Chemosphere,Vol. 39, No. 2, pp.

343-377, 1999
Pergamon © 1999 Elsevier Science Ltd. All rights reserved
0045-6535/99/$ - see front matter
PII: S0045-6535(99)00115-0
TRACE ELEMENT INPUTS INTO SOILS BY ANTHROPOGENIC ACTIVITIES AND
IMPLICATIONS FOR HUMAN HEALTH

Giorgio S. Senesi 1, G. Baldassarre 2, N. Senesi a' ", and B. Radina z

~Department of Geomineralogy,
2Department of Geology and Geophisics,
3Institute of Agricultural Chemistry, University of Bail, Bari, Italy

ABSTRACT

Trace element definition and functions, and inputs into soils from the most important anthropogenic
sources, related and not related to agricultural practices, of general and local or incidental concern, are
discussed in the first part of this review. Trace element inputs include those from commercial fertilizers,
liming materials and agrochemicals, sewage sludges and other wastes used as soil amendments, irrigation
waters, and atmospheric depositions from urban, industrial, and other sources. In the second part of the
review, the most important ascertained effects of soil trace elements On human health are presented. The
possible relations found between some specific soil trace elements, such as Cd, Se, As and others, and
cancer incidence and mortality, and diffusion of other important human diseases are reviewed. Brief
conclusions and recommendations conclude this review. © 1999 ElsevierScienceLtd. All rightsreserved

1. INTRODUCTION

Widespread interest in trace element research in the agricultural, environmental and life sciences
has emerged especially over the last three decades, also urged by the growing social concern with excess
concentrations of a number of elements in the environment as a consequence of anthropogenic emissions
[1]. Since the middle of this century, the consumption of large quantities of trace elements has resulted
from the ever-expanding technological development (Table 1) [2]. As the mine-produced metals are
ultimately dispersed in the ecosystem, the amount of potentially hazardous metals dispersed is
considerable on a cumulative basis. In pretechnological times, the cycling of each trace element had
basically reached a steady state and a rigorous natural control was maintained on its distribution in the
global ecosystem At the present time, calculations using the data in Table 1 suggest that the
anthropogenic inputs have overwhelmed the natural biogeochemical cycles of trace elements on the earth
[2].
Major developments in trace element research have been made in soil sciences, as soils are
considered the most important environmental compartment functioning as a sink for trace elements

343
344

Table 1. Historical changes in primary production of trace elements (x

1,000 metric tonnes/year) (source: [2], compiled from the
Minerals Yearbooks, Bureau of Mines, US Dept. of the Interior,
US Govern. Printing Office, Washington, DC, U.S.A.).
Element Year
1930 1950 1970 1985
Ag -- 6.2 9.4 13
As -- 47.0 49.6 45.0
Bi -- 1.4 3.7 8.3
Cd 1.3 6.0 17 19
0.73 7.2 24 36
Cr 560 2,270 6,057 9,940
Cu 1,611 2,650 6,026 8,114
Hg 3.8 4.9 9.8 6.8
Mn 3,491 5,800 18,240 --
Mo -- 15 82 98
Ni 22 144 629 778
Pb 1,696 1,670 3,395 3,077
Sn 179 172 232 194
V -- 1.8 18 34
W 17 39 32 47
Zn 1,394 1,970 5,465 6,042
Zr . . . . 399 775

released by human activities. In the industrialized countries trace element contents in agricultural soils
have increased significantly over the past century [3]. Further, during recent decades trace inorganic
pollutants have been distributed so widely that even soils in remote regions show increased levels of
certain trace elements of anthropogenic origin [4]. Thus, the present status of trace elements in soils,
either in natural or in agricultural areas, reflects their sources both from parent material and from
anthropogenic addition. Most studies, however, have been performed in the industrialized world, whereas
the inter-tropical regions have been particularly neglected. Further, attention has mostly focused on
geochemically anomalous or polluted areas and data are scarce for areas considered "clean" and
"normal".
Trace elements can enter the soil by a number of pathways, and their behaviour and fate in soils
differ according to their source and species. The most important anthropogenic sources of trace elements
for soils include: commercial fertilizers, liming materials and agrochemicals, sewage sludges and other
wastes used as soil amendments, irrigation waters, and atmospheric deposition from industrial, urban and
road emissions [5].
Commercial fertilizers, liming materials and various agrochemicals that are widely used in high-
production, intensive agriculture may contain trace amounts of several elements as impurities originating
from the parent rock materials or from the processes and chemicals used in their production. Sewage
sludges and effluents, composted urban refuses and other wastes from agrofood industry, which are
 345

increasingly and beneficially recycled in agriculture as soil amendments, also contain variable amounts of
trace dements of various nature and various anthropogenic origins. Trace elements are introduced into the
soil also tl~rough waters used for irrigation, especially waste waters. Atmospheric deposition from
industrial and urban combustion emissions can be an important point source of trace elements for soils.
Once emitted, trace elements may travel long distances in either gaseous form or in particle phase before
deposition, (:an be dispersed over large areas from the point of release, and are difficult to control and
limit. Roadside soils are contaminated with various trace elements primarily from automobile exhaust
emissions. Depending on the location and traffic intensity, contaminated zones can extend up to several
hundred meters from the road.
Long term changes in soil quality can be induced when trace element inputs are sustained over
long periods and when they exceed the rate of loss from the system. Although some trace elements are
essential plant micronutrients, excessive concentrations of them in agricultural soils are a general matter
of concern to society as they may adversely affect the quality of agricultural products and enter the food
chain, or leach down to groundwater and contaminate drinking water resources, and may cause, in both
cases, hazards to the health of humans and animals.
The greatly increased circulation of hazardous trace elements in soils, water and air implies an
inevitable bt, ild-up of such elements in the human food chain. Minamata (methyl mercury poisoning) and
Itai-Itai (Cd) diseases in Japan awakened the public conscience to focus attention on the hazardous role of
trace dements in human health. In terms of quantities being emitted, trace elements are recognized as
important cofactors or cofounders in the etiology of diseases such as cancer, and there is evidence for a
role of environmental and dietary trace elements in human health. The increased exposure results from
the well-documented elevations in the concentrations of several trace elements in body fluids and organ
tissues of co:atemporary populations [6, 7]. Several trace dements, specifically Pb, Cd, Hg, As and others,
are wdl-known to exert adverse effects in humans and no homeostasis mechanism is known for them.
Therefore, aay long-term exposure may be expected to progressively cause more severe disrumptions in
the normal functioning of the organ systems where the elements are accumulating [2].
The main objectives of this review are to discuss the most important anthropogenic sources of
trace dement inputs into soils and health hazards for humans related to trace elements in soils.

2. DEFINITION AND FUNCTIONS OF TRACE ELEMENTS

The term "trace element" is widely used in the literature and may have differing meanings in
various scie:atific disciplines. Generally, it refers to dements that occurr in minute concentrations in
natural and artificial systems. Often it defines elements that are essential or toxic in small quantities to
microorgani;;ms and plant and animal organisms, including humans. However, it often includes elements
with no known physiological functions. A general consensus exists on considering "trace" an element
which is present in the system, e.g., soil and introduced materials, at levels of less than 0.1%. In
346

biochemical and biomedical areas, an element is considered "trace" when it is commonly present in plant
or animal tissues in a concentration lower than 0.01% of the organism.
In this review, the term "trace elements" is used for elements that naturally occur in the soil and
are applied to it by anthropogenic sources in small amounts and that, when present in sufficient
concentrations, become hazardous for the ecosystem in general. Other terms that are often used as
synonymous for most "trace elements" include: "trace or heavy metals", "microelements", "trace
inorganics", and others.
The most extensively studied trace elements in soils and introduced materials are those generally
considered as essential for the nutrition of higher plants, namely, B, CI, Cu, Fe, Mn, Mo, Ni, and Zn. The
micronutrient needs for plants contrast with those for animals, where 14 elements (Si, V, Cr, Mn, Fe, Co,
Ni, Cu, Zn, As, Se, Mo, I and F) are recognized as essential [8, 9]. Despite the interest in trace elements in
environmental and life sciences, little effort has apparently been devoted to deciding the essentiality or
otherwise of other elements. In Table 2 a summary is provided of trace elements essential, uncertain and
potentially toxic to plants and animals [5].
The availability of new analytical techniques has facilitated the rapid and reliable analysis of trace
elements. Determinations of the total trace element contents of soils and materials added to it are of value
in an absolute sense, but it is well known that only the chemical forms of a trace element have biological
significance. Reliable analytical data on chemical forms, speciation and bioavailability of trace elements
in different areas and a valid estimation of their background levels are absolutely necessary to the
legislators for introducing mandatory or guideline levels which are realistic and appropriate.
Problems of data interpretation are especially pertinent when "contamination" or "pollution" by
trace elements are discussed. A "contaminant" trace element for soil may be defined as an element found
in a given soil at a concentration higher than that of its "natural" level in that soil, and where the source of
the additional concentration of the element appears to be human activity. Essential to such a definition is
the need for reliable values for background or baseline concentrations to be established in soils where
human activity has been minimal. The problem is that human activity tends to generate widespread, low
level contamination, and, therefore, even at locations far from any known anthropogenic sources, the
trace element contents of soils (and plants) are not necessarily "natural".
Another important question in evaluating contamination, or pollution, by trace elements is whether
the observed concentration of the contaminant is harmful, and harmful to which system. A trace element
which is harmful to one organism may not be harmful, and may even be beneficial, to another one at that
concentration.
There is no doubt that trace element content and status of soils may influence plant uptake and
concentration of the element in the tissues of food and fodder crops, thus affecting the quality of food and
potable waters with potential implications to human health. Since the suggestion that human cancer might
be linked to the soil environment, especially through copper [10], several efforts have been made in
comparing disease maps with geochemical maps, and noticeable resemblances have been found [11].
 347

Excess or deficiency o f Pb, Cd, Zn, Ni, Se, A1, Hg, Cu, Cr and other trace elements in soils have been
proposed to have a causative role in some typical regional-diffused diseases.

T a b l e 2. Essentiality and potential toxicity o f trace elements to plants and animals

in the terrestrial environment Ldapted from [5]).
iement Essential or Potentially Comments
beneficial to toxic to
Plants Animals Plants Animals
As No Yes Yes Yes Potential carcinogenic
B Yes No Yes Wide species differences
Ba No Possible Relatively nontoxic
Be No No Yes Yes Carcinogenic
Bi No No Yes Yes Relatively nontoxic
CA No No Yes Yes Enriched in food chain;
careinogenic;Itai-itai
disease
Co Yes Yes Yes Yes Relatively nontoxic;
high enrichment factor;
carcinosenic
Cr No Yes Yes Speciation important;Cr6+
very toxic; carcinoi:enic
Cu Yes Yes Yes Toxic at >20 rng/Kg
F No Yes Yes Accumulative toxicity for
plants and animals:
fluorosis
Fig No No Yes Enriched in food chain:
Minamata disease
Mn Yes Yes Yes (pH<5) Among the least toxic
Mo Yes Yes Yes High enrichment in
plants; toxic for animals
at >20 mg/Kg
Ni No Yes Yes Yes Toxic for plants at
>50mg/k~; carcinogenic
lab No No Yes Yes Cumulative poison
Sb No No Yes Relatively nontoxic
Se Yes Yes Yes Yes Toxic for plants
at >50 mg/Kg
Sn No Yes Yes Relatively nontoxic
Ti No Possible Relatively nontoxic;
possibly carcinogenic
TI No No Yes
V Yes Yes Yes Yes Toxic for plants
at > l0 mg/Kg;
Highly toxic in animals;
high enrichment factor;
carcinosenic
W No No Very rare
Zn Yes Yes Toxic at >200mg/Kg

Figure 1 [1] illustrates the marked rise in trace element publications since 1950, and especially in
the 1970s and 1980s, stimulated by the discoveries of the 1960s Although most o f the questions on the
348

role of trace elements in the environment and life are still far from being answered satisfactorily or yet not
being posed, a decline in publication rates is occurring in recent years. A possible reason for this gradual
loss of interest of researchers on trace elements may be that the officially perceived research priorities
have shifted, e.g., to acid precipitation or the greenhouse effect (gaseous emissions from soils, global
warming), and funding for trace element research has become more difficult to obtain.

BO
Plants

03
~16o
0

~20 ~ Soils

80

I t
iq)
0 0

I ~ --'- I ' I i I I
1940 1950 1960 1970 1980
Date
I Figure 1. Trace metal publications (Source: [1]).

3. TRACE ELEMENT INPUTS INTO SOILS BY HUMAN ACTIVITIES

3.1. Application of fertilizers and agrochemicals

Application to soil of commercial fertilizers frequently involves the addition of small quantities of
trace elements contained in them as impurities originating from the parent rock, the corrosion of
equipment, catalysts and reagents used in their manufacture, and materials added to commercial
preparation as coatings, fillers, and conditioners, e.g., gypsum, kaolin, limestone, etc.. Although such
contributions may result in beneficial inputs to soils deficient in trace elements essential for plant
nutrition, contamination problems may arise when their concentrations exceed the toxicity limits and
when trace elements that are potentially harmful for agriculture are added.
 349

Comprehensive information on the contents of several trace elements in commercial fertilizers has
been published [5, 12, 13]. In a series of studies, the contents of several trace elements, including As, B,
Ba, Be, Bi, Cd, Co, Cr, Cs, Cu, Hg, Li, Mn, Mo, Ni, Pb, Rb, Sb, Sc, Se, Sn, Sr, Ti, Ti, V, W, Zn and Zr,
in a number of mineral and synthetic commercial fertilizers of different nature and origin collected from
different manufacturers and distributors in Italy have been measured [14-22]. Data obtained are shown in
Tables 3 and 4, in comparison to the average trace element contents of soil [3, 23-26].
The most abundant trace elements determined in all examined fertilizers are Be, Rb, Sr, Ti, V, As,
Zn, Cr, Co, Mn, Mo, Ni, Pb and Sn, whereas Bi, Sc and Hg are present in the smallest amounts. The
elements Se, Sc and Ba are present only in some samples, and Sb and TI are never detected. As shown in
Figure 2, contents ofNi, Hg, Mo, Co and Pb vary in a relatively limited range of concentration, whereas
Sn, Cu, As,. Cr, Zn, Cd and Bi show wider variations among examined samples.

,i,

11000.

322

~oo l 190 235 4]~ ~

~s
10 11.3
C;e MI
t (Z2,) (21.)

Hf
.l.lO c1,0 .1-0 (13,)
0,51

li
(,,.)

0.01
0,00

Figure 2. Range of contents (mg/Kg) of a number of trace elements in fertilizers. The

~_ variation range for each element is shown between parentheses (Source: [16]).
350

Fertilizers originating from rock phosphates generally contain the highest quantities of trace
elements, followed by those involving carbonate rock materials in their processing. Synthetic nitrogen
fertilizers and potassium sulfate contain the lowest amounts or no detectable presence of several trace
elements, although some important exceptions are apparent.
Data presented in Tables 3 and 4 correspond also to the quantities in grams of trace elements
supplied by 1 metric ton of fertilizer applied to arable soils. Comparing these data with the average trace
element content of soil, also shown in Tables 3 and 4, it appears that As, Cd, Hg, Sn, W and Mo supplied
by almost all examined fertilizers may affect significantly the soil composition after a few applications,
especially to soils that are naturally deficient in these elements. Thus, they may be considered to generally
represent a potential source of soil contamination. The risk of contamination by Co, Cr, Cu, Ni, Pb, Zn,
Li, B, Sc, Ti, Be, Cs, V, Ba, Rb and Sr appears to be limited to elevated additions of fertilizers containing
phosphates or originated from carbonate rock. In no case are Mn, Zr and Bi contributions by fertilizers
expected to appreciably affect the usual soil contents. However, it should be noted that, even if the
addition of some trace elements by fertilizers results in relatively low additions to the total contents in the
soil, it may on occasion affect the soluble and plant available fraction, thus representing a potential source
of contamination and toxicity.
Limestone, which is a mixture of calcite and dolomite, is the liming material most widely used to
correct soil acidity. The trace elements commonly contained in limestones originate from the rock from
which the product is derived. Based on the average contents of trace elements in agricultural limestones
(Table 5), application to soil of an average rate of 4,5 metric tonnes/ha of lime would add an average of
1,480g/ha of Mn, 140g/ha of Zn, and 12g/ha of Cu [5].
Agrochemicals, especially pesticides, including herbicides, fungicides, insecticides, etc., are
widely used in intensive agriculture for the control of weeds, insects and diseases in various crops. The
amount of trace elements introduced into the soil vary according to the type of pesticide used. Some of
them, especially inorganic salts and organo-metallic compounds, contain very high amounts of elements
such as As, Pb, Cu, Zn, Mn, Hg and Sn (Table 5), and can contribute a total of several kg of these
elements to the soil, especially in fruit orchards and vegetable fields. Of the total anthropogenic releases,
the use of arsenicals in agriculture represents about 8% [5]. For example, a single application of lead
arsenate can supply up to 2.3 kg/ha of Pb and 0.5 kg/ha of As [28]. Arsenic levels in orchard soils in
Canada have been measured to be about ten times the level in nontreated soils [28]. Copper sprays used
for disease control on some vegetable crops can enrich Cu in the soil by as much as 11.2 to 16.8 kg/ha per
year [5]. The use of mercurial seed dressings and mercurial fungicides also resulted in some persistent
local contamination of agricultural soils [12].
 351

"Fable 3. Range (first line, minimum or unique value; second line, maximum value)
of trace element contents (mg/Kg) of investigated fertilizers [14, 15, 18,
19] and usual ranges found in soil [3, 23-26]. Data shown also represent
the quantities (in g) of trace elements supplied by an application of 1
metric ton of fertilizer to soil.
Principa
1 As B Bi Cd Co Cr
element
Ammonium 4 N 4.2 0 0.00 0.08 7.7 1.0
sulphate 29.0 0.13 4.80 12.0 4,4
Ammonium 3 N 2.7 <1 0.00 0.08 5.4 <1.0
nitrate 119.7 8.50 l l .5 4.2
Calcium 2 N 2.2 <1 0.07 0.05 8.6 15.4
nitrate 10.1 0.13 2.80 12.8 19.2
Urea 2 N 5.6 0 0.00 0.22 1.0 8.0
33.4 0.11 3.20 1.4 1.6
Calcium 1 N 2.2 <1 0.00 0.03 22.0 23.0
cyanamide
Superphosphate 4 P 2.4 140 0.00 0.10 8.8 39.6
28.5 185 0.09 2.20 21.0 134.0
Triple 1 P 321.5 172 0.51 3.25 16.7 190.0
superphosphate
Potassium 3 K 2.4 20 0.00 0.06 5.8 2.0
sulphate 8.0 30 3.80 7.0 2.8
NP compounds 3 N, P 3.3 25 0.00 0.06 10.0 31.8
126.9 115 0.09 9.30 17.0 110.6
NPK compounds 9 N, P, K 3.0 25 0.00 0.04 10.5 27.0
282.4 185 0.24 7.80 15.7 178
Soil, usual 1.0 2.0 3.0 0.01 1.0 5
range 50.0 100 13.0 0.70 40.0 1,000.0
Soil, extreme <0.1 <0.2 -- 0.01 <0.1 <0.1
range 1,000.0 1,000.0 7.00 1,000.0 35,800

Table 3 continued

Cu Hg Li Mn Mo Ni Pb Se Sn Zn
-~1 0.30 0.3 3 1- 25.0 2.4 0.00 1.8 1
1 0.75 3.2 4 4 32.0 13.6 7.2 6
3 0.75 0.3 3 4 7.0 1.9 0.00 1.4 3
2.88 2.5 65 7 34.2 27.8 10.00 16.2 7
5 0.75 0.4 25 5 26.0 2.4 0.00 1.4 2
15 1.60 3.9 30 7 27.5 8.0 10.8 42
~1 0.72 3.5 2 2 7.2 5.5 0.00 1.8 <1
1 0.75 4.6 8 10.2 48.7 21.6 1
14 0.40 1.7 14 9 48.8 5.9 0.00 0.4 4

20 0.40 1.0 10 8 19.2 3.1 0.00 2.2 55

35 1.20 2.7 119 15 38.2 17.4 19.1 235
38 3.20 3.3 197 21 44.2 13.9 13.25 7.2 138

l 0.00 O. l 4 4 11.0 1.4 0.00 1.8 2

2 0.40 2.0 5 9 16.0 17.4 2.2 6
I1 0.30 0.6 67 10 27.0 0.0 0.00 2.5 16
!2 0.72 5.3 248 21 36.2 9.9 30.6 122
4 0.24 0.5 35 6 9.7 0.0 0.00 1.4 19
:!3 2.70 4.4 141 15 43.5 24.4 19.1 78
2.0 0.01 <1 200 0.2 5.0 2.0 0.10 0.1 10
00.0 0.03 <110.0 3,000 5.0 500,0 200.0 2.00 5.0 300
:10 0.01 <1 1 0.1 0.5 0.1 0.01 <0.1 6
4,000 1.14 5,000.0 70,200 224.0 6,200.0 10,000 225.00 300.0 30,000
 t_o

T a b l e 4. R a n g e (first line, m i n i m u m or u n i q u e value; s e c o n d line, m a x i m u m v a l u e ) o f trace e l e m e n t c o n t e n t s ( m g / K g ) o f

investigated fertilizers [20-22] a n d u s u a l r a n g e s f o u n d in soil [3, 23-26]. D a t a s h o w n also represent t h e quantities
(in g) o f trace e l e m e n t s supplied by an application o f 1 metric t o n o f fertilizer to soil.
Number of Principal
Fertilizers samples element Ba Be Cs Rb Sc Sr Ti V Zr W
~omum 2 N 0.0- 174 <2 3.8 0.00 0.0 0.0 <2 0.00 0.00
sulphate 201 0.03
Ammom~ 2 N 0.0 115 3 5.4 0.00 22.4 0.5 9.8 0.32 0.00
nilra~ 230 5 6.4 34.0 0.6 10.8 1.04 0.20
Calcium 1 N 0.0 I50 9 6.4 0.00 40.0 0.9 7.4 0.00 0.23
ni~
Urea 4 N 0.0 27 <2 3.8 0.00 0.0 0.0 <2 0.00 0.00
69 4.2 0.2 0.33 0.11
Calcium 2 N 100.0 1,934 24 8.8 0.09 44.0 93.8 43.8 3.38 0.00
c~j.a~mde 167.0 2,900 26 10.2 0.12 64.0 146.8 59.0 5.40
SuI~rpho~te 5 P 113.0 2,080 <2 5.6 0.14 31.2 18.0 6.2 0.38 1.47
500.0 4,260 10.2 0.68 62.0 150.0 8.0 6.96 7.04
Triple 2 P 66.7 7,380 <2 9.4 0.50 16.4 61.5 3.4 1.77 1.59
superphosphate 107.0 7,600 12.6 0.72 22.0 110.3 3.6 3.53 4.99
Potassium 5 K 10.6- 2,180- 60- 76.8- 0.00- 22.0- 0.4- 54.2 0.00 0.00
sulphate 19.5 4r360 92 122.0 0.01 78.0 1.5 128.6 0.12 0.75
NP compounds 7 N, P 0.0 2,000 <2 6.4 0.12 <0.1 16.4 45.2 2.59 0.00
338.0 7r500 15.8 0.65 18.0 197.0 374.0 8.24 3.99
NPK compounds 18 N, P, K 0.0 540 17 20.6 0.03 0.0 2.7 34.2 0.00 0.02
47.0 5r640 64 62.0 0.54 55.2 96.6 111.0 6.60 2.03
Soil usual 100.0 0.3 4 20.0 0.50 50.0 80.0 50.0 30.00 0.68
range 3~000.0 10.0 500.0 45.00 lr000.0 24,000 100.0 2,000.0 2.70
Soil extreme 8.0 1 -- 0.2 -- 0.1 -- 20 . . . .
range 33,700 :40 2,000.0 15,000.0 1,000.0
 353

Table 5. Range of contents of major trace elements in

agricultural limestones and pesticides [25, 27, 28].
Trace Limestones Pesticides
element (mgjKS) (%)
As 0.1-24.0 0.8-60
B <1-21 --
Ba 120-250 --
Be 1 --

Cd 0.04-0.1 --
Co 0.4-6.0 --
Cr 10-15 --
Cu <0.3-125 4-56
F <10-1,410 18.45
Fe 100-31,100
Hg 0.05 0.6.42
Mn 20-3,000 1-17
Mo <0.1-92 --
Ni 10-20 --
Pb 20-1,250 11-60
Sc 1 --

Se 0.08-0.1 --

Sn 0.5-4.0 --
Sr 610 --
V 20 45
Zn <1-450 1-30
Zr 20 --

w <1-106 --

3.2. Application of sewages sludges and effluents, municipal refuses, animal and agro-food wastes
Application of pre-treated municipal sludges and urban refuses as soil amendment has become in
the recent years more and more attractive and popular for several reasons. These include: the huge and
always increasing amounts of wastes produced by urban activities, the necessity to get rid of them, the
high cost of incineration and other treatment alternatives, the increasing public concern to protect the
most delicate environments and prevent pollution of the atmosphere and water bodies, and the potential
soil fertilizing capacity of these materials.
Adequate treatment processes, such as digestion of domestic sewage sludges and composting of
urban refuses, have shown high potential for recycling these materials as soil amendments in croplands
This practice is expected to reduce the needs of commercial fertilizers, to produce beneficial effects on
soil fertility in general, and to limit hazards for the ecosystem as a whole.
Besides organic matter and beneficial plant macro- and micronutrients, sewage sludges and
composted urban refuses, contain, however, a wide and variable range of potentially harmful trace
elements. Actually, recommendations and limits for soil application rates of these materials are based on
the fertilizer value (content and quality of organic matter, nitrogen, phosphorus and other macronutrients),
354

and on the type and concentration of trace elements contained. The nature and content of trace elements
in sewage sludges and urban wastes are highly variable and largely dependent on the types and amounts
of urban discharges [29, 30].
The ranges o f concentrations o f several trace elements determined worldwide in sewage sludges
are referred in Table 6 [3, 5, 25, 29, 31-37].

Table 6. Typical ranges o f concentration of trace elements in sewage sludges from various
European countries and North America [3, 5, 25, 29, 31-37], concentrations acceptable
in sewage sludges applied to agricultural land in various European countries and
European Union (EU) [31, 38, 39], and maximum allowable concentrations (ceiling
limits) for sludge application to cropland in U S A [40].
Concentrations Concentrations acceptable*
Element Determined* Various countriesT EU limit values~ Ceiling limits in USA~
As 1-1,800 10 03, N)-75 (Can) 75
B 0.2-1,000
Ba 9-9,000
Be 1-30
Bi <1-100
Cd <1-3,410 8 (DK)-30 (F, Sz) 20-40 85
Co 0.6-1,565 20 03, N)-150 (Can)
Cr 8-99,000 200 (N)-I,200 (G) 1,000-1,750 3,000
Cs 0.45-2.9
Cu 16-23,700 500 03)-3,000 (S) 1,000-1,750 4,300
F 2 -740
Hg <0.1-10,600 5 (Can)-25 (F, G) 16-25 57
Li 1.4-22
Mn 18-7,100 500 03, N')-3,000 (F)
Mo 1-1,000 20 (Can) 75
Ni <1-14,000 30 (DK)-500 (F, S) 300-400 420
Pb 10-26,000 300 03, N)-l,200 if,G) 750-1,200 840
Rb 4-95
Sb 2-44
Se 1-20 14 (Can)-100 (Fr) 100
Sn 40-700
Sr 40-360
Ti <1,000-4,700
V 15-400
W 1-100
Zn 58-50,000 1,000 (Sz)-10,000 (S) 2,500-4,000 7,500
Zr 5-319

*Expressedin mg/Kgdry weight

TCountry abbreviations:(B) Belgium, (Can) Canada, (DK) Denmark, (F) Finland, (Fr) France, (G) Germany, (N) Norway, (S)
Sweden,(Sz) Switzerland.
EC documentcode 86/278/EEC.
USEPAPart 503 sewage sludgeregulations.
 355

Data in Table 6 show that the levels of trace dements found in the majority of sludges are so
variable that it is not possible to generalize about the suitability of sludges as fertilizers, since the trace-
element composition and content may vary widely even for sludges from a single disposal plant. In
general, the concentration and variability of most trace elements increase with progress in urbanization
and industrialization.
Tabile 6 also refers the ranges of permissible trace element concentrations for sludges applied to
agricultural land in various countries [31, 38-40]. The widely differing values are an indication of the
different concern existing in various countries for the soil pollution hazard from trace element applied
with sludges.
Data in Table 7 clearly indicate that, on a global scale, sewage sludges are not a major contributor
of trace elements in soils relative to all other sources. However, on a local scale, sludges may represent
the main source of trace elements in soils [41]. Heavily sludged soils may easily become contaminated by
potentially harmful trace elements that will cause toxic effects to crop plants, possibly decrease their
yield, and degrade the quality of food produced. These effects will, in turn, increase the dietary exposure
of animals ,and humans, and possibly render the soil unsuitable for food crop production.

Table 7. Estimated global inputs of trace elements to soils from

sewage sludges [31, 41].
Invut (106KfJvear) Percentage
Element Sewagesludge Total of total (%)
As 0.01-0.24 52-112 0.02-0.21
Cd 0.02-0.34 5.6-38 0.36-0.89
Cr 1.4-11 483-1,309 0.03-0.84
Cu 4.9-21 541-1,367 0.09-1.54
Hg 0.01-0.8 1.6-15 0.63-5.33
Mn 4.4-11 702-2,633 0.42-0.63
Ni 5-22 106-544 4.04-4.72
Pb 2.8-9.7 479-1,113 0.58-0.87
Sb 0.04-0.2 4.7-47 0.43-0.85
Se 0.01-0.14 6-76 0.17-0.18
V 0.22-1.5 43-222 0.51-0.68
Zn 18-57 689-2,054 2.61-2.78

Data in Table 8 show an example of accumulation of trace elements in the surface 20 cm of soils
which had received prolonged application of sewage sludge [42], in comparison with recommended and
mandatory limit values established by the European Union (EU) for some trace elements in sludged
agricultural soils. The results referred in the first two columns of Table 8 show that the concentrations of
B, Cd, Cr, Mo, Ni, Pb and Se are increased by factors of 1.3-2.4 in the sludge-amended soils, Cu and Zn
are increasd by 3.6 times, and Hg by 38 times. Although rather large increases in most trace element
concentrations are observed in the sludge-amended soils, the concentrations of the treated soils are still
356

within the range considered normal for soils (Tables 3 and 4), and mostly within the recommended or
mandatory limit values established by the EU.

Table 8. Changes in the concentrations of trace elements in the surface 20 cm

of soil following application of 84 metric tonnes of sewage sludge
over a period of 12 years [42], and limits for trace element
concentrations" for sludged soils in the European Union (EU) [38].
Control Treated
Element soil soil recommended mandatory
As 12.3 12.5
B 0.59 0.76
Cd 1.2 1.7 1 3
Co 14.2 14.6
Cr 36.1 61.0 100 200
Cu 25.5 90.5 50 140
Hg 0.018 0.675 1 1.5
Mn 476 480
Mo 0.53 0.68
Ni 28.2 43.3 30 75
Pb 25.7 43.9 50 300
Se 0.238 0.569
Zn 97.9 368.8 150 300
*Expressedin mg/Kgdry weight
Higher concentrationsare permittedon sludgedland where commercialcrops ~e grownexclusivelyfor
animalconsumption.
These limitsmay be exceededto a maximumof 50% in soilsconsistentlyabove pH 7, providedthat no
hazardsto healthor the environment,e.g.,groondwaters,are expected.

A review has been recently published [43] on the effects of long-term (at least 10 year) application
of sewage sludge on the bioavailability and response of crop yields to trace elements using results from
field trials mostly located in the EU and USA. The sludge-borne trace elements appear not to cause
serious toxicity to the majority of crops, even if large amounts of them are added to soil. Phytotoxicity
due to sludge-borne elements is rarely observed in grain crops, whereas harmful effects occur in some
leguminous crops. Cadmium, Ni and Zn are the most bioavallable, whereas plant uptake of Cr and Pb is
insignificant. The concentration of a trace element in plants grown on sludge-treated soils is related to the
sludge application rate, the cumulative application of sludge, and to the time elapsed from cessation of
sludge application. Although contrasting results are obtained due to a variety of factors, which include the
composition of the sludges used, soil type, climatic conditions and cultural practices in the field trials, the
total element input to the soil appears to be the major factor influencing the element concentration in plant
tissues. A trend of a progressive decrease in element uptake is observed with time following sludge
application. The authors [43] conclude that further information is needed to evaluate long-term changes in
factors controlling the sludge-borne trace element bioavailability of soils.
The ranges of trace-element concentrations in municipal solid refuses c~tt~pmtVd by various
methods in different countries are shown in Table 9 [12, 37, 44-49]. Results indicate that these ii~terials
 357

have a highly variable composition and can contain high amounts ofZn, Pb, Cu, Mn and Cr, followed by
lower concentrations ofNi, B and Mo. Arsenic, Co, Cd and Hg show the lowest concentrations. The trend
of importance of trace element contents in composted municipal refuses resembles that of sewage
sludges, although much higher range variability and higher maximum levels are encountered in sewage
sludges (Table 6).

Table 9. Ranges of trace-dement concentrations in variously composted

municipal refuses from various countries [12, 37, 44-49], and
concentrations of trace dements in a municipal compost and in treated
and untreated soils from a field experiment [12].
Concentration" Concentrations" in one field Experiment
Element ranges Municipal Untreated Treated Treated
compost soil soilt soil~
As 1.8-33
B 3.8-245 49 0.83 2.58 1.00
Cd 0.7-11.1 3.1 0.13 0.27 0.22
Co 12-15 . . . . . . . .
Cr 14-444 . . . . . . . .
Cu 44-1,200 64 3.1 7.2 7.2
Fig <0.1-5.0 2.6 0.15 0.16 0.16
Mn 125-600 . . . . . . . .
Mo 40-85 . . . . . . .
Ni 7.1-280 6.8 0.9 1.2 1.1
lab 25-1,800 96 0.8 2.1 2.5
Zn 134-2,200 530 3.4 14 6.8

Expressedin mg/Kg.
r Soonatter the additionof 150metrictonnes/haof the municipalcompost.
t Twoandhalfyearsafterthe addition.

The addition of elevated dressings of municipal compost to rural soils for a prolonged time can
have a pronounced effect on their trace-dement content and potential contamination. The short- and long-
term effects of the addition of 150 metric tonnes/ha of municipal compost to soils of a rural area
considered uncontaminated is illustrated in Table 9 [12]. Results show a significant contamination of the
soil for every element considered, with the exception of a very small effect with Ni and Hg.

3.3. Application of manures and other animal wastes

Farmyard, cattle and cow manures have been traditionally used on croplands for their fertilizer
value due lo their high contents of organic matter and N, P, K plant macronutrients. Land disposal
problems are associated with abundant animal wastes, such as poultry and swine wastes produced locally.
These wastes also have a high potential for fertilizer use on agricultural soils.
Trace elements in animal manures and wastes mostly originate from the rations and dietary
supplements added. Table 10 refers the ranges of concentrations of trace elements commonly found in
various types of manures and animal wastes [5, 25, 35, 50, 51]. Data show that the concentrations of
358

potentially harmful trace elements in these materials are rarely high, and generally lower and less variable
than those found in sewage sludges and municipal refuse composts.

T a b l e 10. Ranges of concentrations (mg/Kgdry weight)

o f trace elements in various manures (cattle, cow,
farmyard manures), poultry wastes and swine
waste [5, 25, 35, 50, 51].
Element Manures Poultry wastes Swine waste
As 0.6-25 0.57-0.66 --
B 0.3-24 . . . .
Ba 70-270 54-57 --
Be <0.03 <0.03 --
Cd 0.14-0.8 0.42-0,58 --
Co 0.3-24 1.2-5.0 11
Cr 5-56 5-10 14
Cu 2-62 4.4-31 13
F 7 . . . .

lag <0.03-0.2 <0.04-0.06 --

Ivln 30-550 166-242 168
Mo 0.05-49 5-42 34
Ni 7.8-30 . . . .
Pb 2.1-16 2.1-3.4 --
Rb 0.06 . . . .
Sb <0.08-0.5 <0.08-0.10 --
Sc 5 . . . .

Se 0.32-2.4 0.38-0.66 --
Sn 3.7-7.4 2.0-4.1 --
Sr 80 . . . .
Ti 50-129 12-27 --
V 3.0-8.0 3.9-4.3 --
Zn 15-250 36-158 198

Despite the generally low concentration o f trace elements, problems o f soil contamination can
arise, for example, with application o f wastes from swine and poultry fed with diets rich in Cu and Zn.
The manure of these animals may then contain Cu and Zn in concentrations, respectively, 10 to 40 times
and 4 to 10 times higher than normal concentrations measured in these wastes. Application o f these
manures at common rates based on their N content, would add to soil 3 to 6 kg Cu/ha/year. Elevated
application rates of slurries produced by pigs on high-copper and -zinc diets would double the total Cu
content of a soil o f average Cu status in a single year, whereas it would take ten years to double the total
level of Z n in soil o f average Z n content [44].

3.4. Inputs by natural freshwaters and wastewaters used for soil irrigation
Surface and ground waters used for irrigation o f croplands contain generally small and variable
concentrations o f several trace elements (Table ! 1) [3, 52-54]. The highest frequency o f detection,
 359

especially in surface waters in U.S.A., are shown by B, Ba, Cu, Zn, Hg and Ag, whereas the other t ra c e
elements are present only in less or much less than 50% o f the examined water samples.
Maximum concentrations found for Ag, Cd and M o in groundwaters are generally lower, and for
Cr, M n and Zn are often higher, than those measured in surface waters, whereas the ranges of
concentrations of B, Co, Cu, Hg and Li are generally similar. Very high concentrations o f Li, followed by
Pb, and sometimes for B are found in stream and ground waters used for soil irrigation in South East Italy
[53, 54]. Several surface waters in the U.S.A. are very rich in B, M n and M o [52].

Table 11. Ranges o f concentrations (mg/L) and frequency o f detection (%, between parentheses) o f trace
elements in surface and ground waters used for irrigation o f croplands [3, 52-54].
Element Stream waters* GroundwatersT Surface waters* Freshwaters~
Ag 0.3-1.0 (58.3) 0.1-11.1 (34.2) 0.001-0.038 (6.6) 0.3
As . . . . 0.005-0.336 (5.5) --
B 0.01-5.40 (83.3) <0.01-2.30 (69.7) <0.001-5.0 (98) --
Ba 0 0 0.002-0.340 (99.4) --
Be . . . . . . 0.3
Cd 0 0.2-1.7 (33.5) <0.001-0.120 (2.5) 0.1
Co <0.007-0.050 (37.5) <0.004-0.050 (25.7) 0.001-0.048 (2.8) 0.2
Cr 0.002-0.225 (50.0) <0.002-0.054 (37.5) <0.001-0.112(24.5) 1
Cs . . . . . 0.02
Cu 0.0003-0.0063 (50.0) <0.0003-0.0105(30.9) <0.001-0,280 (74.4) 3
Hg 0.4-0.8 (62.5) 0.2-0.8 (36.2) -- 0.1
Li 20-240 (5.3) 20-270 (52.6) -- 2
Mn 0.0032-0.0076 (45.8) <0.0026-0.0124(16.5) <0.0003-3.23(51.4) 8
Mo 0 15-1,491 (12.2) <0.002-1.5 (32.7) 0.5
Ni 0 0 <0.001-0.13 (16.2) 0.5
Pb 1.7-25.6 (54.2) -- 0.002-0.140 (19.3) 3
Sb . . . . . 0.2
Sn 0 0 -- 0.009
Sr . . . . . . 70
V . . . . 0.002-0.300 (3.4) 0.5
Zn 0.0017-0.0062 (62.5) <0.0015-0.0110 (59.2) <0.002-0.183 (76.5) 15

Fromn° 24 streamwatersamplesfrom South-EastItaly.

From n* 152 groundwatersamplesfrom South-EastItaly.
Fromn° 1,577surfacewatersin the USA.
Dataabstractedfromthe compilationin [3].

Typical concentration ranges for trace elements in wastewater effluents are summarized in Table
12 [55-61].
Trace elements are minor constituents in municipal wastewater, and their contents are almost
always higher than those in its source water (e.g., compare data in the first column o f Table 12 with those
in Table 11, lhird column).
The occurrence o f trace elements in wastewater is related to the nature and composition o f both
the source water and activities in the urban site where they are produced. Substantial contributions of
360

trace elements may be provided from industrial processing and manufacturing of consumer goods,
deterioration and corrosion of the storage and conveyance facilities in the community and household
water supply systems, and input from domestic sources such as human wastes and consumer goods and
foods used daily. Industrial wastes are also often discharged in many treatment plants of municipal
wastewaters, and a consistently high concentration of trace elements usually is an indication of industrial
waste inputs.
The actual concentration of trace elements in wastewaters may vary considerably among treatment
plants in various communities and, with time, even within a particular treatment plant [60, 62]. Although
conventional wastewater treatment systems are not designed and operated to optimize the removal of
trace elements, they are effectively removed (except for boron) from the wastewater in the form of
suspended solids or as adsorbed forms onto the organic and inorganic solids. Thus, most trace elements
separated during the wastewater treatment are found in sludges originated from them.

Table 12. Ranges of concentrations (mg/L) of trace elements in

wastewaters from municipal treatment plants and their
treated effluents [5 5-61 ].
Element Raw wastewater PrimaryEffluent Secondaryeffluent
As <0.0003-1.9 <0.005-0.03 <0.005-0.023
B <0.123-20.0 <0.001-2.5 <0.1-2.5
Cd <0.0012-2.14 <0.02-6.4 <0.005-0.15
Co . . . . <0.05
Cr <0.0008-83.3 <0.05-6.8 <0.005-2.5
Cu <0.0001-36.5 <0.02-5.9 <0.006-1.4
Hg <0.0001-3.00 <0.0001-0.125 <0.0002-0.01
Mo <0.011-0.874 <0.001-0.02 0.001-0.018
Ni 0.002-111.4 <0.1-1.5 0.003-2.0
Pb 0.001-11.6 <0.2-6.0 0.003-1.0
Se <0.002-10.0 <0.005-0.02 <0.005-0.02
Zn <0.0001-28.7 <0.02-2.0 0.004-1.2

Although consistent removal of several trace elements is not always achieved, and even after
secondary treatment significant amounts may still be present in the effluent, trace element concentrations
of primary effluents are reduced by 70% to 90% through secondary treatment, under the normal operating
conditions (Table 12). A comparison of the experimental data in Tables 11 and 12 with the recommended
maximum concentrations for trace elements in surface and irrigation waters established by governmental
Agencies in U.S.A. (Table 13) [63-65], shows that the trace element concentration in most cases (except
boron) will meet the requirements of irrigation water.
The potential hazard associated with inputs of Cr, As, Se, Hg and Pb through application of
treated wastewater to land may be excluded on the basis of their infrequent occurrence and exceptionally
low concentration in the wastewater, and their attenuated chemical activity in the soil. The application of
these elements through treated effluents is thus not expected to cause any serious concern and not to result
 361

in phytotoxicity, or to expose consumers to potentially hazardous levels. In contrast, B, Cd, Cu, Mo, Ni
and Zn concentrations in wastewaters are considered to present a potentially serious hazard for soil and
potential phytotoxic effects, if they are introduced into the cropland soils in an uncontrolled manner [66].
Thus, the lalCterelements may limit the use of wastewater for irrigation and alert planners to be aware that
concentrations of some trace elements, e.g., B and Cd, may exceed markedly the recommended limits,
thus representing a serious hazard for soil, and may cause serious injury to crops irrigated with these
waters.

Table 13. Surface and irrigation water quality criteria (recommended

maximum concentrations, in mg/L) for trace elements [63-65].
Element Surface Water Irrigation water
FWCPA Continuous use Short-term use
FWCPA* NAS-NAE~and FWCPA!"and
USEPA USEPA
Ag 0.05 . . . . . .
As 0.05 1.0 0.1 10.0
B 1.0 0.75 0.75 2.0
Ba 1.0 . . . . . .
Cd 0.01 0.005 0.01 0.05
Co -- 0.2 0.05 10.0
Cr 0.05 5.0 0.1 20.0
Cn 1.0 0.2 0.2 5.0
Mn 0.05 2.0 0.2 20.0
Mo -- 0.005 0.01 0.05
Ni -- 0.5 0.2 2.0
Pb 0.05 5.0 5.0 20.0
Se 0.01 0.05 0.02 0.05
V -- 10.0 0.1 10.0
Zn 5.0 5.0 2.0 10.0
* Any use.
t For sensitivecropson coarsetexturedsoils.
t Onlyon fine-texturessofts.

Sholl-term use of treated wastewater for crop irrigation is generally considered unlikely to result
in crop injuries due to Cu, Ni, or Zn. However, since these elements may accumulate in the soil, the long-
term toxic effects require further examination [61]. Local hazards may arise even in the short-term with
the use of surface and ground waters particularly rich in Mo, Mn and/or Pb, and wastewater effluents rich
in Cr, Cu and/or Ni. The use of harmful waters for irrigation should thus be carefully planned and
managed, aliso considering the cumulative total loading and specific plant sensitivity.
The annual inputs of Cd, Cu, Ni, Zn and Pb to soil and the time required for a soil to reach the
loading limits of these metals in the wastewater have been calculated on the basis of: (i) the typical trace
element concentrations in wastewater; (ii) the annual water application rate (1.2 m/year); and (iii) the
cumulative total loading limits established by the US-EPA [67, 68] for these metals according to the
cation exchange capacity (CEC) of the receiving soil (Table 14) [61]. Data in Table 14 show that, when a
362

wastewater with typical trace-element concentrations is applied at 1.2 m/year, the time required for a trace
element to reach its limit in the soil varies from a minimum of 83 years (for Cd on soil with CEC less
than 5meq/100g) to more than 3,000 years (for Pb on soil with CEC greater than 15meq/100g). The pH of
the soil to which the metals are applied is assumed to be above 6.5.
Verification of calculations presented in Table 14, however, requires data from long-term field
experiments, which are, unfortunately, rather limited. Most available data for trace-element accumulation
in soil from repeated annual applications of wastewater confirm an either slight or no accumulation [69-
71]. However, accumulations ofZn, Cu, Ni and Cd in surface soil are observed in a long-term experiment
(70 years) where a primary effluent from a wastewater treatment plant is used to irrigate forage [55].
Available information appear, therefore, to confirm that treated wastewaters can be used as irrigation
waters for at least a number of decades before trace elements will accumulate in soil to levels considered
to be potentially hazardous [72].
The amounts of trace elements removed by crops grown on soils irrigated with wastewaters have
been shown to be negligible [61]. The few experimental data available show that no more than 10% of the
wastewater-added trace elements appears in the harvested crops. Long-term irrigation with wastewater
will thus mainly result in the gradual accumulation of trace dements in the soil, which will occur by
several mechanisms of retention, including adsorption and precipitation [61]. Factors that affect the
retention of trace elements by soils include soil texture, pH, soil organic matter, and clay content. Thus,
the potential for harmful effects in the future should not be overlooked, and cropland irrigation with
wastewater should be evaluated case by case.

Table 14. Annual input and calculated time required for wastewater-
irrigated agricultural soils to reach trace-dements loading
limits [61].
Element Typical Annual Suggested Time*
concentration input* ~loadingt
in wastewater
(me/L) (kg/ha) : Ocga~a) (years)
Cd 0.005 0.06 10 167
Cu 0.10 1.20 250 208
Ni 0.02 0.24 250 1,042
Pb 0.05 0.60 1,000 1,667
Zn 0.15 1.80 500 278

For wastewatcr appliedat a rateof 1.2 m/year (waterdepth).

For a soil having a cation exchange capacity (CEC) of 5-15 mcqll00g. For soils with
CEC<5mcq/100g and CEC>15meq/100g, the values given are multiplied for 0.5 and 2,
rcspcctively.

3.5. Atmospheric deposition

The principal anthropogenic sources of trace elements entering the atmosphere as gases, aerosols
and particulates include the combustion of fossil fuels, such as coal and oil, metal production, including
mining and smelting of metallic ores, industrial manufacturing, cement production, refuse incineration,
 363

including the burning of municipal refuses and sewage sludges, wood combustion, and automobile
exhausts [41 ].
Onc,e airborne, trace dements may travel long distance from the source through winds before
deposition onto land and waters. The distance of transport depends on several factors, which include the
type of the emitting source, the physical form and properties, e.g., size and density, of the element,
changes in physical and chemical characteristics during transport, adsorption and solution processes
occurring in the atmosphere, and meteorological conditions.
Trace element concentrations in air are very difficult to measure and pronounced geographical
variability, reflecting a different technological development, exists for a particular element. Global
emission into the atmosphere [2], estimated annual discharge from coal combustion in USA [73], and
representative median concentrations of some potentially hazardous trace dements in the vicinal air over
Europe and North America are shown in Table 15 [3, 25, 74].

Table 15. Global emission into the atmosphere (1000 metric tonnes/year) [2],
estimated annual atmospheric discharge (metric tonnes/year) from coal
combustion in U.S.A. [73], and representative median concentrations (ng/m 3
at STP) of potentially hazardous trace elements for the vicinal air over
Europe and North America (source: [74], from compilations by Bowen [3]
and Kabata-Pendias and Pendias [25]).
Element Global inputs into Atmospheric Vicinal air Vicinal air over
the atmosphere discharge from coal over Europe North America
combustion in U.S.A.
As 18.8 29 . . . .
Ba -- 130 . . . .
Be . . . . 2 0.2
CA 7.6 4.6 20 21
Co -- 6.3 2 3
Cr 30 66 25 60
Cs -- 3 0.5 0.2
Cu 35 -- 340 100
Hg 3.6 38 1 2
Li . . . . 2 --
Mn 38 60 43 150
Mo 3.3 -- 1 2

Ni 56 -- 25 100
lab 332 60 120 2,700
Sb 3.5 3.6 8 12
Se 3.8 110 . . . .
Sn 6.4 -- 20 20
Sr . . . . 2 3
Ti 1,100
V 86 90 30 400
Zn 132 500 1,200 500
364

The two compilations in the third and fourth columns of Table 15 show a generally good
agreement, but substantial differences exist, e.g., for Cu and Pb. Irrespective of the continent, the
concentrations of Cu, Zn, Pb and V in the atmosphere are the largest in absolute, thus suggesting
relatively large fluxes of these metals to the soil surface.
Atmospheric deposition may contribute and alter to different extent the total concentrations of
trace elements in soils, on dependance on the absolute element concentrations in air and deposition
velocity, which varies with particle size distribution, ground cover, and meteorological conditions [4].
Atmospheric inputs of trace elements to soils are important because they are cumulative and difficult to
limit and control, and because soil systems differ markedly in their response to these trace elements
inputs. Although annual estimates of trace-element deposition are subject to a considerable degree of
uncertainity, the orders of magnitude for the amounts of trace elements deposited from air onto soils have
been estimated [4]. The evaluation is based on the atmospheric concentrations measured in a number of
locations in remote regions, including South Pole, North Norway and North West Canada, and in rural,
metropolitan and highly industrialized areas in Europe and North America (Table 16).

Table 16. Amounts (g/ha/year)* of trace elements deposited from atmosphere

onto soils in remote regions (South Pole, North Norway, North West
Canada), and rural, metropolitan and industrialized regions in Europe and
North America (source: [4]).
Element Remote regions Europe North America
1,460T
Be 1.5-6.3 0.2-0.7
Bi 0.4T
Cd <0.01 0.8-978 <0.2-65
Cr <0.01-0.4 1.6-221 1.6-473
Co <0.001-0.04 0.3-58 0.2-36
Cu 0.02-1.6 13-7,726 7.9-1,734
Hg 0.006-0.4 <0.02-4.4 0.2-60
Li 3.6 9.5
Mn 0.006-1.9 14-331 0.1-1,419
Mo <0.3-5.0 0.2-16
Ni 0.8-1.3 6.3-189 <16-189
Pb 0.4-7.2 85-536 71-20,498
Sb 3T --
Sn 2.4-1,261 0.08-110
V <0.001-1.2 7.9-145 <1.6-3,154
Zn 0.02-6.3 20-25,229 <788-2,681
Derived from data for air concentrationpresented in [3], assuminga depositionvelocity of
2mm/secfor remoteregionsand 5mm/secfor rural,metropolitanmadindustrializedregions[4].
t Data published in [251.
 365

Ranges of data referred in Table 16 show that in remote regions the elements Cd, Cr, Co, and V
are deposited in amounts less than 10 mg/ha/year, whereas the greatest deposition are from Cu, Zn and
Pb. Considering the minimum values presented in Table 16 as representative of trace-element deposition
onto soils in rural regions, approximately equal amounts of Cr, Co, Cu, Pb, Mn, Mo, Sn and Zn are
deposited in both geographical areas.
Enrichment factors have been calculated and increased concentrations have been estimated for
trace elements in surface soil (0-15 cm) resulting from atmospheric deposition [4]. The annual increase in
trace-element concentrations from air deposition is very small in soils in remote regions and rural regions,
and results, except for Pb, Be and Cu, less than 0.001% of the typical soil concentration. In the case of
metropolitan regions, the predicted annual increase of Mn, Co, Cr and Be range from 0.01 to 0.06%, those
of V, Cd, Cu and Zn range from 0.3 to 0.7%, and Pb is at 13%. Estimates also show that atmospheric
deposition in industrial regions will substantially increase the concentrations ofPb, Hg, Cd, Cu, V and Zn
in soils.

3.6. Miscellaneous sources

Incidental point sources of trace elements for soil include: corrosion of metal objects and
fragments, dispersion of metallic ores during road transport from mines and mills to the melting site,
downstream leaching from disused mines, airborne dust or leachates from spoil heaps of waste materials
accumulated at the sites where coal, shale and metal ores are mined, milled or smelted, dispersion of
combustion residues, such as cinder and clinker from furnaces, pulverised fuel ash or fly ash from coal-
burning power stations, and others [5, 12].
The type and concentration of trace elements associated to these emissions and introduced into
soil are extremely variable and mainly dependent on the specific site conditions. Serious local
contamination of soils can be detected within several km from the point of release. For example, Purees
[12] reports: (i) greatly elevated levels of Pb in soils along the routes used for the truck transport of lead
ore in Missouri; (ii) abnormally high levels of Ph, Zn, Ag and Cd in soils nearby sites of mines and
smelters of Pb and Zn metal ores; (iii) greatly enhanced levels of As and Cu in soils contaminated by
drainage waters and stream sediments from mining and smelting in South West England; and (iv) levels
of available Cu, Pb, Zn and Cd contents in soils downstream from disused mines in Wales much higher
than those normally found in soils of that area.

4. Effects of soil trace elements on human health

An adverse health effect has been defined as "the causation, promotion, facilitation, and/or
exacerbation of a structural and/or functional abnormality, with the implication that the abnormality
produced has the potential of lowering the quality of life, contributing to a disabling illness, or leading to
a premature death" [75]. Although current environmental levels of toxic trace elements rarely produce
illness or death in the general population, the Sherwin's definition implies that a large segment of the
366

"healthy" population can be suffering from trace element poisoning without even realizing it. Indeed,
most trace elements tend to accumulate in mammalian tissues, even at low exposure doses, thus
representing a subtle environmental health hazard.
Symptoms of trace-element toxicity are usually nonspecific and retrospective, rather than early-
warning or prospective, thus alterations in the vital signs become manifested only after the intoxication
process has advanced. Possible adverse health effects by trace-element poisoning is most likely to be
subclinical, that is, the patient either does not show any symptoms or fails to recognize them, thus
resulting in a health state where an inordinate depletion of the functional integrity of the cell, tissue or
organ has occurred or is taking place. Earliest adverse health effects possibly entailing serious alterations
in cellular ecology may not come to clinical attention until the damage has reached an advanced stage.
With the possible exception of Pb, the current level of sensitivity of clinical tests is inadequate for the
diagnosis of such subtle early biological indicators of the metal interactions with subcellular biochemical
systems. Further, some evidence exists which suggests a synergistic toxicity of hazardous trace elements
[76, 77], so that the risks in the low-dose, low-rate exposure region may be considerably enhanced [78].
Finally, trace elements can elicit their toxicity as potential cofactors in other diseases.
Actual experimental verification of the long-term health effects of low-level exposures to
hazardous trace elements remains difficult and expensive. Epidemiological studies usually consist of
estimates of the probability of health effects based on the interpretation of experimental and statistical
data often resulting from different analytical approachs and protocols. Further, the worldwide risks of
trace-element poisoning are far from being universally accepted, especially when economic benefits stand
versus risks of exposure.
Assessment of the likelihood of risks to humans from potentially hazardous trace elements
introduced into soil by various anthropogenic activities requires a knowledge of the potential for transfer
of each element from the soil to crops and animals, including humans. Transfer coefficients (mobility) of
several trace elements in the soil-plant system are summarized in Table 17 [79].However, the amount of
hazardous trace elements in food is connected to the concentration in soil by intricate relationships which
are not yet well understood.
Transfer of trace elements from soils to crops is prevalently a function of the element species,
input rate and amount of the element in the soil, soil pH, crop species and cultivar grown. Some trace
elements can be increased in edible crop tissues when elevated amounts of the element are applied to
acidic soils (Cd, Zn Ni), or alkaline soil (Mo). Cultivar selection can be used to reduce food-chain transfer
of some trace elements. Further, grazing livestock may inadvertently ingest soil polluted with trace
elements, thus causing a much greater direct exposure than that occurring via plant uptake. Estimation of
food-chain transfer of trace elements from the soil is critical to the valid estimation of the potential for
human exposure and health hazards.
Nowadays ample evidence exists on health effects related to ingestion & t r a c e elements by food
crops originated from soils contaminated by anthropogenic activities. Concern for the transfer of Cd into
 367

the human fi~od chain is considerably greater than that for other trace dements [80], because of the high
bioavailability, high toxicity, and long body retention time of Cd. The human diet, and in particular the
vegetable/gnfin component, represents the major source of Cd exposure [81]. Therefore, the high mobility
of Cd in the soil-plant system represents a potential hazard to human health when levels of Cd in soils are
raised by anthropogenic inputs of various nature.The elevated Cd content determined in polluted soils of
the basin of ~IheJintsu river in Japan has been related to the outbreak of a disease with severe bone pains,
the Itai Itai disease, occurred in this region early in this century [82]. Food crops grown in this area and
drinking water result heavily contaminated by Cd, which is believed to cause renal tubular disfunction
followed by osteomalacia and osteoporosis.

Table 17. Transfer coefficients for trace elements in

the soil-plant system (source: [79]).
Element Transfercoefficient
As 0.01-0.1
Be 0.01-0.1
Cd 1-10
Co 0.01-0.1
Cr 0.0l-0.1
Cu 0.1-1
Hg 0.01-0.1
Ni 0.1-1
Pb 0.001-0.1
Se 0.1-10
Sn 0.014).1
TI 1-10
Zn 1-10

In Japan, 9.5 % of paddy soils, 3.2% of upland soils and 7.5% of orchard soils have been
estimated to be severely contaminated by Cd and Zn due to the release from several non-ferrous metal
mines and smdters and Zn-ore wastes [83]. Food crops, especially rice, grown on such soils, are thus
contaminated and have resulted in a substantial increase of the dietary intake of Cd and the average Cd
concentration in renal cortex in the Japanese population [84-86]. Metabolic models [87] suggest that the
average daily intake of 100-180 lag Cd by residents in the highly polluted areas in Japan can cause
excessive renal Cd accumulation in about 5-10°,4 of the people exposed. Further, the calculated intake rate
of 42-69 lag of Cd per day in the "unpolluted" areas [88], over an extended period of time, can result in
0.5-1% of the population above the critical level. Assuming that 5-10°,4 of the human population actually
ingest an average of 32 lag Cd per day, which is typical of many countries [84, 89], and that this intake of
Cd can result in 0.1% of the population having Cd concentrations in the renal cortex above the threshold
for proteinuria, the total number of persons likely to accumulate Cd to the stage of renal disfunction is
estimated to be 250,000-500,000 [2]. However, the people actually at risk from environmental Cd
368

poisoning is probably considerably higher and believed to be mostly in Japan and central Europe where
the soils are often contaminated with this element [79, 83].
Much interest has been recently raised on the possible relations between soil trace elements and
human cancer, and the literature is beginning to suggest that the availability of specific trace elements
affects both cancer incidence and mortality [90]. Early research results show the existence of links
between stomach cancer incidence and soil Co, Cr and Zn concentrations in Cheshire and North Wales
[91]. In Finland, high levels of Zn and Cu in soils and plants seem related to elevated cancer mortality,
while elevated soil Mn appears to reduce cancer incidence [92, 93]. Breast cancer appears more common
in those areas in U.S.A. that have soils deficient in I [94], while many cancers seem less frequent where
soil, and hence food, contains elevated Se amounts [95, 96].
More recently, results of large scale correlation and regression studies conducted using North
American cancer mortality data and a variety of environmental variables, including the mineral contents
of soils, have shown that, in addition to carcinogens, cancer mortality may be also influenced by the soil
levels of certain macronutrients and trace elements, which include Se, Li, I, Hg, Cd, Mn, Zn Zr and Ba
[97-100]. Cancers of the digestive, respiratory and reproductive systems appear to be frequently
associated with soils with particularly elevated levels of Be, Ba, Hg and Sr, or low levels of Se [99].
Selenium appears to play a protective role, reducing cancer mortality from many types of digestive
malignant neoplasms and in certain respiratory and reproductive cancers, especially those of ovary and
breast [97].
Results of a very recent correlation, factor analysis and stepwise multiple regression study on the
possible relationships between Chinese age-standardized cancer mortalities and 69 soil characteristics
established at 4,130 locations throughout China [101], indicate that As, Cs, Sb and TI levels in soil are
significantly (p<0.05) negatively correlated with specific cancers, and can explain much of their variance.
On the contrary, soil Ge and Hg contents display the most frequent significant (p<0.05) positive
correlations with cancer mortality. Chen et al. [101] conclude that, although in such large scale analyses
some apparently significant correlations are likely to be generated by chance and others may reflect
colinearity, and not causal relationships, at least some of the soil elements that show repeated statistically
significant associations with specific cancers appear to meet, at least in part, both the consistency and
biological plausibility criteria for causality. These elements include As, Cs and Hg, while the possible
roles of Sb and Ge in carcinogenesis is less obvious.
Although the Chinese data [101] reveal repeated negative correlations between soil As levels and
cancer mortality, thus supporting the position of several researchers who have shown that As has unique
anticancer properties and is far more likely to protect against eareinogenisis than to pomote it, a still
widespread contrasting belief is that As is a potent carcinogen. Results of a study on the distribution of As
in North American soils and water supplies, which explain much of the variation in cancer mortality,
represent the strongest support to the hypothesis that As is a major cause of cancer [102].
 369

Differently from As, the finding that Chinese mortality from numerous cancer shows a marked
positive correlation with soil Hg levels [101] confirms the results obtained in the U.S.A. where a similar
strong positive correlation has also been found, especially for cancers of the digestive tract [97, 99].
A geographically Iow-Se belt exists in China on a large scale, which coincides very well with the
distribution of Keshan disease (an endemic eardiomyopathy) and Kaschin-Beck disease (an endemic and
chronic ost~mgenesis joint disease) [103, 104]. In the Northeast China, where these two diseases are
mainly diffilsed, large areas of soils are deficient in Se, whose content is lower than that of non-disease
areas in China [105-107]. Selenium in these soils is shown to be either mainly adsorbed by humic acids in
forms unavailable to plants [106], or highly volatilized [108]. Thus, food crops grown on these soils are
deficient in Se, and a low Se circulation in soil-plant-animal-human ecosystem is induced [106].
Endemic goitre disease caused by iodine deficiency and fiuorosis caused by fluorine excess in
rural areas of Northeast China appear linked, respectively, to low I levels in drinking waters and grains
grown on the soils in this area and to F excess in drinking waters and topsoils of the region [106, 109].
A deficiency in either Se or Mn, as well as an excess of Zn, are found to be related to a weakening
of the function of the respiratory chain [92]. The abundance of Zn in Finnish foodstuffs may prevent the
adsorption of Se, and a shortage of Mn in many areas may reduce the utilization of Se in the cells [93].
Multiple sclerosis clusters studied in Saskatchewan have been proposed to be linked with excess Pb, Ni
and Zn in soil [110].

5. CONCLUSIONS

Nowadays, trace-element inputs are still increasing in the global environment and so they are in
most soils. Thus, it is of importance to know more about the long-term behaviour of trace elements in
agricultural soils, in particular with regard to effects on crop uptake and leaching to water bodies used as
drinking water. Crop uptake and leaching depend on conditions of soils, crops, and climate. In particular,
only soluble and available fractions of trace elements are expected to be transferred to waters and affect
plant nutrition. Thus, several factors including the chemical and physical properties of soil, agronomic
practices, geopedoclimatic conditions, and plant tolerances to the various trace elements have to be duly
considered to obtain a more complete picture of the actual hazard from trace element additions to soil by
anthropogenic sources. These factors must be considered when long-term trends in the behaviour of trace
elements are to be established.
An alternative approach would be to predict the long-term behaviour of trace elements on the basis
of models using existing information on the occurrence and chemical behaviour of trace metals in
agricultural soils. In order to develop such predictive models, it is necessary to account for the inputs of
trace elements from different sources, and the hehaviour of trace elements in soil-crop ecosystems under
different climatic conditions. However, these models would be difficult to calibrate or verify, as long-
term datasets on trace elements in natural ecosystems are scarce. Furthermore, there would still be a
370

number of uncertainties, such as future trends in inputs of trace elements and changes in land use and
environmental conditions.
In conclusion, geology, through its impact on soils and hence locally grown food and water
supply, appear to be the long established aspect of the environment which plays a key role in variations of
cancer and other human diseases incidence [111]. Although it is not possible to claim that environmental
trace elements necessarily cause cancer and other diseases, enough evidence exists which shows that trace
elements may have an influence, and this should prompt public health measures which, at least, could
reduce human health problems.
Much more research is needed to test the validity of hypotheses based on the existence of close
relationships between trace elements in the environment and human health. Worldwide laboratory and
clinical studies are essential, as are statistical analyses of links between human diseases and the
environment.

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