The abundances of chemical elements in urban soils

Journal of Geochemical Exploration 147 (2014) 245–249

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The abundances of chemical elements in urban soils Vladimir Alekseenko a, Alexey Alekseenko b,⁎ a b

Southern Federal University, Russia National Mineral Resources University (University of Mines), Russia

a r t i c l e

i n f o

Article history: Received 4 March 2014 Accepted 6 August 2014 Available online 16 August 2014 Keywords: Urban environmental issues Soil pollution Trace elements Heavy metals Environmental geochemistry

a b s t r a c t For the first time the abundances (the average concentrations) of chemical elements are given for the soils of urban landscapes. The figures were established by authors on the base of average concentrations of chemical elements in the soils of more than 300 cities and settlements in Europe, Asia, Africa, Australia, and America. The major part of data (sampling, analyses and their statistical treatment) was obtained directly by authors as a result of special studies conducted for more than 15 years. The concentrations of elements were defined by the spectral, gravimetric, neutron activation and the X-ray fluorescence methods of analyses. The control of sampling and also inner and outer laboratory controls of analyses were carried out. The ordinary and the control analyses were carried out in the certified and accredited laboratories, including arbitration laboratory. The sufficiently numerous published materials of different researchers were also used. © 2014 Elsevier B.V. All rights reserved.

1. Introduction One of the most important indicators for characterising the large geochemical systems is the average content of their constituent chemical elements (Geochemistry, 2006). The biggest geochemical system is the Earth's crust. The data on its chemical composition to a depth of 16 km were first published in 1889 by the American scientist F.W. Clarke. On the proposal of the Russian geochemist A.E. Fersman the average contents of chemical elements in this system, as well as in other major geochemical Earth systems (hydrosphere, atmosphere, pedosphere, in the main types of rocks, etc.) are called the abundances or “the Clarkes” (Perelman, 1975). Abundances express the average concentrations of chemical elements in geochemical systems, for example, the abundance of lead in the Earth's crust, the abundance of copper in carbonate rocks, and the abundance of manganese in living matter. In the time of life existence, or at least in the time of the existence of human beings, the abundances of chemical elements within the Earth's crust have not been changed dramatically due to migration and concentration processes except the radioactive elements and their decay products and also noble gases. However, significant changes took place in the distribution of chemical elements. But within the biosphere not only the distribution, but also the abundances of elements have changed during

⁎ Corresponding author at: National Mineral Resources University (University of Mines), Department of Geoecology, 22 line, 2, Faculty of Mining, 199106 SaintPetersburg, Russia. Tel.: +7 963 696 43 14. E-mail address: [email protected] (A. Alekseenko).

http://dx.doi.org/10.1016/j.gexplo.2014.08.003 0375-6742/© 2014 Elsevier B.V. All rights reserved.

the last centuries (Alekseenko, 2006; Bowen, 1979; Kabata-Pendias, 2010). The rate of a number of geochemical changes taking place during the last decades in the biosphere has become catastrophically high. Such changes are often connected with human activities (Cicchella et al., 2008a; Motuzova and Karpova, 2013). To study these changes and to make better informed decisions on diminishing their adverse impact on living organisms, and especially on people, it is necessary to estimate the contemporary abundances of chemical elements in geochemical systems susceptible to the highest anthropogenic impact and having a significant effect on the development and existence of living organisms. One of such systems is the soil of urban landscapes (Cicchella et al., 2005; Gerasimova et al., 2003; Motuzova and Bezuglova, 2007; Norra and Stüben, 2003). At present certain demand arose for a conversion from a qualitative to a quantitative description of geochemical processes in urban soils and for valid (quantitative) impact forecast (Birke and Rauch, 2000; Cicchella et al., 2003, 2008c; Crnković et al., 2006; Doichinova et al., 2006; Imperato et al., 2003; Li et al., 2001; Linde et al., 2001; Lorenz and Kandeler, 2005; Madrid et al., 2006; Morel and Dе Kimpe, 2000; Norra et al., 2006; Papa et al., 2009; Pouyat et al., 2007; Thuy et al., 2000; Tume et al., 2008 and others). The prerequisites for this are: 1 — the changes of environmental and geochemical situations have begun to affect the life safety and, as a result, the sustainable development of both particular regions and whole countries (Bityukova and Kasimov, 2012; Cicchella et al., 2008b; Shayler et al., 2009); 2 — many problems have passed from the category of “pure” geochemical to economic and even political (Alekseenko et al., 2002; Bityukova et al., 2011; Pickett et al., 2008); 3 — in such branches

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V. Alekseenko, A. Alekseenko / Journal of Geochemical Exploration 147 (2014) 245–249

Table 1 The list of cities and regions taken into account in this work. No. City, region, country

The data was obtained Directly by authors

From literature and from certain researchers

Millionaire-cities (with the number of population more than 700,000 people) 1 Adelaide, Australia + 2 Almaty, Kazakhstan + + 3 Beijing, China + + 4 Belgrade, Serbia + 5 Berlin, Germany + 6 Bishkek, Kyrgyzstan + 7 Budapest, Hungary + 8 Cairo, Egypt + 9 Chelyabinsk, Russia + + 10 Cologne, Germany + 11 Da Nang, Vietnam + + 12 Donetsk, Ukraine + + 13 Hamburg, Germany + 14 Hong Kong, China + 15 Istanbul, Turkey + + 16 Kiev, Ukraine + 17 Krasnodar, Russia + + 18 Krasnoyarsk, Russia + + 19 London, United Kingdom + + 20 Lviv, Ukraine + 21 Madrid, Spain + + 22 Minsk, Belarus + + 23 Moscow, Russia + 24 Naples, Italy + + 25 Novosibirsk, Russia + 26 Palermo, Italy + 27 Paris, France + 28 Perm, Russia + 29 Rome, Italy + 30 Rostov-on-Don, Russia + 31 Saint-Petersburg, Russia + + 32 Samara, Russia + + 33 Seville, Spain + 34 Shenzhen, China + 35 Stockholm, Sweden + + 36 Ulan Bator, Mongolia + 37 Vienna, Austria + 38 Yerevan, Armenia + + Half-millionaire cities (with the number of population 300,000–700,000 people) 1 Aktobe, Kazakhstan + + 2 Arkhangelsk, Russia + + 3 Astana, Kazakhstan + 4 Astrakhan, Russia + 5 Barnaul, Russia + + 6 Bielefeld, Germany + 7 Brest, Belarus + 8 Cheboksary, Russia + 9 Cherepovets, Russia + 10 Gold Coast, Australia + 11 Gomel, Belarus + 12 Grodno, Belarus 13 Helsinki, Finland + 14 Irkutsk, Russia + 15 Kaliningrad, Russia + 16 Karaganda, Kazakhstan + 17 Kaunas, Lithuania + 18 Kemerovo, Russia + 19 Kostanay, Kazakhstan + 20 Mariupol, Ukraine + 21 Mogilev, Belarus + 22 Novokuznetsk, Russia + 23 Novorossiysk, Russia + 24 Orenburg, Russia + 25 Oskemen, Kazakhstan + 26 Pavlodar, Kazakhstan + 27 Semey, Kazakhstan + 28 Sevastopol, Russia + + 29 Shymkent, Kazakhstan + 30 Simferopol, Russia + 31 Smolensk, Russia + + 32 Stavropol, Russia +

Table 1 (continued) No. City, region, country



Half-millionaire cities (with the number of population 300,000–700,000 people) 33 Taraz, Kazakhstan + 34 Tomsk, Russia + 35 Ulan-Ude, Russia + 36 Varna, Bulgaria + 37 Vitebsk, Belarus + 38 Vladimir, Russia + 39 Vladivostok, Russia + Cities with a local significance (with the number of population 100,000–300,000 people) 1 Aktau, Kazakhstan + + 2 Amiens, France + 3 Artemivsk, Ukraine + 4 Atyrau, Kazakhstan + 5 Babruysk, Belarus + + 6 Baranovichi, Belarus + 7 Barysaw, Belarus + 8 Biysk, Russia + 9 Cherkasy, Kazakhstan + 10 Cherkessk, Russia + 11 Dresden, Germany + 12 Exeter, United Kingdom + 13 Horlivka, Ukraine + 14 Kyzylorda, Kazakhstan + 15 Lecce, Italy + 16 Magadan, Russia + 17 Mezhdurechensk, Russia + 18 Noginsk-Elektrostal, Russia + 19 Oral, Kazakhstan + 20 Orsha, Belarus + 21 Padua, Italy + + 22 Petropavl, Kazakhstan + 23 Petrozavodsk, Russia + 24 Pinsk, Belarus + 25 Plymouth, United Kingdom + 26 Rubtsovsk, Russia + 27 Taldykorgan, Kazakhstan + 28 Temirtau, Kazakhstan + 29 Veliky Novgorod, Russia + 30 Verona, Italy + 31 Zhytomyr, Ukraine + Regions where small towns were studied (with the number of population less than 100,000 people) 1 Almaty Province, Kazakhstan + 2 Altai Krai, Russia + 3 Brest Region, Belarus + 4 Chernihiv Oblast, Ukraine + 5 East Kazakhstan Province, + Kazakhstan 6 Gomel Region, Belarus + 7 Grodno Region, Belarus + 8 Hainuat Province, Belgium + 9 Ile-de-France Region, France + 10 Jewish Autonomous Oblast, Russia + 11 Karagandy Province, Kazakhstan + 12 Kiev Oblast, Ukraine + 13 Komi Republic, Russia + 14 Krasnodar Krai, Russia + 15 Krasnoyarsk Krai, Russia + 16 Kuyavian-Pomeranian + Voivodeship, Poland 17 Leningrad Oblast, Russia + 18 Minsk Region, Belarus + 19 Mogilev Region, Belarus + 20 Moscow Oblast, Russia + 21 Murmansk Oblast, Russia + 22 Novosibirsk Oblast, Russia + 23 Rostov Oblast, Russia + 24 Stavropol Krai, Russia + 25 Sukhum District, Abkhazia + 26 Vitebsk Region, Belarus + 27 Volyn Oblast, Ukraine + 28 Zaporizhia Oblasst, Ukraine +

V. Alekseenko, A. Alekseenko / Journal of Geochemical Exploration 147 (2014) 245–249 Table 1 (continued) No. City, region, country



Regions where small settlements, villages, hamlets were studied 1 Altai Krai, Russia + 2 Aqaba Governorate, Jordan + 3 Kiev Oblast, Ukraine + 4 Krasnodar Krai, Russia + 5 Kymenlaakso Region, Finland + 6 Primorsky Krai, Russia + 7 Republic of Dagestan, Russia + 8 Rostov Oblast, Russia + 9 Tomsk Oblast, Russia + Regions where tourist and recreational areas were studied 1 Apulia, Italy + 2 Austria + 3 Bavaria, Germany + 4 Burgas Province, Bulgaria + 5 Canarian Islands, Spain + 6 Cuba + 7 Devonshire, United Kingdom + 8 Dobrich Province, Bulgaria + 9 Issyk Kul Province, + Kyrgyzstan 10 Kaliningrad Oblast, Russia + 11 Krasnodar Krai, Russia + 12 Leningrad Oblast, Russia 13 Luxor Governorate, Egypt + 14 Ma'an Governorate, Jordan + 15 North Rhine-Westphalia, + Germany 16 Northern Mariana Islands, USA + 17 Queensland State, Australia + 18 Red Sea Governorate, Egypt + 19 Republic of Crimea, Russia + 20 San Marino + 21 South Sinai Governorate, Egypt + 22 Stavropol Krai, Russia + 23 Sukhum District, Abkhazia + 24 Vladimir Oblast, Russia + 25 Yvelines Department, France +

of geochemistry as environmental geochemistry, biogeochemistry and the geochemical barriers doctrine many advances have been achieved (Alekseenko, 2000; Giaccioa et al., 2012; Kabata-Pendias, 2010; Perelman and Kasimov, 1999; Saet et al., 1990). Particularly high ecological and geochemical changes, mainly related to human activities, engulfed the geochemical system of urban soils (Alekseenko, 2000). Settlements occupy only about 5% of the land area, but virtually the entire population of the planet lives within them (Johnson et al., 2011). The main deposing medium in cities is soil, which ecological and geochemical conditions largely determine the life safety of citizens (Tarzia et al., 2002). All this makes us consider that one of the priority tasks of the environmental geochemistry is to establish the average contents (abundances) of chemical elements in the soils of settlements. The authors have devoted more than 15 years of research carried out specifically to this objective. 2. Materials and methods Ongoing studies included sampling, chemical analysis and processing the received information. The geochemical properties of urban soils from more than 300 cities in Europe, Asia, Africa, Australia, and America were evaluated (Table 1). In each settlement samples were collected uniformly throughout the territory, covering residential, industrial, recreational and other urban areas. The sampling was carried out directly from the soil surface and specifically traversed pits, ditches and wells from the upper 30 cm soil horizon. The preliminary studies have shown that within this horizon,

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Table 2 The abundances in the Earth's crust, Earth's soils and urban soils (mg/kg). Element

Ag Al As B Ba Be Bi C Ca Cd Cl Co Cr Cs Cu Fe Ga Ge H Hg K La Li Mg Mn Mo N Na Nb Ni O P Pb Rb S Sb Sc Se Si Sn Sr Ta Ti Tl V W Y Yb Zn Zr

Element number

47 13 33 5 56 4 83 6 20 48 17 27 24 55 29 26 31 32 1 80 19 57 3 12 25 42 7 11 41 28 8 15 82 37 16 51 21 34 14 50 38 73 22 81 23 74 39 70 30 40

Abundance in the Earth's crust

Earth's soils

Urban soils

0.07 80,500 1.7 12.0 650.00 3.8 0.009 – 29,600 0.13 170 18.0 83.0 3.7 47.0 46,500 19.0 1.4 – 0.08 25,000 29.0 32.0 18,700 1000 1.1 19.00 25,000 20.0 58.0 – 930 16.0 150 470 0.5 10.0 0.05 295,000 2.5 340 2.5 4500 1.0 90.0 1.3 20.0 0.3 83.0 170.0

0.50 71,300 5.0 10.0 500.00 6.0 – – 13,700 0.50 100 8.0 200.0 5.0 20.0 38,000 30.0 5.0 – 0.01 13,600 40.0 30.0 6300 850 2.0 1000 6300 – 40.0 – 800 10.0 100 850 – 7.0 0.01 330,000 10.0 300 – 4600 – 100.0 – 50.0 – 50.0 300.0

0.37 38,200 15.9 45.0 853.12 3.3 1.12 45,100 53,800 0.90 285 14.1 80.0 – 39.0 22,300 16.2 1.8 15,000 0.88 13,400 34.0 49.5 7900 729 2.4 10,000 5800 15.7 33.0 490,000 1200 54.5 58 1200 1.0 9.4 – 289,000 6.8 458 1.5 4758 1.1 104.9 2.9 23.4 2.4 158.0 255.6

the main changes occur and the upper soil layer is the geochemical centre of soil (Perelman and Kasimov, 1999). The number of samples in each locality ranged from 30 to 1000. Considering the great importance of the defined contents, quantitative and quantitative emission spectral, gravimetric, X-ray fluorescence, and partly neutron activation analyses were carried out in parallel approximately in the samples. In a volume of 3–5% of the total number of samples, sampling and analyses of the inner and external controls were conducted. Calculation of random and systematic errors allowed to consider the sampling and analytical laboratory work as good. Separately for each settlement the results of analyses of all samples were subjected to standard statistical treatment with the establishment of the laws of distribution and average contents of all the elements. Thus the average content of chemical elements which characterise the studied cities was obtained. For one more control all of the samples collected within a single settlement were selected for an overall sample. The results of its analyses were compared with the average content in soils of the city. The convergence of concentrations is satisfactory and good.

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Fig. 1. The A.E. Fersman's half-logarithm graph of the abundances of chemical elements in the Earth's crust.

3. Results

The considered figures of the abundances in urban soils give us an ability to conclude that: the abundances of chemical elements in urban soils has in many aspects inherited general trends from the Earth's crust and the Earth's soils. They are, first of all: extreme irregularity of the abundances; the connection between the concentrations of elements and their atomic masses, which leads to the prevailing of light elements; the prevailing of even-atomic elements and especially of elements with the 4-divisible atomic masses of leading isotope in this geochemical system. For the further exposure of features of the abundances of chemical elements in urban soils we consider, as it did A.E. Fersman for the Earth's crust (Fig. 1), the half-logarithm graph (Fig. 2) with the curved lines of the abundances of the odd-atomic and the even-atomic chemical elements. Figs. 1 and 2 show the following:

The abundances (average concentrations) of chemical elements in urban soils established by the authors (Table 2) were compared with the existing data on the abundances of chemical elements in the Earth's crust and the Earth's soil cover (Vinogradov, 1959).

a. Chemical elements are distributed extremely irregularly in urban soils, what is also typical for the Earth's crust and soils. b. Nine elements (O, Si, Ca, C, Al, Fe, H, K, N) make the 97.68% of the considering geochemical system. These elements and also Zn, Sr,

For every city the average concentrations of elements in soils were determined. To avoid the errors related to unequal number of samples, each city was then represented by only one “averaged” sample. The published data and the materials kindly provided by a number of researchers were also incorporated into the research (Table 1). As a result the rows in which each city was presented by an average content of chemical elements in soils for all the elements were written. The statistical processing of this data allowed to calculate the average concentrations of chemical elements in urban soils. They can be considered as the abundances (average concentrations) of chemical elements in urban soils.

Fig. 2. The half-logarithm graph of the abundances of chemical elements in urban soils.


c.

d.

e.

f.

Zr, Ba, and Pb essentially prevail over the trend line. Analogously as in the Earth's crust we could name them surplus in this geochemical system. Part of them could be considered as “inherited” from the concentrations in the Earth's crust; another part is explained as a result of intensive technogenic activity in the cities. Chemical elements with the abundances significantly lower than the trend line, are divided to insufficient. They are: Li, Be, Sc, Ge, Ag, and Hg, and also Ta, Tl, and Cd. Most of them are rare: Li, Be, Sc, Ge, Ta, and Tl, six of the nine of insufficient. The abundances of chemical elements in urban soils are irregularly decreasing in proportion with the increasing atomic masses. Therefore, the evolution of organisms in this system occurs in the conditions of light elements' prevalence. It corresponds to the conditions of the evolutional development of the living matter on the Earth. The irregularity of element decreasing may be somewhat connected, as stated above, with the technogenic influence. The Oddo–Harkins rule, which holds that elements with an even atomic number are more common than elements with an odd atomic number, is saved in the urban soils but with some technogenic complications. Among the considered abundances the even-atomic elements make 91.48% of the urban soils mass. As it is in the Earth's crust, elements with the 4-divisible atomic masses of leading isotope (O — 16, Si — 28, Ca — 40, C — 12, Fe — 56) are sharply prevailing in urban soils.

4. Conclusion In spite of significant differences between abundances of several elements in urban soils and those values calculated for the Earth's crust and the Earth's soil cover, the general patterns of element abundances in urban soils repeat those in the Earth's crust in a great measure. The established abundances of chemical elements in urban soils can be considered as their geochemical (ecological and geochemical) characteristic, reflecting the combined impact of technogenic and natural processes occurring during certain time period (the end of the XX century– beginning of the XXI century). With the development of science and technology the abundances may gradually change. The rate of these changes is still poorly predictable. The authors hope that the abundances of chemical elements presented for the first time may and will be used during various ecological and geochemical studies. Acknowledgements The authors would like to acknowledge the researchers from the Institute of Biosphere Geochemistry: E.V. Vlasova, A.Yu. Petrov, and S.N. Voronets. A.A. Trofimov, I.A. Karlovich, G.Yu. Yamskikh, and I.V. Borisova are also acknowledged for their help during the sampling and data earning. The samples were also taken by A.V. and E.V. Alekseenko, O.A. and A.Yu. Yudov, S.A. Buzmakov, and N.G. Ivashchenko. Several results of soil sample analysis were obtained from distinguished scientists of CIS: M.S. Panin, L.P. Rikhvanov, N.V. Baranovskaya, A.I. Syso, V.S. Bezel, P.V. Zaritskiy, V.N. Zuev, N.E. Kisel, Z.V. Lysenkova, T.M. Minkina, N.N. Miroshnichenko, V.V. Rudskiy, S.B. Yashchinin, and S.E. Kalyuga. The authors gratefully acknowledge all of them. The Vice-President of the Russian Academy of Sciences N.P. Laverov is acknowledged for reviewing an earlier version of the manuscript. References Alekseenko, V.A., 2000. Ecological Geochemistry. Logos, Moscow, (627 pp., in Russian). Alekseenko, V.A., 2006. The Ecological Geochemical Changes in the Biosphere. Development, Estimation. Universitetskaya Kniga, Moscow, (520 pp., in Russian). Alekseenko, V.A., Suvorinov, A.V., Alekseenko, V.Ap, Bofanova, A.B., 2002. Metals in the Environment. The Soils of Geochemical Landscapes of Rostov Region. Logos, Moscow, (312 pp., in Russian). Birke, M., Rauch, U., 2000. Urban geochemistry in the Berlin metropolitan area. Environ. Geochem. Health 22, 233–248.

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