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Standards for the contents of heavy metals and metalloids in soils

Article  in  Eurasian Soil Science · March 2012

DOI: 10.1134/S1064229312030131

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ISSN 10642293, Eurasian Soil Science, 2012, Vol. 45, No. 3, pp. 321–328. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Yu.N. Vodyanitskii, 2012, published in Pochvovedenie, 2012, No. 3, pp. 368–375.

DEGRADATION, REHABILITATION,
AND CONSERVATION OF SOILS

Standards for the Contents of Heavy Metals and Metalloids

in Soils
Yu. N. Vodyanitskii
V.V. Dokuchaev Soil Science Institute, Russian Academy of Agricultural Sciences, per. Pyzhevskii 7, Moscow, 119017 Russia
Email: yu.vodyan@mail.ru
Received October 19, 2010

Abstract—In line with the presentday ecological and toxicological data obtained by Dutch ecologists, heavy
metals/metalloids form the following succession according to their hazard degree in soils: Se > Tl > Sb > Cd >
V > Hg > Ni > Cu > Cr > As > Ba. This sequence substantially differs from the succession of heavy elements
presented in the general toxicological GOST (State Norms and Standards) 17.4.1.028, which considers As,
Cd, Hg, Se, Pb, and Zn to be strongly hazardous elements, whereas Co, Ni, Mo, Sb, and Cr to be moderately
hazardous. As compared to the general toxicological approach, the hazard of lead, zinc, and cobalt is lower
in soils, and that of vanadium, antimony, and barium is higher. The new sequence also differs from that of the
metal hazard in soils according to the Russian standard on the maximal permissible concentration of mobile
metal forms (MPCmob): Cu > Ni > Co > Cr > Zn. Neither an MPCmob nor an APCmob has been adopted for
strongly hazardous thallium, selenium, and vanadium in Russia. The content of heavy metals in contami
nated soils is very unevenly studied: 11 of them, i.e., Cu, Zn, Pb, Ni, Cd, Cr, As, Mn, Co, Hg, and Se, are
better known, while the rest, much worse, although there are dangerous elements (Ba, V, Tl) among them.
DOI: 10.1134/S1064229312030131

INTRODUCTION is also applied for assessing the hazard of metals/met

The soil chemistry distinguishes heavy metals as a
special group of elements because of their toxic effect
exerted on plants upon their high concentrations.
However, there is no common opinion on the hazard
degree of any particular heavy metal in soils. Only
three heavy metals, i.e., Pb, Cd, and Hg, were men
tioned in the Global Monitoring Program adopted by
the UNO in 1973 (cited after [15]). Later, in the report
delivered by the Executive Director of the UN Envi
ronmental Program (UNEP), seven other heavy met
als (Cu, Sn, V, Cr, Mo, Co, and Ni) and three metal
loids (Sb, As, and Se) were added to the list of the most
hazardous elements [32].
These recommendations still form the basis for
monitoring heavy elements in soils. The Ministry of
Natural Resources and Ecology of the Russian Feder
ation controls the total content of nine heavy metals in
soils [12]. For some metals (V, Mn, Pb), maximum
permissible concentrations (MPC) were adopted; for
others (Cd, Cu, Ni, and Zn), approximate permissible
concentrations (APC) were introduced; and, for the
third group of metals that are not described by any
standards (Co, Cr), the soil’s contamination degree is
estimated by the empiric criterion, i.e., a fourfold
excess of the background values.
The Russian sanitary hygienic GOST 17.4.10283
classifies As, Cd, Hg, Se, Pb, and Zn as highly hazard
ous elements, whereas Ni, Mo, Cu, and Sb as moder
ately hazardous ones [11]. This list of general toxicity
alloids in the soils despite the fact that it ignores the
interaction between the pollutants and soil compo
nents, which leads to misinterpretation of their toxic
ity. Later, special attention was paid to six heavy ele
ments in soils, i.e., Ni, Cu, Zn, Cd, Pb, and As; and
APC criteria were developed for them (cited after [1]).
In western countries worried about the environ
ment condition, the development of standards is
intensely promoted. The toxicity was assessed on the
basis of the impact of heavy metals/metalloids on bio
logical objects in soils and soil solutions. Dutch ecolo
gists have generalized the research data on the toxicity
of heavy metals/metalloids in soils.
The aim of this paper is to compare the Russian and
the Dutch lists of hazardous metals/metalloids in soils
and to attract attention to the most dangerous ele
ments.
THE GROUP OF HEAVY METALS
AND METALLOIDS
The metals with their atomic mass heavier than
50 are usually regarded as heavy metals [27]. However,
the known lists of heavy metals are not precise. The
number of heavy metals is not usually specified: the
vague phrase “more than 40 chemical elements” is
common [28]. Nevertheless, a list comprising 19 ele
ments (Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Mo, Cd,
Sn, Sb, Te, W, Hg, Tl, Pb, and Bi) is often cited [28].
This list of metals does not contain Ba, lanthanides,

321
322 VODYANITSKII

HМ HМD ASSESSMENT OF HEAVY METALS

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 AND METALLOIDS TOXICITY IN SOILS
23 24 25 26 27 28 29 30 31 32 33 34
4
V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se ACCORDING TO THE RUSSIAN
37 38 39 40 41 42 44 45 46 47 48 49 50 51 52
5 AND DUTCH CRITERIA
Rb Sr Y Zr Nb Mo Ru Rh Pd Ag Cd In Sn Sb Te
55 55 57 72 73 74 75 76 77 78 79 80 81 82 83
Let us scrutinize the paper by Dutch ecologists [36]
6
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi dealing with the standardization of the heavy
metal/metalloid content in soils and sediments. The
58 59 60 62 63 64 65 66 67 68 69 70 71
essence of this paper consists in the mathematical har
Ce Pr Nd Sm Eu Cd Tb Dy Ho Er Tm Yb Lu
90 92 monization of a large number of experimental studies
Th U on the influence of heavy metals/metalloids on the
biota and plants. The list of references includes 160
Fragments of the longperiod option of the Mendeleev titles of publications. The maximum permissible addi
Periodic System including heavy metals (HM) and heavy tion (MPA) of the heavy metal/metalloid content in
metalloids (HMD).
the soil is the key idea upon the standardization of the
soil contamination. The MPA is calculated proceed
and actinides. Antimony included in this list is a met ing from the following condition:
alloid, and soil scientists usually also add another met MPA = NOEC : 10,
alloid, i.e., As [31]. In the later edition of textbook where the abbreviation NOEC stands for no
[29], only eleven elements are classified as the most observed effect concentration, i.e., the maximal con
typical contaminating heavy metals: Pb, Cd, Hg, Zn, centration exerting no significant influence on the
Mo, Ni, Co, Sn, Ni, Cu, and V. It appears appropriate growth and reproduction of the test organisms. The
Dutch ecologists took into account the influence of
to add heavy metalloids (their former name was semi contaminated soils on soil fauna representatives
metals) to the group of heavy metals. Two of them, i.e., (earthworms and arthropods), on the development of
Sb and As, are included as hazardous metalloids on microbiological processes, and the response of plants.
many lists of heavy elements. In this case, all the ele In addition, the biological effect of heavy elements
ments from V (atomic mass 50.9) to U (atomic mass passing into the solution (in laboratory experiments
238) constitute the group of natural heavy metals and with suspensions) and into the ground and surface
metalloids, except for halogens (the 17th group) and water (under natural conditions) was taken into con
noble gases (the 18th group), which do not refer to sideration.
heavy metals and metalloids (Fig. 1). The transura Let us analyze the MPA values; they permit us to
nium elements were artificially obtained; therefore, we rank a large set (17) of heavy metals/metalloids and to
don’t consider them. Thus, 57 elements form the distinguish the most hazardous among them in the
group of heavy metals and metalloids. soils. Let us make several comparisons for this pur
pose. First, let us compare the set of elements toxicity
Not all heavy elements entering soils as pollutants according to the general toxicological criterion with
are similarly hazardous for plants, biota, and ground the set of their toxicity in soil according to the MPA
water. At present, the general toxicological GOST value and then the sequence of element toxicity
operates in Russia, dividing heavy metals/metalloids according to their mobility to the same sequence
according to the MPA values.
into three classes by their hazard degree [11]. How
ever, this versatile classification of elements does not Comparison of the elements toxicity according to the
general toxicological criterion to the sequence of the ele
take into account the specific features of the deposit
ments toxicity in the soil according to the MPA values.
ing environments; therefore, it appears to be more The MPA values vary very widely, i.e., from
suitable for the air and water than for soils. Pollutants 0.0061 mg/kg for a light metal Be (the most toxic ele
entering soil interact with its active phase (clay miner ment) to 253 mg/kg for Mo (the least toxic element).
als, oxides and hydroxides of iron and manganese, and The wide range reflects the difference in the hazard
organic substance) and change their own activity degree of the elements in the soils. For subdividing the
either increasing or decreasing their hazard. Let us elements by their hazard on the MPA basis, we refer
take Pb as an example. The high biological hazard of the elements with MPA < 1 mg/kg to the first class; the
Pb is manifested in experiments with its salts. How elements with 1 mg/kg < MPA < 10 mg/kg, to the sec
ever, in soil, lead forms stable complex compounds ond class; and those with MPA > 10 mg/kg, to the
third class (Table 1). Above all, the absence of ele
with organic ligands, which become much less hazardous ments recognized as very hazardous in soils (beryllium
for living organisms than metal ions are [24]. In this case, and thallium) on the list of elements standardized in
the share of these complexes in the water extract can Russia stands out. At the same time, the hazard of Pb
exceed 90% of the total lead content. As we show below, and Zn in the soils is not as high as in other media: they
the lead hazard in soils is assessed now as low. may be classified as the low dangerous third group

EURASIAN SOIL SCIENCE Vol. 45 No. 3 2012

 STANDARDS FOR THE CONTENTS OF HEAVY METALS AND METALLOIDS 323

Table 1. Hazard of metals/metalloids according to the Russian general toxicological standard (cited after [11]), according
to the MPCmob for soils (cited after [1]), and according to the Dutch standards for soils [36]
Russia
Hazard class The Netherlands, MPA for soils
General toxicological standard MPCmob for soils
1. Highly hazardous As, Cd, Hg, Se, Pb, Zn <1: Be, Se, Tl, Sb, Cd
2. Moderately hazardous Co, Ni, Mo, Cu, Sb, Cr Cu(3), Ni(4), Co(5), Cr(6) 1–10: V, Hg, Ni, Cu, Cr, As, Ba
3. Low hazardous Ba, V, W, Mn, Sr Zn(23) >10: Zn, Co, Sn, Ce, Pb, Mo
Note: For the numbers, the dimension is in mg/kg.

according to the MPA values for the soil. This is also IRREGULARITY IN THE INVESTIGATION
true for Mo, which may be moved from the second OF HEAVY METALS AND METALLOIDS
group of moderately dangerous substances to the low IN SOILS
dangerous third group. Let us investigate the distribution of heavy met
On the contrary, the hazard of the other elements in als/metalloids in publications listed in the Poch
the soil appears to exceed the general toxicological vovedenie i agrokhimiya (Soil Science and Agrochem
level. For example, this is true for Sb, which has proved istry) abstract journal in 2010 [30]. Having calculated
to be highly hazardous in soil. The first group of highly the total number of all the records about heavy met
hazardous elements in the soil contains the light metal als/metalloids in the publications listed in the Soil
Be and the heavy metal Tl. The hazard of Ba and V is Contamination section, we came up with the percent
underestimated in soil; they should be referred to the of works devoted to each element. The interest of soil
second group of moderately hazardous elements. scientists in heavy metals appeared to be very uneven:
The comparison of the toxicity sequences of the ele some elements were paid apparently excessive atten
ments arranged according to their mobility in the soil tion, whereas others were paid either low attention or
with that of their toxicity in the soil according to the MPA no attention at all. Let us the rank elements in decreas
values. Practically, the hazard of heavy metals is
assessed in Russia according to the MPCmob criterion
for mobile compounds soluble in an acetate–ammo Table 2. Maximally permissible concentration of mobile
nium buffering solution with pH 4.8. Despite the dif forms of heavy metals/metalloids in soils (MPCmob) ac
ference in the procedures, the values of two criteria cording to the Russian standards (cited after [1]) and the
maximal permissible addition MPA of heavy metals and
(the MPCmob and MPA) turned out to be close for a metalloids by the data of Dutch ecologists [36] in mg/kg
number of metals, i.e., Cr, Ni, Cu, and Zn (Table 2).
In general, both approaches show values of the same Metal/metalloid MPCmob MPA
order. This provides reasons to use the MPA values
found for estimating the soil contamination in Russia Beryllium (Be) – 0.0061
for the elements for which there are no MPCmob stan Selenium (Se) – 0.11
dards, and the content of some elements is not taken Thallium (Tl) – 0.25
into account at all. Despite the difficulty of the deter
Antimony (Sb) – 0.53
mination of these elements (in particular, low clarkes)
in soils, some progress has been achieved lately in this Cadmium (Cd) – 0.76
area thanks to the use of emission spectroscopy with Vanadium (V) – 1.1
inductively coupled plasma and neutron activation Mercury (Hg) – 1.9
[16, 19, 21]. At present, the degree of the soil contam
Nickel (Ni) 4 2.6
ination with the metals for which there is no
MPC/APC is estimated according to the following Copper (Cu) 3 3.5
empiric dependence: MPC = (3–5) × background Chromium (Cr) 6 3.8
[12]. However, this method seems to be too rough. Arsenic (As) – 4.5
In conclusion, let us point out that the set of 18 ele Barium (Ba) – 9.0
ments (with 17 heavy elements among them) is not
Zinc (Zn) 23 16
wide enough taking into account that a total of
57 heavy metals are known. The necessity for a ura Cobalt (Co) 5 24
nium MPC is evident, as the technogenic share of this Tin (Sn) – 34
undoubtedly toxic element rose abruptly after the Sec Lead (Pb) – 55
ond World War. Thus, extremely important studies of
Molybdenum (Mo) – 253
the hazard in soils should proceed for other heavy
metals/metalloids. Note: A dash stands for not determined.

EURASIAN SOIL SCIENCE Vol. 45 No. 3 2012

324 VODYANITSKII
ing order according to their mentioning in publica
tions (%): Cu (13.5), Zn (12.2), Pb (12.2), Ni (8.3),
Cd (7.8), Cr (7.4), As (6.1), Mn (4.4), Co (3.9),
Hg (2.2), Se (2.2), Fe (1.7), Mo (1.7), Ba (1.7),
W (1.3), V (1.3), La (1.3), Ce (1.3), Sb (0.9), Sr (0.9),
Sm (0.9), Th (0.9), U (0.9), Y (0.4), Pr (0.4), Nd (0.4),
Gd (0.4), Lu (0.4), Rb (0.4), Eu (0.4), Hf (0.4), Dy
(0.4), Cs (0.4), Ta (0.4), Tb (0.4), Au (0.4), Ga (0.0),
Ge (0.0), Zr (0.0), Nb (0.0), Ru (0.0), Rh (0.0), Pd
(0.0), Ag (0.0), In (0.0), Sn (0.0), Te (0.0), Re (0.0),
Os (0.0), Ir (0.0), Pt (0.0), Tl (0.0), Bi (0.0), Ho (0.0),
Er (0.0), Tm (0.0), and Yb (0.0). If the 57 heavy metals
were studied evenly, 1.75% of the publications would
have been dedicated to each of them. In fact, with the
elevated interest in the 11 leading elements (Cu, Zn,
Pb, Ni, Cd, Cr, As, Mn, Co, Hg, and Se), the atten
tion to the remainder appears to be low and even zero
for 20 elements including extremely dangerous Tl. As
for the other hazardous elements, low attention is
given to Sb (0.9%) and V (1.3%). Let us discuss in
more detail those elements whose hazard in the soils is
underestimated.
Thallium ranks 58th among the elements in the
earth’s crust with its clarke being 0.7 mg/kg [13]. It is
regarded to be a very dangerous metal [44, 45], more
dangerous than mercury [51]. This is proved by its
lower MPA value—0.25 and 1.9 mg/kg for thallium
and mercury, respectively—although there is no
MPC/APC for Tl in soils.
Thallium inhibits the germination of seeds, chloro
phyll formation, and the operation of many enzymes.
Its ionic radius is close to that of K+; as a result, Tl+
replaces potassium in metabolism processes. Thallium
is very mobile in soils; its availability for plants
depends on its total content in the soil and on the form
of its compounds [44, 45]. The content of Tl in plants
usually reaches (and often even exceeds) half of its total
content in the soil [44, 45]. The coefficient of the bio
logical consumption of Tl reaches 80 in acidic soils with
a low content of organic matter. Thallium is toxic for
organisms in both its oxidation forms (Tl+ and Tl3+),
and its toxicity is comparable to that of Cd and Hg.
Austrian and Chinese soils contain 0.30 and
0.58 mg of Tl/kg, respectively [38]. Vast provinces with
a positive thallium anomaly have been revealed, i.e.,
soils almost everywhere in France are enriched in thal
lium (they contain 1.51 mg of Tl/kg on the average)
[38]. The zonal soils of the Russian Plain contain 0.4–
0.6 mg of Tl/kg [26]. In the south of Western Siberia,
the average content of thallium in the soils is much
higher, namely, 2.8 mg/kg [18]. This territory repre
sents a positive geochemical anomaly.
In the center of the population’s intoxication with
thallium in Western Ukraine, the concentration of this
metal reached 20–130 mg of Tl/kg in the soot of
brickwork chimneys [17]. Tl extracted from the earth’s
bowels by mining and chemical metallurgical enter
prises is emitted to the environment to poison it [13,
37, 41, 49].
Vanadium ranks 19th among the earth’s crust ele
ments with its clarke being equal to 136 mg/kg [13]. It
is referred to the hazardous heavy elements in soils
[17]. Vanadium mainly forms anionic complexes;
however, these complexes are neutral and cationic in
an acidic environment. This difference in charge
results in the widely varying chemical properties of the
metal. In acidic soils, the vanadyl cation VO2+, is more
stable; it is firmly fixed by humus. More vanadium is
fixed in stable humic acids than in fulvic acids. The sit
uation becomes more dangerous in a neutral medium.
The metavanadate anion VO3−, predominates there and
becomes more mobile and toxic for plants and biota
[17]. Let us specify that the vanadium hazard is higher
in the cities, where soils are alkalized. A very notice
ably negative effect of vanadium on human health is
registered in the town of Chusovoi, where the operat
ing metallurgical enterprise emanates vanadium
among other metals [2].
Vanadium is not referred to biophilic elements with its
coefficient of biological consumption being about 0.1.
The accumulation of V decreases the crop yield [17].
The background content of V is thrice exceeded in
Moscow soils [33].
Antimony occupies the 62nd place among the
earth’s crust elements with its clarke being 0.2 mg/kg
[13]. Sb has a low MPA (0.53), which testifies to its
high hazard. Antimony is regarded to be a hazardous
pollutant of soils in the USA and EU [40, 42]. Accord
ing to its toxicity and distribution, it occurs among the
first ten most hazardous pollutants of the biosphere
[3, 50]. Antimony is accumulated in coal and in Sb–
Au ores. In coal ash, the content of Sb varies from
10 to 500 mg/kg [5].
Soils are contaminated with technogenic antimony
in the vicinity of ferrous and nonferrous metallurgical
plants upon cement and brick production and upon
coal combustion [5]. In Great Britain, soils and plants
in the zones of formerly developed mineral deposits
are highly contaminated with antimony. The industrial
contamination may raise the Sb content in the soils up
to extreme values (200–280 mg/kg) [5].
Antimony may exist with four oxidation degrees
(–III, 0, III, and V) with Sb(III) and Sb(V) being the
most widespread forms in the soils. Antimony’s
behavior is for the most part controlled by its oxidation
degree. Under oxidative conditions, Sb(V) forms
–
Sb(ОН ) 6 complexes, which produce unstable Sb2О5
sediments [35]. Antimony (III) forms the stable
hydroxide Sb(ОН)3 only in a highly reductive medium
[39, 40]. Sorption processes almost do not participate in
fixing antimony in the soils. The mobile form of Sb(V)
is stable in a wide range of ЕН [42], which is one of the
reasons for antimony’s hazard to the environment.
Chromium ranks 21st among the earth’s crust ele
ments with its clarke being 122 mg/kg [13]. The chro
mium clarke in the world soils is 70 mg/kg [35].
EURASIAN SOIL SCIENCE Vol. 45 No. 3 2012
 STANDARDS FOR THE CONTENTS OF HEAVY METALS AND METALLOIDS
Contamination with Cr considerably affects the
biological activity of the soil. The catalase activity of
chernozems and the soil’s ability for cellulose decompo
sition decrease. The worsening of the soil’s respiration
inhibits important biochemical processes [14]. Cr exerts
a highly toxic effect on the chernozem’s biota [22].
In a small amount, chromium stimulates the
growth of agricultural crops; an excess of it however
promotes various diseases. A wide distribution of tech
nogenic Cr in the environment is unfavorable for
humans and animals. In the USA, Cr ranks third
among the pollutants by its abundance at waste dis
posal sites, and it ranks second (after Pb) among the
inorganic pollutants [6]. The Cr toxicity depends on
its oxidation status. Cr occurs in two states in soils. The
oxyanion chromate CrO24−, is highly mobile and more
toxic in soils and groundwater. On the contrary, the
reduced ion Cr(III) forms either a weakly soluble
hydroxide or stable complexes with soil minerals [2, 46].
A large amount of Cr is accumulated in urban soils.
The content of Cr reaches 1000–2000 mg/kg in the
urbic horizon of urban soils in the town of Chusovoi
[8]. Industrial waste water flows into rivers and con
taminates alluvial soils in that industrial town. In
Perm, the content of Cr reaches 600–1400 mg/kg in
the alluvial soils of minor river floodplains upon its
background content averaging 80 mg of Cr/kg [7].
Although the soil is contaminated with chromium via
ground water only locally, the contamination degree
may be very high.
Barium. The clarke of this metal in the earth’s crust
is 390 mg/kg [13]. The content of barium varies widely
in the upper soil layer and in the parent rock: from 16
to 2370 mg/kg [20].
In Russia, the Ba hazard in soils is underestimated,
now it should be referred to the group of moderately
dangerous elements. A Ba excess in soil, water, and
food (especially in combination with an Sr excess)
may disturb the calcium metabolism and results in a
serious skeletalsystem disease known as endemic
osteoarthritis [10]. It is not by chance that a strict
MPA for Ba equal to 100 mg/kg is adopted for the
wastewater sediments used as an organic fertilizer in
the USA [17]. At the same time, the maximal level of
Pb and Zn in the wastewater sediments in the USA is
500 and 1500 mg/kg, respectively, whereas the content
of Co is not standardized at all [34]. This difference
points unambiguously to the greater danger of Ba as
compared to Pb, Zn, and Co in organic fertilizers,
which agrees with the low value of the Ba MPA
obtained by Dutch ecologists.
Barium is accumulated in the dust of some indus
tries: it is a byproduct of coke plants, engineering
works (foundries and cast iron processing shops), and
cement production. Hazardous emissions are pro
duced by Baprocessing plants as well as oreprocess
ing enterprises specialized in mining and beneficiation
of barite, strontium, and manganese ores [17].
EURASIAN SOIL SCIENCE Vol. 45 No. 3 2012
325
Soils are contaminated with Ba in many cities. In
Tomsk, the barium content in urban soils 5 times
exceeds the background value [16]. In the town of
Chusovoi contaminated with metallurgical industrial
wastes, the share of technogenic Ba is considerable
(35–74%). The content of Ba in a technozem in the town
of Chusovoi constitutes 270–1000 mg/kg [9]. About
onethird of the Ba is of technogenic nature in the air
contaminated urban soils in the city of Perm [9].
INFLUENCE OF SORPTIONAL
AND BUFFERING SOIL PROPERTIES
ON THE MPA VALUES
The MPA values listed in Table 1 are true for a stan
dard soil containing 25% clay particles (<2 µm) and
10% humus. For a particular contaminated soil, the
MPA value of the metal/metalloid should be adjusted
by a number of parameters. We distinguish two of them.
(1) Updating the MPA for heavy metals/metalloids
depending on the content of clay and humus as the
principal bearing phases in the given soil. First, let us
pass from the content of clay (<2 µm) adopted in the
Western countries to the content of clay (<1 µm) rec
ognized in Russia. To the first approximation, we take
that the clay content (<1 µm) determined by the parti
clesize analysis in Russia is 1.5 times lower than the
clay content (<2 µm) adopted in the Western practice.
Next, for correcting the MPA values, we modified the
relationship equation that the Dutch ecologists used
for updating the values of the background content of
metals/metalloids in a particular soil with account for
the L clay content and the H humus content. In the
new equations, dependences of the MPA on L and H
were obtained with the preserved argument for each
metal/metalloid. The MPA values for Sb, Se, Mo, and
Tl do not depend on the silt and humus content. The
MPA values of the other elements depend either on
the content of clay particles or also on the humus. For
all the elements, the initial correlation dependences
are linear except for Pb, for which we had to simplify
the initially complex relationship to a linear equation.
The correlation dependences between the MPA values
of the heavy metals and the clay (<1 µm) and humus
content are listed in Table 3.
For a soil with a different texture and humus con
tent, the MPA values of the heavy metals may be cal
culated proceeding from the relationship equations
obtained by the Dutch ecologists for nearly all the
studied elements (Table 3). For example, the MPA
decreased approximately by three times though
unevenly for elements in the lighttextured soil with
5% clay and 2% humus as compared to the standard
humus soil. The MPA values manifested a greater
decrease for Cd and V and, lower, for Sb, although, in
general, the lists of hazardous and nonhazardous ele
ments remained the same. This permits using the
MPA values of the elements in the standard soil as a
measure of their hazard.
326 VODYANITSKII

Table 3. Regression equations for the relationship between ments with known MPAs. For urban soils in Tomsk, a
the MPA (mg/kg) of the heavy metals/metalloids and the more than 5times increase of tantalum (Ta), anti
content of clay (<1 µm) L and humus H (%) in the soil, ini mony (Sb), uranium (U), and terbium (Tb) as com
tial data [36] pared to the background was revealed; the content of
Heavy element Relationship equation MPA = rubidium (Rb), hafnium (Hf), ytterbium (Yb), and
lutetium (Lu) was exceeded by 2–3 times and more
V 0.066L [16]. However, these elements are absent in the Dutch
Cr 0.23L list of MPAs, which complicates establishing the per
Co 1.44L
missible concentrations for them.
Ni 0.15L
Cu 0.1(1.5L + H) CONCLUSIONS
Zn 0.27(3L + H) According to the presentday ecotoxicological data
As 0.13(1.5L + H) obtained by Dutch ecologists, heavy metals/metal
Se 0.11
loids form the following succession in soils according
to their hazard degree: Se > Tl > Sb > Cd > V > Hg >
Mo 253 Ni > Cu > Cr > As > Ba. This succession differs con
Cd 0.014(1.5L + 3H) siderably from the succession of heavy metal hazards
Sn 0.9L registered in the general toxicological GOST
Sb 0.53
17.4.1.028, which considers As, Cd, Hg, Se, Pb, and
Zn as highly hazardous elements, whereas Co, Ni,
Ba 0.54L Mo, Cu, Sb, and Cr as moderately hazardous ele
Hg 0.032(3L + H) ments. As compared to the general toxicological
Tl 0.25 approach, the hazard of Pb, Zn, and Co is lower, while
Pb 1.57(1.5L + H)
that of V, Sb, and Ba is higher. The new sequence also
differs from that of the metal hazard in soils according
to the Russian standard for the maximal content of
mobile forms of metals (MPCmob): Cu > Ni > Co > Cr >
(2) Updating the MPC/APC of heavy metals/met Zn. Neither an MPCmob nor an APCmob is adopted in
alloids depending on the content of other important Russia for highly hazardous Tl, Se, and V.
bearing phases in a given soil: iron hydroxides and
manganese oxides. These phases manifest certain The content of heavy metals in contaminated soils
selectivity. Iron hydroxides fix predominantly Co, As, is studied very unevenly: 11 of them are studied best of
V, Cr, Zn, Ni, and Pb. The list of manganophilous all: Cu, Zn, Pb, Ni, Cd, Cr, As, Mn, Co, Hg, and Se.
metals is shorter: Pb, Co, and Ba [4, 43]. Since these The remaining 46 elements are studied much worse,
bearing phases play an important role in fixing heavy although there are hazardous elements among them,
metals, the reagents intended for the selective dissolu i.e., Ba, V, and Tl. In Russia, there is a lack of evidence
tion of iron and manganese (hydr)oxides are applied in about the content of these elements in the soils, and it
different schemes of heavy metal compounds fraction is these elements that soil scientists and ecologists
ating [23]. should focus their attention on.
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