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ELSEVIER

The Science

of the Total

Environment

162 (1995)

l-11

Rapid geochemical assessment of agricultural-industrial


pollution from stream sediment dispersion flows, South
Siberia (Irkutsk Region)
G.A. Belogolova, P.V. Koval , V.D. Pampura
Institute

of Geochemistry,

Siberian

Branch,
Received

Russian Academy

of Sciences, PO Box 4019, Irkutsk-33,

30 July 1992: accepted

Russian

Federation

14 June 1994

Abstract
Geochemical surveys were undertaken for dispersion flows in Irkutsk, and its surroundings, with the aim of
selecting a rapid pollution assessment approach (1 sampling point/l4 km). Bottom sediments (< 0.25, 0.251, l-3
mm fractions), overflood sediments ( < 0.25, 0.25-l mm), surface water and plants were sampled. The samples were
analyzed by rapid semi-quantitative (partly quantitative) atomic emission spectroscopy (AES) methods for Ag, Pb,
Zn, Cu, As, Ni, Co, MO, Cr, Li, Ga, Ge, Y, Bi, Sn, Mn, V, Ti, W, Be, P and B, as well as for Hg, F and U (by
quantitative methods). Single-element maps, maps of geochemical classes (element associations) and ecological-geochemical regionalizations were compiled. The average concentration of the majority of trace elements in water and
alluvial sediments are similar to those for other regions of the world. Overflood sediments (particularly the fine
grained fraction) are enriched in the majority of trace elements. Anomalies in the fine fraction of over-flood
sediments are large and they coincide with hydrogeochemical and biogeochemical anomalies. Pollution anomalies
correlate with industrial and economic activity: the industrial-settled zone of Irkutsk (Ag, Cu, Zn, Pb, Hg, Ni, Cr); the
zone around Shelekhov with an aluminium plant (F, U, Cu, MO, Pb, Cr, Ni); and the agricultural zone (Ni, Co, Ti, V,
P, F, U, Mn, Hg). Small-scale geochemical surveys on the fine fractions (< 1 mm) of overflood sediments, based on
cheap and rapid semi-quantitative multi-element AES analysis (up to 50 elements) may be successfully applied to the
assessment of pollution by heavy metals and trace elements over large areas.
Keywords:
Siberia

Geochemical mapping of the environment; Agricultural-industrial

pollution; Stream sediments; South

1. Introduction

ning of further studies, requires an approach


based on the general geochemical changes of the
surface cover of the Earth. This is particularly
significant for areas of intensive human economic
activity and rapid change of environmental conditions.
Considering
knowledge of prospecting and

Rapid assessment of the environmental chemical situation


over large areas, aimed
at
ecological-geochemical
regionalization
and plan-

*Corresponding

author.

0048-9697/95/$09.50
0 1995 Elsevier
SSDI
0048-9697(95)04319-I

Science

BV. All

rights

reserved

GA Belogoloua /Sci. Total Environ. 162 (1995) l-11

geochemical
mapping,
ecological-geochemical
surveys of stream sediment dispersion flows may
be applied to such areas in conjunction with hydrological networks.
The present work considers the initial results of
an ecological-geochemical
study of sediment dispersion flows in the Irkutsk region and the NearAngara agricultural-industrial
zone.
2. Geology and landscape

Most of the region is composed of Jurassic


terrigenous sequences from the southern margin
of the Siberian Platform which overlap Precambrian magmatic and metamorphic complexes on
the surrounding Platform, and occupy a small
area in the south-west. The predominant relief is
moderately dissected hilly plains of denudation.
The regions are drained by the Angara River and
its tributaries.
A significant part of the area is covered by
remnants of taiga. Precipitation is the main source
which feeds the river. North-west winds are predominant along the Near-Angara industrial zone.
The industrial center of the region is Irkutsk
with > 600000 inhabitants. It is adjacent to the
town of Shelekhov, with a large aluminium plant
to the south-west. Agricultural activity is mainly
concentrated in the northern part of the area.
The natural regional ecosystems are very vulnerable.
3. Materials and methods

Stream sediments (l-3; 0.25-l; < 0.25 mm),


overflood silts (0.25-l;
< 0.25 mm>, river water
and willow branches, as well as water and surface
mosses were sampled at the same sites at a density of 1 sampling site/l4
km. Trace elements
were concentrated from the unfiltered waters by
co-precipitation
with aluminium
hydroxide [ll].
Biogeochemical samples were ashed at < 450 C.
All samples were analyzed by rapid semiquantitative optical emission spectroscopy for 22
elements: Ag, Pb, Zn, Cu, As, Ni, Co, MO, Cr, Li,
Ga, Ge, Y, Bi, Sn, Mn, V, Ti, W, Be, P and B [5].

Table 1 presents the determination


limits. Reference samples, ST-lA, SGD-lA, CT-lA, SG-2 and
SG-3, were used for quality control [7]. Standard
deviations were 30-50%. Hg, F and U were determined by quantitative atomic absorption (AAS)
as well as quantitative atomic emission spectroscopy (AES) methods. Part of the samples were
analyzed for the majority of the above elements
by quantitative methods (AES, AAS).
The Multi-dimensional
field computer programme [3] was used for data processing. This
provides statistical parameters,
single-element
maps, determination
of geochemical classes (associations of elements) and geochemical (multielement) class maps. The pattern of the latter
significantly depends upon the background values
which are selected. According to the Multi-dimensional field procedure, a concentration corresponding to 50% of the frequency level was chosen as background. An average background value,
calculated from the l-3-mm fraction of the stream
sediments, was accepted for stream sediment
maps.
4. Results

The average concentration


of a number of
chemical elements were determined in various
media (Tables 2 and 3). As a result, > 70 singleelement and multi-element
geochemical maps
were compiled. The maps indicate significant
anomalies and typical associations of elements.
Figs. 1-5 illustrate examples of such maps.
Table 1
Detection
troscopya

limits

0.01
4s
Pb
2.0
Zn 30
cu 10
As 30
Ni
2.0
co
2.0
MO 0.3
mm

Fig. 1. Distribution pattern of Ag in different media of dispersion flows.

PLgg-

for elements by optical


__--_
Cr 10
Li 10
Ga 6.0
Ge 1.0
Y
Bi Ii3
Sn 2.0
Mn 50

emission spec-

__-.-.
V
10
Ti 100
W
1.0
Be 10
B 10
Hg 0.005
U
1.0

GA

A9

n-10a2ppm)

Belogolow

/Sci.

Stream sediment
Size frOcti0n (mm) : f-3

Total En&on.

1.3

I.3

3.0

m
mu
100
* 100

34.0

O-Sampling

POinfS

Overbank sediment
A9
(n-fd*zPpm) Size fraction (mm) : d 0.25
. . . %3

A9
nofOm2mkg/Z)
_-:1

I-II

Stream

A9

n. W*pprn )

10.0

l-

162 (1995)

s&men+

Size fraction(mm) : 40.25

St ream

water

f.3

(;.A. Brlogolotur

/Sci.

Total Entiron.

162 (1995)

I-11

Moss
A9
(n.foappm)
4.5
6

a
r5
22

Fig. 2. Distribution pattern of Ag in willow branches and mosses.

Surface waters in the region are soft. The average concentrations of the majority of trace elements analyzed are comparable with those of
river water from other world provinces. However,
they are marked by lower Ag and Pb concentrations and a higher Mn, P, F and U content.
The anomalous concentrations of different elements in surface waters are observed over almost
the whole region (Fig. 5). Silver, F, Cu, Co and Ni
anomalies are particularly high. The left bank of
the Angara River near Shelekhov is marked by
increased F concentrations.
The average composition of the alluvial sediments of different facies are comparable, in gen-

eral, with those for alluvial soils from other regions of the world (Table 3) [4,10]. Overflood
sediments, as distinct from stream sediments, also
show increased concentrations together with a
dispersion of the majority of trace elements, except for Pb. This is especially evident for those
elements which form the intensive anomalies in
river water, e.g. Ag and Cu. The composition of
different alluvium fractions from the same facies
(bottom or top overflood sediments) are markedly
similar.
Geochemical
anomalies from alluvium
are
observed over the whole area of the industrial
zone, (Fig. 4). Overflood sediment anomalies, par-

.- .~~~~~~
Fig. 3. Distrihution

pattern of Ph in different media of dispersion flows.

G.A. Belogolotia

Pb
@pm,

/ Sci. Total Environ.

162 (19951 I-II

Stream

Overbank
sedimen f
Size frdction(mm): 40.25

water

. . . . . _. .
. . . ..I.
. . , . ..
. . . . . - *.. .

Pb

&earn

WOmm)

Size fraction (mm) : I-3

sediment

Pb
IPPml

Branches ofwill~w

G.A. Belogolorn / Sci. Total Entiron. I62 (1995) I -I I

6
7

Fig. 4. Multi-element geochemical map of overflood sediments.


l- 12 - geochemical classes:
1. Ag/400 Cu/60 Zn/17.5 Cr/S.l Pb/5.6 Ni/4.3 P/4.2 Sn/3.1 V/2.7 Co/2.5 B/2.3 Mo/2.2
2. Ag/50 Pb/4.2 Cu/4.0 Ni/Z.S B/2.5 Cr/2.3 Zn/2.2
3. Ag/5.0-3.0 G/3.1-2.1 Ni/2.8-2.0 Cr/2.2-2.0 PbVB Mn/2.1 PCr/2.0
4. Cu/6.0-4.0 Ni/4.8-3.4 Cr/2.7 B/2.5-2.0 Li/2.0
5. Pb/12.0-6.0 Cu/S.O-3.0 Ni/4.0-2.5 Cr/3.5-2 B/2.5-2.0 Zn/2.2-2.0 Mn/2.3-2.0
6. Ni/5.2-5.3 Cu/3.0-1.7 Mn/2.3-2.0 B/3.0 LiAg V/2.0
7. Ni/4.8 Cu/6.0-2.0 Li/2.5 Cr/2.5 V/2.5 Mq2.3 Mo/2.0 B/2.0 Pb/1.7 Ga/1.6
8. Ni/4.0-3.7 B/3.0-2.7 Q/2.2-2.0 Mn Cu LiV/2.0 Co/l.8 Pb/l.6
9. B/3.0-2.2 Cr/2.4-1.7 Ni/2.0-1.7 Li MoP/2.0
10. Cr/3.5 Ni/3.0 V/2.9 Pb/2.3 B/2.2 Co/2.0 MnP/2.0
11. Li/3.0 Ni/3.0 Mn/2.2
12. Mn/2.5-1.8 P/2.3 Ni MO Li/2.0
Numbers indicate contrast coefficients (ratio of sample to background).

titularly, Ag, Cu, Zn and Co, are the largest and


most contrasting. Their boundaries are markedly
different from similar bottom sediment anomalies
and are more compatible with hydrogeochemical
and water-moss anomalies (Fig. 1, 2). Elongation
of such anomalies usually conforms to the direction of the Near-Angara industrial zone. Some
elements, for instance Pb, which form vast
anomalies in overflood sediments and plants do

not exhibit remarkable anomalies in water (Fig.


3). At the same time Pb anomalies were discovered in the sandy fraction (l-3 mm) of bottom
sediments. These anomalies are confined to boat
stations and probably result from the mechanical
destruction of industrial refuse.
The multi-element
anomalies in overflood sediments are marked by a wider set of elements and
high contrast coefficients, this is due to the above

G.A. Belogolota

/Sri.

Total Endron.

v
0,

162 (1995)

I-II

-V

f&m

Fig. 5. Multi-element geochemical map of water dispersion flows


1-9 - geochemical classes:
1. Ag/52.3 Cu/31.0-5.1 Sn/2.5 Zn/2.8 Ni/8.7 Co/7.1 P/7.1 Mn/2.2 Cr/2.0
2. F/40.5-16.2 Cu/8.3-2.0 CO/~.? Cr/3.8 Mo/3.6 Pb/3.4 V/3.3 Zn/2.5 U/2.1
3. F/9.1 U/2.4
4. F/4.2-2.0 Ti/2.4
5. Co/15 Ni/11.3 Ti/h.S Mn/3.8-2.9 F/3.1 U/2.7 V/2.6 Pb/2.3 Cr/2.3 Sn/2.0
6. Co/lO.S-6.0 Ni/7.2-3.0 Ti/6.1-3.1 P/4.7-2.4 F/3.4 Mn/2.9-2.3 UPb/2.2
7. Ni/3.3 F/2.8 Sn/1.7
8. Sn/2.3
9. Ti/3.4-2.8 Co/2.9-1.9
Numbers indicate contrast coefficients (ratio of sample to background)

mentioned composition differences of stream and


overflood sediments. Anomalies with high Ag, Cu,
Pb, Zn, Ni and Cr, concentrations (classes 1-3,
Fig. 4), which surround Irkutsk, are common for
an industrial center [S]. The adjacent areas are
distinguished by the associations and lower contrast coefficients of pollutants (Fig. 4).
5. Discussion
The levels of elements in different natural me-

dia, particularly background values for alluvial


sediments, for the majority of elements, are comparable with values for data from other regions
and continents. Significant differences for Ag. Pb,
Mn, P, F and U may characterise the regional
pattern and require further investigations.
The anomalous concentrations of a number of
biologically active elements (Ag, Pb, Zn, Cu, Ni,
Co, MO, Cr, Sn, P, Hg and U) in alluvial sediments are OS-2 orders higher than the background values. At the same time, the concentra-

G.A. Belogolow

Table 2
Concentration of trace ( fig/l)
Elements
-.__
4
Pb
Zn
CU

Ni
CO

Sn
V
Ti
Cr
P
U
Jk
FCO;
HCO,
clso:K+
Na+
Ca? Mg

and major (mg/l)

/ Sci. Total Environ.

162 (1995)

l-l

elements in surface waters (Irkutsk region)

Element contents
Irkutsk region
Background
Average

Maximum

Minimum

Average element
content in river
waters [2,6]

0.03
0.4
20
6
0.9
0.5
0.4
4
13
3.8
160
0.57
0.03
0.3
9.2
109.3
17.6
12.9
10.5
8.9
31.1
6.4

8.8
2.5
219.0
139.0
8.1
4.9
18.7
26.1
68.3
26.6
1500.0
3.0
0.5
5.6
33.6
222.0
105.1
70.0
260.0
31.0
60.0
25.0

0.02
0.1
5
1.1
0.1
0.1
0.1
0.5
1
0.5
5
0.02
0.003
0.02
2.4
30.5
4.3
4
0.5
1.3
4.8
1.9

0.3
3
20
7
0.3
0.2
0.5
3
1
20
0.04
0.1
58.4
7.8
11.2
2.3
6.3
14.6
4.1

0.02
0.1
15
3
0.4
0.2
0.3
4
7
3.0
100
0.4
0.1

Maximum
permissible
concentration [l]

(0.2)
(1)
(20)
(7)
(2.5)
(0.3)
C-J
(1)
(3)
(1)
(40)
(0.5)
(0.07)
to.11

50
30
5000
1000
100
1000
100
100
100
100
0.5
l-l.5
-

350
500
50
120
180
100

__-

Note: concentrations according to Gordeev [2] are in brackets.

lions of the majority of contaminants in surface


waters do not exceed the medical standards, accepted in Russia 1121. However, this does not
indicate high quality and environmental
wellbeing. Firstly, in soft water, the toxic biological
effects of heavy metals markedly increase [9].
Secondly, the pollution increase in the upper layer
of overflood sediments as compared with stream
sediment, results in the general level of pollution
increasing over the whole area, as well as an
accumulation of toxic elements in soils and plants.
This is particularly true for the highly mobile and
biologically active elements.
Anomalous
geochemical associations in the
surface layer of over-flood sediments, which involve lithophile
and chalcophile elements and
concentrate toxic elements, indicate a significant
disturbance of the natural environment, caused
by man. These disturbances are evident from the
differences in anomaly sizes and outlines in vari-

ous facies of alluvial sediments (Fig. 1). They may


be applied for the assessment of man-made effects of the anomalous fields. In this case, the
mode of supergene element top migration should
be considered as is evident from a comparison of
Ag (Fig. 1) and Pb (Fig. 3) anomalies.
The above conclusions are confirmed by the
correlation between the anomalous element distribution
in different stream sediments and
economic activity in the region. It is exemplified
by the sketch map of ecological-geochemical
regionalization, compiled using multi-element
and
single-element geochemical maps (Fig. 6). Three
main zones, marked by a set of elements, are
distinguished: the industrial-settled
zone (Irkutsk
city) with developed machine building, food and
other industries (Ag, Cu, Zn, Pb, Hg, V, Ni, Cr,
Cd); the Shelekhov zone with the aluminium plant
(F, U, Cu, MO, Pb, Cr, Nil; and the agricultural
zone (Ni, Co, Ti, V, P, F, Mn, Hg).

Hg
U

Pb
Zn
cu
Ni
co
MO
Cr
Sn
V
Ti
P

0.11/8.8
ll/lOO
83/2200
70/2200
32/220
15/33
1.6/11
49/440
4.1/11
85/165
2036/4400
122/550
-

mm

0.02
8
58
19
28
10
1
39
3.9
78
1944
96
-

Background
0.05/3.0
12/200
51/100
22/150
16/30
10/20
1.8/5
57/200
3.8/6
52/80
2370/6000
115/300
-

Average

< 0.25

Contents

region

0.02
5.7
52
19
15
7.8
1.9
52
3.8
52
1920
96
-

mm

0.02/0.4
8.5/100
41/80
17/40
9.8/20
6.9/20
1.1/2.0
30/60
2.3/4
39/80
2139/5000
73/150

Average

___-

0.25-l

sediments

Background

in bottom

indicates average concentrations


[lo] and Kabata-Pendias
[4].

dry wt.) Irkutsk

maximum
concentrations,
numerator
in alluvium
according
to Shacklett

0.02
8
39
19
19
10
1
52
3.8
58
1931
96
0.01
2.5

Averagea

0.1 l/6.6
11/110
64/1100
51/2200
28/110
12/33
1.5/22
58/550
4/22
77/166
2306/4400
130/660
0.04/1.5
3.4/17

0.25-l

Background

sediments

flows (ppm,

< 0.25

in overflood

dispersion

Average

Contents

in alluvial

aDenominator
indicates
bAverage
concentrations

As

Elements

Table 3
Element content

0.02
5.8
39
16
7.8
5.7
1.0
19.2
1.9
29
1931
52.6

Background

l-3

mm

0.05/4.4
28/2200
S6/220
32/220
16/44
11/33
1.8/4.4
38/88
4.2/110
60/165
1776/3300
96/220

Averagea
0.02
6
40
15
10
8
1
30
3.0
40
1700
80
-

Background

-.-

--

0.05

18
58.5
27
19
9
5.8
54
4.5
58
2000
-

Average contents
alluviumb

in

IO

G.A. Be1ogoloc.n

/ Sci. Total En&on.

162 (1995)

I-11

6. Conclusions

Medium-to-small
scale geochemical mapping of
stream dispersion flows, based on multi-element
semi-quantitative
optical emission spectroscopy,
may be successfully applied for rapid pollution
assessment and monitoring over large areas, planning further economic evaluations and detailed
environmental study.
The fine ( < 0.25 mm) fraction of the overflood
sediment surface layer (O-10 cm) is the preferred
sampling media. However, for detailed study of
the environment, in addition to the analysis of
natural and man-made effects, simultaneous sampling of several related media (fine fraction of
overflood and stream sediments, water, plants) is
essential.
Geochemical comparisons of different media
and fractions from dispersion flows, as well as
different biota, is a promising approach for environmental assessment as well as for recognition
of pollution sources and trends.
Acknowledgements

Fig. 6 Map of ecological-geochemical


regionalization
(Shrlckhov-Irkutsk).
I !i --~ gcochcmical classes in flood sediments (numerator)
and surface waters (denominator): 1-8 - industrial-settled
zone of Irkutsk:

The authors are indebted to F. A. Akhmadulin


for conducting the field work, the analysts for
performing the analysis on samples and Irkutsk
city administration
for financial support. We are
also grateful to Ms. M. Yu. Khomutova for translation of the text into English.
References
[l]

6. Ag, Cu; Pb, Zn, Ni, Cr,/Ag, Cu, Co, Zn, Ni, Uz
7. cu, Ni, Ph. Cr, Ag;/F,, U,
8. Ph, Cr, Ni, Ag, Mn, Co, Cu, ZnJctm1I ~-- zone of Shelekhov aluminium plant:
0. Vu,,, Hg, Ag: Pb,/F:,, Pi Pb, Ni, Cu, MO,
II). Ni, V, Co, 1.i: U,/F:,, Cu, MO, Pb, U,
I I. Uj Ni, B, Cr,iF,
12-15
agricultural zone:
1. Hg,,f+
1.;. ,/Co,, Ni,, Ti,,
14. Ni : P, Li 1 U_,i Mn, Cr2/Co,, Ni, Ti, P4 U1 F7 Mn,
i5. Ni, B, Cr-. Ti. MnZ/Co,,, Ni,,, Ti, F, Mn,.

[2]
[3]

[4]
[5]

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/ Sci. Total En&on.

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