Total content of Cu, Ni, Zn,Mnand theirweakly bound (WB) compounds inpodzols of natural (b

Cu Ni

Total content WB Total content WB

Background territory (more than 80 km from the metallurgical smelter)42–47 0.4–0.9 58–70 2–4

Technogenic territory (36–48 km from the metallurgical smelter)65–104 21–77 164–225 61–80

Technogenic wasteland (7–17 km from the metallurgical smelter)1050–1136 152–301 1101–2025 152–156


All this serves as evidence of soil contamination as a real risk tobiogeocenosis. The contaminated soils exert an adverse effect on groundwaters as well. The composition of water extracts was also changed(Table 1). Parallel with decreasing pH in them, the content of Cu andNi increased to a greater extent.

Being connected with ground waters, pH of the soil water revealedchanges from slightly acid to slightly alkaline and even alkaline, thusvarying in the range of 6.32–8.9. The ground water in springs andwells located in a distance of 2 km from the enterprise was contaminat-ed, showing262–350mkg l−1 of Ni and200–350mkg l−1 of Cu. In a dis-tance of 5 km from the smelter the concentration of these elements inthis water showed 225 and 363 mkg l−1 respectively being declinedin a distance to 20 km (Dauwalter, 1999; Henriksen et al., 1994). Oneshould notice that the Ni efficiency coefficient in water accounts for100 mkg l−1 and for Cu it is 2000 mkg l−1 (Bespamyatnov and Krotov,1985).

The water of springs 1 and 2 is sulfate–hydrocarbonate magne-sium–calcium, while in springs 3 and 4 it is regarded to a type ofhydrocarbonate–sulfate magnesium–calcium water (Table 3). Themaximum content of nickel (130 mkg l−1) was found in spring 4.

The information presented in Environmental Atlas of theMurmanskregion (1999) testifies the fact that the groundwaters are enrichedwithsulfates and nickel at the entire territory of the Kola Peninsula.

3.2. The state of soils in Rostov District under the influence of aerosolemission of the Novocherkassk power station

Chernozem is the main type of soil in this district. The chernozemhad a clay content of 286 g kg−1 and a physical clay content of471 g kg−1, pH(water) of 7.3, organic C content of 22 g kg−1, CaCO3 con-tent of 1 g kg−1, and exchangeable Ca and Mg contents of 29.5 and5.5 mM kg−1, respectively.

Most pollutants are deposited on the surface of soils within 5 kmfrom the source of contamination (Novocherkassk power station)along the main wind direction — northwest direction (Table 4). Theheavy metal contents gradually decrease with distance; their contentsin remote soils (more than 20 km) approach the background level.The mobility of metals in the contaminated soils varied analogously totheir total content: the share of LB compounds increased appreciably.In the soils closest to the Novocherkassk power station, the share of

ackground) and technogenic landscapes of theMonchegorsk surrounding area,mg kg−1.

Zn Mn

Total content WB Total content WB

48–72 16–18 462–490 124–137

53–75 16–22 266–300 21–62

62–90 3–10 1008–1154 3–8



Table 4Total content of Cu, Ni, Zn, Pb, theirweakly bound (WB) compounds and strongly bound (SB) compounds in chernozem of natural (background) and technogenic landscapes placed from1 to 20 km to the northwest of the Novocherkassk power station.

Cu Ni Zn Pb









Background territory (more than 20 km from the power station)30 10/90 35 10/90 68 12/88 24 15/85

Technogenic territory (5–15 km from the power station)59 30/70 50 20/80 113 35/65 43 26/74

Technogenic territory (0–5 km from the power station)75 36/64 74 33/77 140 42/58 65 40/60

5G.V. Motuzova et al. / Journal of Geochemical Exploration xxx (2014) xxx–xxx

weakly bound compounds of Cu, Ni, Zn and Pb increased by 2.7–3.3times (Table 4).

3.3. The state of artificially metal contaminated soils and the efficiency oftheir remediation

The content of metal in the chernozem of the steppe zone (withoutmetal addition)was 68mg kg−1 for Zn and 24mg kg−1 for Pb (Table 5)and corresponds to the background content of metals in soils (Minkinaet al., 2008, 2009).

The total metal content in the soil contaminated under field experi-mental conditions increased by 5.2 times for Zn and by 4.6 times for Pb.As was noted above, in clean soils, metals predominantly occurred inthe strongly bound state (85–88% of the total amount). The hazard ofsoil contamination with metals is related not only to the increase inmetal content, but also to the increase in metal mobility.

In the background soils, the share of weakly bound metal com-pounds was no more than 12–15% (Table 5); in the contaminatedsoils, theymade up almost one third and one half of the total metal con-tent for Zn and Pb.

The contamination of ordinary chernozem with Zn and Pb underfield experimental conditions was accompanied by an increase thetotal content ofmetals and theirmobility: the relative content ofweaklybound compounds increased by 2–3 times. The artificial contamina-tion of the soils resulted in an increase in the content of Zn and Pbweakly bound compounds above their MPC (100 mg kg−. 1 for Znand 32 mg kg−1 for Pb in soil (Methodological Guidelines on theDetermination of Heavy Metals in Agricultural Soils and Crops,1992)). The share of weakly bound metal compounds in the contam-inated soils decreased to the level typical for the clean soils or evenbelow (in the case of Zn).

The aim of the remediation of the polluted soil bymetals is to reducetheir mobility. The total content of metals in the soils with ameliorantsremained almost similar to that in the contaminated soils (Table 5).However, the group of weakly bound compounds and, hence, the mo-bility of metals decreased because of the decrease in the absolute con-tent of all mobile Zn and Pb forms: exchangeable, complex, and

Table 5Total content of Zn and Pb, their weakly bound (WB) compounds and strongly bound (SB) compof metals and nitrogen in grain after 1 year of soil contamination (Rostov region).

Experimental treatments Total content,mg kg−1


Zn Pb Zn Pb

Without metal addition 68 24 12/88 15/8Metal 356 110 32/68 38/6Me + chalk, 5 mg m−2 + manure 359 114 11/89 13/8LSD0.95 16 6 – –


specifically sorbed ones. The simultaneous application of manure andchalk enhanced the sorption effect each of themand resulted in the con-siderable decrease in the content of weakly bound Zn and Pb com-pounds. Already in the first year of their simultaneous use, the groupratio and, hence, the mobility of metals were similar to the analogousparameters of the initial soil.

The analysis of the group composition of heavymetal compounds inthe reclaimed soils revealed themechanism of ameliorant action on themobility of heavy metals in soils. The share of complex forms in weaklybound compound group decreased for Pb and remained stable for Zn.This could be related to the fact that the stabilization of organic manurecompounds with the formation of stable organomineral complexes oc-curred in the presence of chalk. These complexes strongly fixed heavymetals and made them unavailable for extraction by the reagentsused. The addition of 10% of humic acids to calcite under model experi-mental conditions increased the adsorption of Zn compared to the pureCaCO3 (Brummer et al., 1983).

The share of specifically sorbed forms inweakly bound compounds ofZn and Pb increased under ameliorants applying for 4–13% (Table 5). Theincrease in the sorption activity of Fe–Mn (hydr)oxides in calcareous soilsplays an important role in the fixation of pollutants.

Thus, the application of ameliorants significantly decreased the mo-bility of Zn and Pb. This effect was presumably due to the strong bindingof metals by carbonates through chemisorption and formation of low-soluble Zn and Pb compounds and to the additional fixation in theform of complexes at the addition of organic material (Minkina et al.,2011).

A close correlationwas found between the contents ofweakly boundZn and Pb compounds in the soil and their concentration in the barleygrain and straw (R = 0.76 ± 0.19–0.96 ± 0.07).

The soil contamination led to the accumulation of HMs in the plants.The concentrations of Zn and Pb in barley grain exceeded the corre-sponding MPC values (50.0 mg kg−1 for Zn and 0.5 mg kg−1 for Pb ingrain crops (Methodological Guidelines on the Determination ofHeavy Metals in Agricultural Soils and Crops, 1992)). Barley plants aremore resistant to contamination of ordinary chernozem by Zn than Pb.The content of Zn in barley grain was in 3 times higher under

ounds in chernozem (0–20 cmupper layer), spring barley productivity and the contents

Contents ofmetal in grain,mg kg−1

Contents ofnitrogen in grain,mg kg−1

Productivity, g m−2

Zn Pb Zn Pb Zn Pb

5 23.0 0.3 1.75 1.75 280.3 280.32 65.4 2.5 1.69 1.56 268.9 230.67 41.4 0.5 1.63 1.69 275.4 279.0

4.0 0.4 0.16 0.16 12.5 13.2




contamination compared to the control and exceed MPC of Zn in 1.3times. Pb applying in the soil to reveal the increase of its concentrationin barley grain in 8 times and exceed MCL of Pb in 5 times.

The nitrogen was reduced in grain growing on soil contaminated byPb. As a consequence the grain of barley growing in soil contaminatedby Zn and Pb is not suitable for fodder purposes and for brewing accord-ing Russian standards (GOST 5060-86, 1990).

Effect of ameliorants addition had a positive impact on the produc-tivity of barley. A decrease in the mobility of metals in the soil underthe impact of the ameliorants resulted in a significant lowering of theZn and Pb concentrations in barley grain (Table 5). Nitrogen has in-creased in barley grain to the control level in the soil, contaminated byPb, where chalk and manure were used as ameliorants.

4. Conclusions

Heavy metals that entered the soil from technogenic sources wereabsorbed by soil components with different strengths. Strong fixationof heavymetals protects ecosystems from the effects of pollution. How-ever it could be the cause of potential danger, because it was accumulat-ed by soils. The ratio of weakly bound heavy metal content to thestrongly bound content of metals is a very informative parameter forthe assessment of the ecological state of the polluted soils.

The real ecological thread of soil pollution by heavy metals was pro-vided by the increase of heavymetalmobility in soils. It leads to the dan-gerous ecological consequences:

- negative influence on the plants, cultivated of polluted soils;- negative influence on the underground water in the polluted soil;- degradation of the important properties of soils, providing their fer-tility (acid–base equilibrium, humus state, nitrogen content).

There is only onepossibility to improve the depredated soils— to de-crease the heavy metal mobility in the polluted soils.

Acknowledgments

This researchwas supported by the Russian Foundation for Basic Re-search, projects nos. 13-05-00583, 14-05-00586, 12-05-33078, and 11-05-90351-RBU, and a grant from the Ministry of Education and Scienceof Russia No. 1894, grant no. МК-6448.2014.4.

References

Arinushkina, E.V., 1970. Handbook on the Chemical Analysis of Soils. MGU, Moscow (inRussian).

Avtsin, A.P., Zhavoronkov, A.A., Rish, M.A., Strochkova, L.S., 1991. HumanMicroelementoses:Aetiology, Classification, Organopathology. Medicine, Moscow (in Russian).

Bespamyatnov, G.P., Krotov, Yu.A., 1985. The Maximum Allowable Limit of Chemical Sub-stances in the Environment. Chemistry, Leningrad (in Russian).

Bowen, H.J.M., 1979. Environmental Chemistry of the Elements. Academic Press, N.Y. 333.Brummer, G., Tiller, K.G., Herms, U., Clayton, P., 1983. Adsorption–desorption and/or pre-

cipitation–dissolution processes of zinc in soils. Geoderma 31 (40), 337–354.


Chekushin, V.A., Bogatyrev, I.V., Caritat, P. de, Niskavaara, H., Reimann, C., 1996. Annual at-mospheric deposition of 17 elements in eight catchments of the central Barents Re-gion. In: Reimann, C., Äyräs, M., Chekushin, V.A. (Eds.), Kola Project — InternationalReport, Catchment Study. NGU Report 96.088, pp. 79–99.

Dauwalter, M.V., 1999. Composition of groundwaters in the influence zone of mining andmetallurgical enterprises in the Murmansk region. Ecologo-geographical Problems inthe North of Kola Peninsula. Proceeding of the Kola Research Centre, Apatity.

Dobrovolsky, V.V., Aleschukin, L.V., 1964. Some landscape-geochemical features of thenorthern taiga of the Kola Peninsula. Soviet Soil Sci. 10 (in Russian).

Dospekhov, B.A., 1968. Procedure of Field Experiments. Kolos, Moscow (in Russian).Environmental Atlas of the Murmansk region, 1999. Murmansk (in Russian).GOST 5060-86, 1990. Malting barley. Specifications/state standards. Cereals, Legumes and

Oilseeds. Part 2 (Moscow. (in Russian)).Gregurek, D., Reimann, C., Stumpfi, E.F., 1998. Trace elements and precious metals

in snow samples from the immediate vicinity of nickel processing plants, KolaPeninsula, northwest Russia. Environ. Pollut. 102 (2–3), 221–232.

Henriksen, A., Kamari, J., Posch, M., Forsius, M., Wilander, A., Moiseenko, T., 1994. Criticalloads for surface waters in Scandinavia and Kola region. Critical loads and criticallimit values. Proceeding of the Finish–Swedish Environmental conference, Vaasa,Finland, pp. 97–109.

Jaffe, D., Cerundolo, B., Rickers, J., Stolzberg, R., Baklanov, A., 1995. Deposition of sulfateand heavy metals on the Kola Peninsula. Sci. Total Environ. 160–161, 127–134.

Kelley, J.A., Jaffe, D.A., Baklanov, A., Mahura, A., 1995. Heavymetals on the Kola Peninsula:aerosol size distribution. Sci. Total Environ. 160–161, 135–138.

Kovalsky, V.V., 1982. Geochemical Ecology. Nauka, Moscow (in Russian).Kryutchkov, V.V., Makarova, T.D., 1989. Aerotechnogenic Effects on Ecosystems in the

Kola Peninsula, Apatity (in Russian).Lukina, N.V., Nikonov, N.V., 1996. Biogeochemical Cycles in Forests Affected by

Agrotechnogenic Contamination, Apatity (in Russian).Meers, E., Unamuno, V.R., Laing, G.Du., Vangronsveld, J., Vanbroekhoven, K., Samson, R.,

Diels, L., Geebelen, W., Ruttens, A., Vandegehuchte, M., Tack, F.M.G., 2006. Zn in thesoil solution of unpolluted and polluted soils as affected by soil characteristics.Geoderma 136, 107–119.

Methodological Guidelines on the Determination of Heavy Metals in Agricultural Soilsand Crops, 1992. TsINAO, Moscow (in Russian).

Mineev, V.G., 1989. Laboratory Manual of Agricultural Chemistry. MGU, Moscow (inRussian).

Minkina, T.M., Motuzova, G.V., Nazarenko, O.G., Kryshchenko, V.S., Mandzhieva, S.S., 2008.Forms of Heavy Metal Compounds in Soils of the Steppe Zone. Eurasian Soil Sci. 41(7), 708–716.

Minkina, T.M., Motuzova, G.V., Nazarenko, O.G., Mandzhieva, S.S., 2009. Group composi-tion of heavy metal compounds in the soils contaminated by emissions from theNovocherkassk power station. Eurasian Soil Sci. 42 (13), 1533–1542.

Minkina, T.M., Motusova, G.V., Nazarenko, O.G., Mandzhieva, S.S., 2010. Heavy MetalCompounds in Soil: Transformation upon Soil Pollution and Ecological Significance.Nova Science Publishers, Inc., New York978-1-60876-466-2.

Minkina, T.M., Motusova, G.V., Mandzhieva, S.S., Nazarenko, O.G., Simunic, I., 2011. Trans-formation of heavy metal compounds during the remediation of contaminated soils.Agriculturae Conspectus Scientificus. 76 (1), 19–25.

Minkina, T.M., Motuzova, G.V., Mandzhieva, S.S., Nazarenko, O.G., Burachevskaya, M.V.,Antonenko, E.M., 2013. Fractional and group composition of the Mn, Cr, Ni, and Cdcompounds in the soils of technogenic landscapes in the impact zone of theNovocherkassk power station. Eurasian Soil Sci. 46 (4), 375–385.

Motuzova, G.V., 1999. Microelements in Soils: Systemic Organization, Ecological Signifi-cance, and Monitoring (Moscow. (in Russian)).

Norseth, T., 1994. Environmental pollution around nickel smelters in the Kola Peninsula(Russia). Sci. Total Environ. 148 (2–3), 103–108.

Paton, G.I., Viventsova, (Ruth), E., Kumpene, J., Wilson, M.J., Weitz, H.J., Dawson, J.J.C.,2006. An ecotoxicity assessment of contaminated forest soils from the Kola Peninsula.Sci. Total Environ. 355, 106–117.

Vinogradov, A.P., 1957. Geochemistry of Rare and Dispersed Elements in Soils (Moscow.(in Russian)).

Weber, J., Karczewska, A., 2004. Biogeochemical processes and the role of heavy metals inthe soil environment. Geoderma 122, 105–107.


http://refhub.elsevier.com/S0375-6742(14)00036-3/rf0005





































































Download - Soil contamination with heavy metals as a potential and real risk to the environment

Top Related