13
ISSN 10642293, Eurasian Soil Science, 2011, Vol. 44, No. 7, pp. 781–793. © Pleiades Publishing, Ltd., 2011. Original Russian Text © N.P. Chizhikova, S.E. Sirotskii, G.V. Kharitonova, A.S. Manucharov, N.S. Konovalova, E.V. Utkina, 2011, published in Pochvovedenie, 2011, No. 7, pp.848–860. 781 INTRODUCTION The rapid development of China results in the environmental pollution of the Amur River basin, a large transboundary geosystem, on whose floodplain soils the main regional arable lands occur [1, 11]. The basin of the Sungari River, one of the largest Amur tribu taries, completely occurs within Chinese territory. The study of the finely dispersed components is of importance in the analysis of the environmental status of the biosphere’s ecosystems. Due to the large spe cific surface and the crystal chemistry of the minerals, these components control the exchange of the ecosys tems with the environment, which is based on the interactions between the clay minerals and water. The most dynamic interactions take place in the zone of the recent sedimentogenesis: the bottom sediments and suspensions of rivers and lakes. The bottom sedi ments of surface water bodies are conventionally used as indicators of the technogenic pollution rate and scope [24, 27]. The aim of this work was to study the mineralogical and chemical features of the finely dispersed compo nent of the bottom sediments in the Amur River. This work continues our study of the Amur River ecosystem [20]. A close correlation between the min eralogies of the finely dispersed components of the humusaccumulative horizons of the catchment soils, silt deposits, bottom sediments, and suspensions in the Amur River was previously revealed. In this work, our attention was focused on the behavior of the microele ments in the fine component of the bottom sediments and the electronmicroscopic study of the mineral morphology. The content of microelements in some components of the Amur ecosystem (the water, algae, macrophytes, and ichthyofauna) was considered. OBJECTS AND METHODS OF STUDY The works were conducted in the plain part of the central and lower Amur basin. The river is mainly fed in the central Amur basin (between the cities of Blagoveshchensk and Khabarovsk), where the main tributaries (the Zeya, Bureya, Sungari, and Ussuri) flow into the river (Fig. 1). The middle Amur acquires features of a lowland river flowing to the Amur–Sun gari Plain, the Russian part of which is named the Central Amur Lowland. This is a low (absolute heights of 45 to 100 m) waterlogged plain with several levels of river terraces and a vast floodplain up to 10–30 km in size. It is surrounded by the Khingan–Bureya Moun tains in the west and northwest, the folded volcanic Mineralogy and Chemistry of Finely Dispersed Bottom Sediments in the Amur River N. P. Chizhikova a , S. E. Sirotskii b , G. V. Kharitonova b , A. S. Manucharov c , N. S. Konovalova d , and E. V. Utkina b a Dokuchaev Soil Science Institute, Russian Academy of Agricultural Sciences, per. Pyzhevskii 7, Moscow, 119017 Russia b Institute of Water and Ecological Problems, Far East Division, Russian Academy of Sciences, ul. Kim Yu Chena 65, Khabarovsk, 680000 Russia c Faculty of Soil Science, Moscow State University, Moscow, 119991 Russia d Institute of Tectonics and Geophysics, Far East Division, Russian Academy of Sciences, ul. Kim Yu Chena 65, Khabarovsk, 680000 Russia Received October 12, 2010 Abstract—The mineralogy and chemistry of the fine fractions separated from the bottom sediments (aqua sols) in the Amur River were studied in the subfractions of the fractional peptization differing in the binding strength between the waterpeptized and aggregated components. Detritus of quartz, field spars, and strongly degraded layered silicates mainly passes into the waterpeptized state. Interstratified layered silicates with dif ferent combinations of chlorite and mica layers prevail in the aggregate subfraction. The distribution of the microelements in the bottom sediments, the waterpeptized and aggregated clays, and the residues after their separation was determined. The content of iron, manganese, zinc, and copper in the clay subfractions was higher than in the bottom sediments and in the residue after the separation of the clay subfractions by 2–4 times, which confirmed the functional significance of the clay minerals. The presence of diatomic algae in the components of the bottom sediments was revealed by scanning electron microscopy. The contri bution of the diatoms to the accumulation of iron, manganese, zinc, and copper was shown. DOI: 10.1134/S1064229311070039 MINERALOGY AND MICROMORPHOLOGY OF SOILS

Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

Embed Size (px)

Citation preview

Page 1: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

ISSN 1064�2293, Eurasian Soil Science, 2011, Vol. 44, No. 7, pp. 781–793. © Pleiades Publishing, Ltd., 2011.Original Russian Text © N.P. Chizhikova, S.E. Sirotskii, G.V. Kharitonova, A.S. Manucharov, N.S. Konovalova, E.V. Utkina, 2011, published in Pochvovedenie, 2011, No. 7, pp. 848–860.

781

INTRODUCTION

The rapid development of China results in theenvironmental pollution of the Amur River basin, alarge transboundary geosystem, on whose floodplainsoils the main regional arable lands occur [1, 11]. Thebasin of the Sungari River, one of the largest Amur tribu�taries, completely occurs within Chinese territory.

The study of the finely dispersed components is ofimportance in the analysis of the environmental statusof the biosphere’s ecosystems. Due to the large spe�cific surface and the crystal chemistry of the minerals,these components control the exchange of the ecosys�tems with the environment, which is based on theinteractions between the clay minerals and water. Themost dynamic interactions take place in the zone ofthe recent sedimentogenesis: the bottom sedimentsand suspensions of rivers and lakes. The bottom sedi�ments of surface water bodies are conventionally usedas indicators of the technogenic pollution rate andscope [24, 27].

The aim of this work was to study the mineralogicaland chemical features of the finely dispersed compo�nent of the bottom sediments in the Amur River.

This work continues our study of the Amur Riverecosystem [20]. A close correlation between the min�

eralogies of the finely dispersed components of thehumus�accumulative horizons of the catchment soils,silt deposits, bottom sediments, and suspensions in theAmur River was previously revealed. In this work, ourattention was focused on the behavior of the microele�ments in the fine component of the bottom sedimentsand the electron�microscopic study of the mineralmorphology. The content of microelements in somecomponents of the Amur ecosystem (the water, algae,macrophytes, and ichthyofauna) was considered.

OBJECTS AND METHODS OF STUDY

The works were conducted in the plain part of thecentral and lower Amur basin. The river is mainly fedin the central Amur basin (between the cities ofBlagoveshchensk and Khabarovsk), where the maintributaries (the Zeya, Bureya, Sungari, and Ussuri)flow into the river (Fig. 1). The middle Amur acquiresfeatures of a lowland river flowing to the Amur–Sun�gari Plain, the Russian part of which is named theCentral Amur Lowland. This is a low (absolute heightsof 45 to 100 m) waterlogged plain with several levels ofriver terraces and a vast floodplain up to 10–30 km insize. It is surrounded by the Khingan–Bureya Moun�tains in the west and northwest, the folded volcanic

Mineralogy and Chemistry of Finely Dispersed Bottom Sedimentsin the Amur River

N. P. Chizhikovaa, S. E. Sirotskiib, G. V. Kharitonovab, A. S. Manucharovc,N. S. Konovalovad, and E. V. Utkinab

a Dokuchaev Soil Science Institute, Russian Academy of Agricultural Sciences, per. Pyzhevskii 7, Moscow, 119017 Russiab Institute of Water and Ecological Problems, Far East Division, Russian Academy of Sciences,

ul. Kim Yu Chena 65, Khabarovsk, 680000 Russiac Faculty of Soil Science, Moscow State University, Moscow, 119991 Russia

d Institute of Tectonics and Geophysics, Far East Division, Russian Academy of Sciences, ul. Kim Yu Chena 65, Khabarovsk, 680000 Russia

Received October 12, 2010

Abstract—The mineralogy and chemistry of the fine fractions separated from the bottom sediments (aqua�sols) in the Amur River were studied in the subfractions of the fractional peptization differing in the bindingstrength between the water�peptized and aggregated components. Detritus of quartz, field spars, and stronglydegraded layered silicates mainly passes into the water�peptized state. Interstratified layered silicates with dif�ferent combinations of chlorite and mica layers prevail in the aggregate subfraction. The distribution of themicroelements in the bottom sediments, the water�peptized and aggregated clays, and the residues after theirseparation was determined. The content of iron, manganese, zinc, and copper in the clay subfractionswas higher than in the bottom sediments and in the residue after the separation of the clay subfractionsby 2–4 times, which confirmed the functional significance of the clay minerals. The presence of diatomicalgae in the components of the bottom sediments was revealed by scanning electron microscopy. The contri�bution of the diatoms to the accumulation of iron, manganese, zinc, and copper was shown.

DOI: 10.1134/S1064229311070039

MINERALOGY AND MICROMORPHOLOGYOF SOILS

Page 2: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

782

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

CHIZHIKOVA et al.

Sikhote�Alin mountain range in the east and south�east, and the Eastern Manchuria Mountains in thesouth.

The climate is characterized by a combination oftemperate continental and monsoon features [3]. Themean annual temperature is 0.6–1.1°C; the meanannual precipitation in the region under study variesfrom 400–500 mm in the west to 600–700 mm in thesoutheast with an extremely nonuniform distributionamong the seasons. The high peak of the summer pre�cipitation (40–50% of the annual amount falls inJuly–August) creates conditions for temporary sur�face waterlogging; the moisture index of the territory ishigher than 1 [21].

In geological terms, the plain is characterized bythe wide development of Quaternary sediments over�lapping the older layers of argillites, siltstones, sand�stones, and volcanogenic sedimentary rocks. TheQuaternary deposits consist of a sedimentary complexof alluvial and lacustrine�alluvial facies: clays andloams, as well as sands, gravels, and pebbles [5]. Poorlypermeable loamy and clayey sediments are the soil�forming rocks in the major flat area of the basin.According to Nikol’skaya [15], epidote�group miner�als (protobase, zoisite) are predominant in the heavyfraction of the Quaternary deposits; iron minerals(goethite, menaccanite, and magnetite) are found insignificant amounts. Feldspars (mainly acid plagio�clases) and dark�colored minerals (biotite, amphib�oles) are identified along with quartz in the light frac�tion. The differences in the mineralogy of the alluvialand lacustrine�alluvial sediments of the left and rightbanks of the Amur River are determined by the abla�tion zones. The sources of ablation for the left river

bank are the Khingan–Bureya Mountains mainlycomposed of quartz�feldspar and biotite granitoids(the protobase�ore mineralogical province). Thesources of ablation for the right river bank are the par�ent rocks of the Sikhote�Alin western slopes, wherethe covers composed of basic lavas (basalts, andesite�basalts, and their tuffs) are widely developed (the epi�dote�zoisite�ore mineralogical province).

The soil cover of the Central Amur Lowland ismainly of middle�Quaternary age. During the lateQuaternary period, the evolution of the alluvial lacus�trine plans mainly occurred from the superaqual to theneoeluvial landscapes because of the climatic changestoward an increase in humidity and was accompaniedby the enhanced waterlogging and desalinization ofthe soils with solonetzicity signs [12].

The objects of the study were the finely dispersedcomponents of the bottom sediments. The bottomsediments were sampled in the zones of accumulationin the region between the Sungari River’s mouth andthe Amur estuary. The Amur water was sampled annu�ally in the region between the city of Blagoveshchenskand the river estuary from 1997 to 2007. The objects ofthe biogeochemical sampling were the seston, pery�phyton, macrophytes, and ichthyofauna of the AmurRiver. The seston (planktonic microorganisms withsome inorganic impurities) was sampled with a small�cell plankton net (cell diameter of 0.01 mm). Theplanktonic microorganisms in the Amur mainly con�sist of diatomic algae. The periphyton (algae foulingthe gravel�pebble substrate) was sampled by the wash�ing method. The macrophytes include limnanth (Lim�nanthemum), arrowhead (Sagittaria), and pondgrasses(Potamogeton); the ichthyofauna consists of ordinaryfish. Sewage sludge was also sampled from the Kha�barovsk treatment facilities. The sewage sludge is atechnical analogue of seston: the water is fed into thewater supply system directly from the Amur River. Thedata on the microelement composition of a 1�m�longcore of the bottom sediments from Lake Udyl linkedto the Amur by the Ukhta branch, where the bottomsediments have been accumulating for about ten thou�sand years, were used for comparison (Fig. 1). Thecore was analyzed by 5�cm layers.

The work was based on the study of the chemistryand mineralogy of the finely dispersed component ofthe bottom sediments from reference plots (Fig. 1).The clay subfractions obtained by the fractional pepti�zation of the bottom sediments—water�peptized clay(WPC) and aggregated clay (AC)—were separated bythe Gorbunov method [6]. No coagulating agent wasused to avoid the loss of microelements. The sus�pended matter from the water samples was coagulatedby the addition of HCl to the complete precipitation,washed with distilled water to a negative reaction to

52

132 138

48

China

Bureya

Amur

Sungari Uss

uri

Gorin

Nikolaevsk�on�

Amur

Amur

Zeya

I

II

III

2 3

4

1

5

6

7

8

48

132 138

Lake Udyl

Ta

ta

r S

tr

ai

t

Blagoveshchensk

Khabarovsk

AmurskKomsomolsk�on�

Fig. 1. Schematic map of the region studied: (I) Zeya–Bureya Plain; (II) Central Amur Lowland; (III) Udyl–KizinLowland; (IV) Amur–Amgun’ Lowland; bottom sedimentsampling sites: (1) Lugovaya branch; (2) Romashkin Island;(3) Amurskaya branch; (4) Kafa branch; (5) city of Amursk;(6) Gorin River; (7) settlement of Takhta; (8) Pal’vinskayabranch.

Page 3: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

MINERALOGY AND CHEMISTRY OF FINELY DISPERSED BOTTOM SEDIMENTS 783

Cl– ions, and treated with a 10% H2O2 solution toremove the organic matter.

The identification of the minerals was performedon a Carl Zeiss Jena HZG�4a universal X�ray diffrac�tometer (Ni�filtered KαCu radiation; 40 kV, 30 mA,goniometer rotation speed: 2 degrees/min). Orientedpreparations were used for the X�ray diffractometry.They were analyzed in the air�dry state (20°C) afterincineration at 550°С for 2 h and saturation with eth�ylene glycol. The X�ray diffraction patterns were inter�preted using the conventional procedures [10, 17].The semiquantitative estimation of the content of clayminerals in the WPC and AC was performed by theBiscaye method [22].

The X�ray diffraction determination of the miner�alogy of the bottom�sediment fine fractions was sup�plemented by the electron�microscopic study using aCarl Zeiss EVO 40 HV scanning electron microscope(magnification ×50000). The samples were preparedby suspending in ethanol, drying, and Au coating. Aquadrant back scattering detector was used along withthe secondary electron detector for the analysis of thephases with high atomic numbers. In the imagesobtained with the quadrant back scattering detector,the phases with high average atomic numbers arereflected brighter than the phases with lower atomicnumbers. More than 500 images were thus obtained.

The total and microelement compositions of thebottom sediment fractions were determined by theenergy�dispersive X�ray fluorescence (EDXRF)method on a WRA�30 spectrometer. To obtain compa�rable data, the macroelement composition of the

components of the water–bottom sediments–algae–macrophytes–ichthyofauna system was analyzed byemission spectral analysis (ESA) on STE�1 and DFS�8instruments. All the samples were preliminarily driedat 105°C and incinerated at 450°C. The water in thedry residue was determined by ESA [14]. The differ�ences observed between the results of these methodsare related to the fact that the ESA is a semiquantita�tive method, in distinction from EDXRF, which istherefore preferable. However, ESA is widely used forsolving some geochemical problems until now [19].

RESULTS AND DISCUSSION

The behavior of the WPC and AC points to thesimilarity of their accumulation in the bottom sedi�ments. An increase in their content is observed alongthe Amur’s longitudinal profile. The content of WPCincreases from 2% in the Lugovaya branch to 8–10%in the lower course (Pal’vinskaya branch, settlement ofTakhta), and the content of AC increases from 12 to16–17% (Table 1). The abrupt increase in the contentof the fine bottom sediments in the Amurskaya branch(WPC, 9%; AC, 22%) is related to the estuary effect ofthe Ussuri River, where increased alluviation has beennoticed recently [13].

The average degree of the aggregation of the bot�tom�sediment clay (the AC/WPC ratio) is signifi�cantly lower than the corresponding values for thehumus�accumulative horizons of the Central AmurLowland soils (2.1 and 8.4, respectively). By the

Table 1. Contents of the fine fractions in the bottom sediments of the Amur River basin and their clay minerals, %

Sample WPC ACAC components

kaolinite + chlorite hydromicas interstratified structures

Point 1, Lugovaya branch 2.4 11.6 16.4 48.6 35.0

Point 2, Romashkin Island 7.2 12.1 9.9 62.0 28.1

Point 3, Amurskaya branch 8.7 22.5 8.5 60.5 31.0

Point 4, Kafa branch 4.5 11.2 16.9 67.2 15.9

Point 5, city of Amursk 6.6 13.2 19.3 40.4 40.3

Point 6, Gorin River 9.0 14.2 10.9 71.2 17.9

Point 7, settlement of Takhta 9.8 15.7 12.1 66.3 21.6

Point 8, Pal’vinskaya branch 8.2 16.8 11.7 62.4 25.9

Note: The WPC minerals could not be identified because of their imperfect structures.

Page 4: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

784

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

CHIZHIKOVA et al.

degree of aggregation, the bottom sediments approachthe soil�forming rocks of the lowland [20].

The X�ray structural analysis of the subfractionsobtained by the fractional peptization of the bottomsediments indicates significant differences in the min�eralogy between the WPC and AC. In the entire stud�ied segment of the Amur, the bottom sediments con�tain WPC, whose main components are highly dis�persed quartz and fragmentary forms of feldspars(Fig. 2) accompanied by strongly disordered layeredsilicates. According to the electron spectroscopy data,the WPC contains many skeletons of centric diatomicalgae (Fig. 3), which probably resulted in the highcontent of total silica. The identified layered silicates

include kaolinite and strongly hydrated hydromicas,mainly of the trioctahedral type. The proportions ofthe main mineral phases in the layered silicates couldnot be calculated for the reason that no oriented prep�arations were obtained because of the presence ofhighly dispersed quartz and fragmentary feldspars.

Most of the clay minerals are concentrated in theAC (Fig. 2). The clay minerals mainly consist of trioc�tahedral hydromicas with some dioctahedral struc�tures (40.4–71.2%) and disordered interstratified for�mations of several types: mica�smectites, chlorite�smectites, and kaolinite�smectites. The total contentof these structures varies from 15.9 to 40.3%. Kaoliniteand chlorite are also present; the degree of the chlorite

0.13

80.

334

0.35

5

0.42

6

0.44

1.0

1.0

1.0

1.0

1.0 1.

0

1.0 1.

0

1.0

1.0

~1.

8~

1.8

~1.

8

1.0

1.0

0.70

0.70

0.70

0.70

0.70

0.70

0.74

1.0

1.0 1.

01.

0

1.0

1.0

1.0

1.0

1.4

1.4

1.4

1.4

0.74

0.70 1.

01.

01.

0

0.74

0.74

0.74

0.70

0.70

0.42

6

0.35

50.

355

0.35

50.

334

0.33

40.

334

0.13

80.

138

0.13

80.

334

0.33

40.

334

0.33

40.

355

0.35

50.

355

0.35

5

0.13

80.

138

0.42

60.

426

1

2

3

4

5

6

7

8

а b cI

0.33

40.

355

0.47

1.0

1.0

1.0

1.0

1.0

1.0

1.0

1.0

1.0 1.

0

1.7

1.7

1.0

1.0

0.70

0.70

0.700.

700.

700.

70

1.0

1.0

1.0

1.0

1.0

1.0

1.0

1.4

1.3

1.2

1.6

0.70

1.0

1.0

0.70

0.70

0.70

0.35

50.

355

0.35

50.

334

0.33

40.

334

0.33

40.

334

0.33

40.

334

0.35

50.

355

0.35

50.

355

1

2

3

4

5

6

7

8

а b cII

1.2

0.50

0.47

0.47

0.47

0.70

0.50

0.47

0.50

~1.

8~

1.8

1.8

1.8

0.70

1.2

1.2

1.3

1.4

1.2

0.50

0.50

0.47

0.50

1.4

0.70

0.70

0.70

0.50

0.47

1.2

1.21.

01.

4

1.4

1.3

1.0

1.0

0.70

Fig. 2. X�ray diffraction patterns of the fine bottom�sediment component: (I) WPC; (II) AC; the sampling sites are given in Fig. 1;(a) air�dry samples; (b) samples after solvation with ethylene glycol; (c) samples after incineration at 550°C.

Page 5: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

MINERALOGY AND CHEMISTRY OF FINELY DISPERSED BOTTOM SEDIMENTS 785

degradation significantly varies among the studiedsamples of the bottom sediments. The total content ofthese two components is 8.5–19.3%. This category ofclays also contains highly dispersed quartz, but its con�tent is significantly lower. Skeletons of diatomic algaeare also found (Fig. 4).

The differences in the AC composition of the bot�tom sediments within the region between the Sungari’smouth and the Amur estuary are determined by thetype of accumulation and the estuary effects of thelarge tributaries. The highest content of kaolinite�smectites with a high content of smectite layers is

observed in the clays of the lacustrine accumulationzone (the water intake region of the city of Amursk,downstream of Lake Padali, point 5), and the highestcontent of hydromicas is found in the deposits at theGorin River confluence (mountain river, point 6). TheAC mineralogy of the bottom sediments in the Amur ischaracterized by the presence of kaolinite�smectites,which are widely distributed in the surface deposits andsoils of the Amur basin, as was noted previously [16].

After the separation of the fine WPC and AC frac�tions from the bottom sediments, clastic minerals(quartz, feldspars, micas) with different degrees of

(e)

1 µm 1 µm

1 µm 200 nm

200 nm 200 nm

(c) (d)

(f)

(а) (b)

Fig. 3. WPC photomicrographs: (a–d) WPC and centric diatom skeleton microstructures; (e, f) fragmentary feldspars (scanningelectron microscopy).

Page 6: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

786

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

CHIZHIKOVA et al.

weathering and dispersions prevail in the residue(Fig. 5). Many pennatic and centric diatoms are observedin the samples of the bottom sediments (Fig. 6). It can beseen (Figs. 3, 4) that the highest content of diatoms(predominantly centric and fragmentary pennatic dia�toms) is concentrated in the fine fractions, and theyare almost absent in the residue after the separation ofthe clays.

The composition of the clay minerals in the finebottom sediments of the Amur basin corresponds tothe petrographic�mineralogical class of terrestrial eco�systems of smectite–hydromica composition [7–9].

The separation of the clay into the water�peptized andaggregated subfractions, which is frequently used forstudying the genesis of soils, allows assessing the het�erogeneity of the fine bottom�sediment component.General tendencies are observed for the soils and bot�tom sediments. As in the soils of the Central AmurLowland, the bottom�sediment WPC contains morefine quartz, feldspars, and hydromicas. The WPCminerals have an imperfect structure and are disordered.The AC minerals are characterized by a more perfectstructure and the presence of phases with a labile struc�tural component. The subfractions obtained by the frac�

3 µm(а)

200 nm

300 nm

1 µm

2 µm

1 µm(b)

(c) (d)

(e) (f)

Fig. 4. AC photomicrographs: (a, b) AC and centric diatom skeleton microstructures; (c, d) mica–hydromica plates; (e) micro�aggregates and crystallites of clay minerals; (f) inclusions of minerals with higher atomic masses than clay minerals (scanning elec�tron microscopy; on the left, the secondary electron and quadrant back scattering detector, respectively).

Page 7: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

MINERALOGY AND CHEMISTRY OF FINELY DISPERSED BOTTOM SEDIMENTS 787

tional peptization contain skeletons of diatomic algae,most of which are found in the WPC.

The bulk analysis (Table 2) revealed some interest�ing tendencies in the distribution of the microele�ments among the fractions of the bottom sediments.Because of the predominance of fine quartz and feld�spars, the bottom�sediment WPC contains loweramounts of aluminum and iron than the AC (16.97–18.38 and 19.07–20.76% for Al, and 10.02–12.99 and13.85–16.16% for Fe, respectively). The total contentof potassium in the clays is also high: 3.23% on theaverage in the WPC due to feldspar potassium and3.02% in the AC due to K�hydromicas.

The clay fractions are usually characterized byhigher total contents of iron and manganese comparedto the residue after the separation of the clays and theentire bottom sediments. The average content of ironis 11.8 and 14.9% in the WPC and AC, respectively. Itscontent in the entire bottom sediments and the residueafter the separation of the clays is significantly lower(4.9 and 2.9%, respectively). The high content of totaliron corresponds to the presence of chlorites andinterstratified mica�smectite structures in the finecomponent of the bottom sediments [4]. It is known[23] that iron is one of the main growth regulators ofthe diatomic alga population (after silicon and nitro�gen). The highest content of iron in the clay fractionsof the bottom sediments (WPC, 12.99; AC, 16.16%),which was found in the Kafa branch (point 4), isrelated to the sedimentation of minerals under theconditions of the slow flow in this river segment. Thelowest iron content (WPC, 10.02%; AC, 13.85%),which was recorded in the Gorin River’s mouth (point 6),is due to the significant decrease in the content of allthe layered silicates and an increase in the content ofquartz.

In the Amur bottom sediments, the contents ofmicroelements do not exceed their average contents inthe sedimentary rocks. At the same time, the contentsof zinc and strontium are lower than this level by a fac�tor of more than 1.5 [2]. The fluvial and lacustrine(Lake Udyl) deposits in the Amur basin are character�ized by similar microelement compositions. The high�est (more than by 1.5�times) excess of manganese,zinc, and copper compared to their average contentsin the sedimentary rocks is observed in the sewagesludge: 2300, 410, and 200 mg/kg, respectively.

The fine fractions contain significantly largeramounts of zinc, copper, nickel, and rubidium thanthe residue after the separation of clays (Table 3). Theaverage contents of zinc are 146, 180, and 59 mg/kg inthe WPC, AC, and the residue, respectively. The cor�responding values for Cu are 41, 40, and 20 mg/kg.The accumulation of the microelements by the finecomponents of the bottom sediments can be related tothe formation of surface complexes of heavy metal

cations with clay minerals [25, 28, 29]. At the sametime, the contents of zinc and strontium in the residueafter the clay separation are higher than those in the

1 µm(а)

2 µm(b)

2 µm(c)

10 µm(d)

Fig. 5. Photomicrographs of the residue after the clay sep�aration; corroded grains of clastic minerals: (a–d) feld�spars with different degrees of weathering and dispersion.

Page 8: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

788

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

CHIZHIKOVA et al.

3 µm(а) 1 µm(b)

3 µm(c) 1 µm(d)

1 µm(e) (f) 200 nm

Fig. 6. Photomicrographs of the bottom sediments: (a) in the center, two parallel skeletons of pennatic diatoms; below on theright, a centric diatom skeleton; (b) side view of a centric diatom skeleton; (c) in the center, fragments of pennatic diatom skele�tons with wide septa and a centric diatom; (d) fragment of a large centric diatom; (e) centric diatom valve; (f) fragment of a pen�natic diatom skeleton.

fine fractions by 2–3 times. For example, the averagecontents of zirconium in the WPC, AC, and the resi�due from the separation of the clays are 141, 176, and371 mg/kg, respectively.

The generalized data on the contents of the microele�ments in the separate components of the water–bottomsediments–algae–macrophytes–ichthyofauna systemin the region between the city of Blagoveshchensk andthe Amur estuary are given in Table 4. The microele�ment composition of the Amur water is compared with

the average contents (clarkes) of the microelements inthe water of land rivers [26]; the composition of theAmur and Lake Udyr’ bottom sediments, the algae(seston, periphyton), the sewage sludge, the macro�phytes, and the ichthyofauna (Table 2) is comparedwith the average contents (clarkes) of the microele�ments in the sedimentary rocks (clays and shists) [2].The contents of iron and manganese in the water canexceed the average contents (clarkes) of these ele�ments in the river water by more than 1.5 times. The

Page 9: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

MINERALOGY AND CHEMISTRY OF FINELY DISPERSED BOTTOM SEDIMENTS 789 Table 2. Total macroelement contents in the bottom�sediment fractions from the Amur River, %

Sample SiO2 Al2O3 Fe2O3 TiO2 MnO CaO MgO K2O Na2O

WPC/AC

Point 1, Lugovaya branch

Point 2, Romashkin Island

Point 3, Amurskaya branch

Point 4, Kafa branch

Point 5, city of Amursk

Point 6, Gorin River

Point 7, settlement of Takhta

Point 8, Pal’vinskaya branch

Residue after the clay separation from the bottom sediments

Point 1, Lugovaya branch –

Point 2, Romashkin Island –

Point 3, Amurskaya branch –

Point 4, Kafa branch –

Point 5, city of Amursk –

Point 6, Gorin River –

Point 7, settlement of Takhta –

Point 8, Pal’vinskaya branch –

Note: (dash) the element’s content is below the method’s detection limit.

50.8853.35���������� 16.97

20.76���������� 12.03

14.13���������� 0.82

1.11�������� 0.23

0.27�������� 4.82

1.49�������� 2.26

3.76�������� 3.60

3.03�������� 1.91

1.29��������

53.7854.62���������� 17.07

19.86���������� 12.08

14.20���������� 0.98

1.02�������� 0.36

0.24�������� 2.93

1.50�������� 2.06

3.55�������� 3.28

2.82�������� 1.91

1.14��������

54.2055.49���������� 18.38

19.90���������� 12.91

14.86���������� 0.98

1.18�������� 0.15

0.19�������� 3.62

1.73�������� 2.56

2.15�������� 3.02

2.93�������� 1.18

0.49��������

51.0153.74���������� 17.40

19.95���������� 12.99

16.16���������� 0.93

1.16�������� 0.18

0.34�������� 4.02

1.73�������� 2.39

2.68�������� 3.06

3.11�������� 1.48

0.19��������

53.2955.24���������� 17.46

19.55���������� 12.28

15.66���������� 0.95

1.14�������� 0.25

0.22�������� 4.41

1.77�������� 2.62

2.20�������� 2.94

3.00�������� 1.35

0.15��������

56.4258.28���������� 17.51

19.07���������� 10.02

13.85���������� 0.82

0.99�������� 0.14

0.12�������� 1.26

1.00�������� 2.24

1.62�������� 3.67

3.33�������� 2.14

0.30��������

53.8054.77���������� 17.93

19.63���������� 11.20

15.62���������� 0.92

1.14�������� 0.27

0.24�������� 2.63

1.78�������� 2.55

2.26�������� 3.64

2.96�������� 1.67

0.15��������

55.6156.25���������� 18.19

19.63���������� 10.69

14.78���������� 0.91

1.14�������� 0.24

0.18�������� 2.17

1.49�������� 2.41

2.21�������� 3.14

2.94�������� 1.79

0.15��������

74.4767.10���������� 12.89

14.84���������� 2.44

3.81�������� 0.61

0.73�������� 0.08

0.11�������� 1.69

1.69�������� 0.15

0.38�������� 3.40

3.27��������

74.7465.99���������� 12.09

14.90���������� 2.38

4.75�������� 0.80

1.01�������� 0.06

0.11�������� 1.51

1.56�������� 0.44

0.20�������� 2.92

3.04��������

70.8064.47���������� 13.37

16.37���������� 3.91

6.43�������� 0.89

1.05�������� 0.16

0.20�������� 1.43

1.57�������� 0.54

0.35�������� 2.77

3.03��������

74.0968.00���������� 12.03

13.90���������� 2.37

3.99�������� 0.69

0.67�������� 0.06

0.08�������� 1.66

1.64�������� 0.42

0.37�������� 3.04

3.04��������

71.5567.19���������� 12.69

15.73���������� 2.98

4.82�������� 0.58

0.73�������� 0.05

0.14�������� 1.53

1.64�������� 0.05

0.70�������� 3.08

3.04��������

75.9967.90���������� 12.54

14.37���������� 3.11

4.95�������� 0.66

0.82�������� 0.06

0.10�������� 0.71

0.71�������� 0.42

0.26�������� 2.46

2.69��������

73.1867.66���������� 12.48

15.54���������� 2.92

5.26�������� 0.83

0.88�������� 0.06

0.13�������� 1.53

1.70�������� 0.10

0.24�������� 3.02

3.19��������

73.4664.75���������� 12.85

15.41���������� 2.94

4.96�������� 0.74

0.80�������� 0.06

0.07�������� 1.53

1.35�������� 0.30

0.64�������� 2.92

2.81��������

Page 10: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

790

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

CHIZHIKOVA et al.

contents of copper, zinc, strontium, and zirconium aresignificantly lower than these values; the other ele�ments are within the 1.5�fold changes in the averagecontents (clarkes) of the microelements in the riverwaters.

The microelement composition of the algae(seston, periphyton) is similar to that of the fine bot�tom�sediment fractions. In the biological objects, thecontent of microelements regularly increases in theseries seston ~ periphyton > macrophytes > ichthyo�

Table 3. Total microelement contents in the bottom�sediment fractions from the Amur River, mg/kg

Sample Ni Cu Zn Ga Pb Rb Sr Y Zr

WPC/AC

Point 1, Lugovaya branch

Point 2, Romashkin Island

Point 3, Amurskaya branch

Point 4, Kafa branch

Point 5, city of Amursk

Point 6, Gorin River

Point 7, settlement of Takhta

Point 8, Pal’vinskaya branch

Residue after the clay separation from the bottom sediments

Point 1, Lugovaya branch

Point 2, Romashkin Island

Point 3, Amurskaya branch

Point 4, Kafa branch

Point 5, city of Amursk

Point 6, Gorin River

Point 7, settlement of Takhta

Point 8, Pal’vinskaya branch

5072���� 36

43���� 140

193������� 16

33���� 35

36���� 108

152������� 230

117������� 21

31���� 124

173�������

5255���� 51

34���� 142

187������� 28

36���� 0

0�� 114

130������� 155

104������� 27

30���� 160

218�������

5263���� 45

34���� 139

159������� 25

28���� 25

0���� 126

145������� 176

103������� 28

31���� 140

165�������

6056���� 49

39���� 158

192������� 29

29���� 0

28���� 125

144������� 203

113������� 23

30���� 143

192�������

4355���� 42

45���� 151

188������� 27

28���� 0

0�� 123

144������� 187

105������� 27

28���� 146

164�������

4747���� 36

33���� 147

162������� 31

25���� 37

41���� 131

144������� 76

61���� 21

30���� 125

155�������

6048���� 33

50���� 135

173������� 24

35���� 0

0�� 125

141������� 140

101������� 25

29���� 145

167�������

4974���� 33

44���� 155

186������� 25

35���� 42

33���� 138

140������� 146

92������� 28

30���� 146

175�������

1625���� 40

13���� 44

73���� 22

24���� 24

33���� 120

124������� 387

358�������

2930���� 396

424�������

328

���� 2226���� 49

74���� 9

13���� 17

33���� 95

125������� 269

260������� 26

29���� 470

510�������

2647���� 22

49���� 75

105������� 14

14���� 30

35���� 118

141������� 280

243������� 35

34���� 349

297�������

2520���� 14

23���� 51

68���� 22

14���� 17

33���� 104

116������� 357

326������� 30

30���� 429

453�������

2112���� 6

18���� 61

81���� 29

29���� 20

29���� 107

121������� 353

296������� 27

32���� 307

316�������

340

���� 1026���� 81

102������� 11

17���� 14

20���� 100

113������� 175

150������� 23

30���� 297

291�������

1222���� 19

29���� 52

116������� 12

26���� 27

24���� 102

128������� 317

282������� 30

29���� 349

306�������

2632���� 27

33���� 58

104������� 13

9���� 16

29���� 111

124������� 337

276������� 32

33���� 370

338�������

Page 11: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

MINERALOGY AND CHEMISTRY OF FINELY DISPERSED BOTTOM SEDIMENTS 791

Tabl

e 4.

Mic

roel

emen

tal c

ompo

siti

ons

of t

he

wat

er,

bott

om�s

edim

ent

ash

, an

d bi

olog

ical

obj

ects

in t

he

Am

ur R

iver

(em

issi

on s

pect

rosc

opic

an

alys

is)*

Ele

men

t

Riv

er w

ater

s [2

6]R

iver

wat

er,

n =

85

Sed

imen

tary

ro

cks

([2]

)B

otto

m s

edi�

men

ts, n

= 5

1U

dyl b

otto

m

sedi

men

ts, n

= 2

5S

ewag

e sl

udge

, n =

6S

esto

n, n

= 2

4P

eryp

hyto

n,

n =

30

Mac

roph

ytes

, n

= 1

4Ic

hthy

ofau

na,

n =

39

µg/

dm3

mg/

kg a

sh

Mn

7–10

670

Fe*

410–

670

4.65

Ni

0.3–

2.5

95

Cu

3–7

57

Zn

15–

2080

Sr

50–

7045

0

Zr

0.8–

2.6

200

Pb

1–3

20

Not

es:

the

aver

age

valu

es a

nd

the

min

–m

ax r

ange

s ar

e gi

ven

abo

ve a

nd

unde

r th

e li

ne,

res

pect

ivel

y; (

n) th

e n

umbe

r of

rep

lica

tes;

*th

e da

ta o

n th

e co

nte

nt o

f iro

n (

exce

pt fo

r it

s co

nte

nt

in t

he

rive

r w

ater

) ar

e gi

ven

in p

erce

nt.

500

–14

2���

������

����66

030

0–

1000

������

������

������

��54

010

0–

800

������

������

�����

2300

600

–10

000

������

������

������

�����

2100

400

–60

00���

������

������

�����

1500

400

–60

00���

������

������

�����

1600

300

–60

00���

������

������

�����

9010

–30

0���

������

������

970

15–

2750

������

������

�����

2–

41–

6���

�����

2–

52

–6

������

��2

–5

1–6

������

��4

–7

1–10

������

����

3–

61–

10���

������

�1–

21–

3���

�����

0.1

0.00

1–1

������

������

����

1.5

0–

4.5

������

������

2810

–40

������

�������

2010

–30

������

�������

3520

–60

������

�������

196

–30

������

����

256

–60

������

����

64

–10

������

����

4 4��

2.2

0.1–

5.9

������

������

���20

10–

40���

������

����20 20���

�20

010

0–

300

������

������

�����

5020

–10

0���

������

������

4020

–80

������

�������

3020

–10

0���

������

������

2020

–30

������

�������

2.1

0.1–

8.3

������

������

���80

0–

300

������

�������

6030

–10

0���

������

������

410

300

–60

0���

������

������

��22

030

–80

0���

������

������

170

10–

800

������

������

���14

6–

60���

������

�12

06

–30

0���

������

����

138

–32

������

����

160

100

–30

0���

������

������

��10

010

0���

����10

010

0���

����10

010

0–

200

������

������

�����

100

100

�������

300

100

–40

0���

������

������

��10

010

0–

200

������

������

�����

0.7

0–

5.3

������

������

370

200

–60

0���

������

������

��20

010

0–

300

������

������

�����

200

200

�������

140

60–

200

������

������

���10

060

–20

0���

������

������

304

–80

������

����

43

–4

������

��

1.0

0–

7.8

������

������

2010

–40

������

�������

136

–20

������

����

2520

–40

������

�������

3310

–10

0���

������

������

206

–80

������

����

146

–80

������

����

76–

10���

������

Page 12: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

792

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

CHIZHIKOVA et al.

fauna. Only a little accumulation of strontium isobserved in the macrophytes compared to the seston:100 and 300 mg/kg of ash, respectively.

Thus, the algae have the highest accumulationcapacity for heavy metals of the biological objects inthe Amur ecosystem. The accumulation of manga�nese, iron, copper, and zinc in them suggests that theseelements can accumulate in the fine fractions of thebottom sediments also due to diatomic algae.

CONCLUSIONS

The study of the fine bottom sediments from theAmur River showed that their clay minerals corre�spond to terrestrial ecosystems of smectite–hydrom�ica composition [7–9]. The water�peptized clays ofthe bottom sediments contain more fine quartz, feld�spars, and hydromicas. The total silica of the bottomsediments includes, along with quartz, the silica ofdiatom skeletons. The WPC minerals have an imper�fect structure and are disordered. The ACs consist oflayered silicates, which can have a higher degree ofstructuring.

In the total composition of the bottom sediments,the contents of the microelements do not exceed theiraverage contents in the sedimentary rocks. The con�tents of iron, manganese, zinc, and copper in the clayfractions are higher than in the entire bottom sedi�ments and the residue after the separation of the claysby more than two times. The accumulation of micro�elements by the fine components of the bottom sedi�ments can be related to the formation of surface com�plexes of heavy metal cations with clay minerals. Therevealed high accumulation capacity of the diatomicalgae for iron, manganese, zinc, and copper and theirhigh contents in the clay fractions suggest that theaccumulation of these elements in the fine fractions ofthe bottom sediments can also due to the diatomicalgae.

REFERENCES

1. P. Ya. Baklanov and B. A. Voronov, “Global andRegional Risks for Sustainable Nature Management inthe Amur River Basin,” Izv. Ross. Akad. Nauk, Ser.Geogr., No. 2, 17–24 (2010).

2. A. P. Vinogradov, “Average Contents of Chemical Ele�ments in the Main Types of Volcanic Rocks,”Geokhimiya, No. 7, 555–571 (1962).

3. G. N. Vitvitskii, “Climate in the Southern Regions ofthe Far East,” in Southern Regions of the Far East(Nauka, Moscow, 1969), pp. 70–97 [in Russian].

4. Yu. N. Vodyanitskii and V. V. Dobrovol’skii, Iron Min�erals and Heavy Metals in Soils (Ross. Akad. S–Kh.Nauk, Moscow, 1998) [in Russian].

5. “Khabarovsk Krai and Amur Oblast: Part 1. GeologicalDescription,” in Geology of the USSR (Nedra, Moscow,1966), Vol. 19, pp. 645–658, 686–687 [in Russian].

6. N. I. Gorbunov, Mineralogy and Physical Chemistry ofSoils (Nauka, Moscow, 1978) [in Russian].

7. B. P. Gradusov and N. P. Chizhikova, “Factors andGeography of River�Runoff Clay Minerals,” Dokl.Akad. Nauk SSSR 234 (2), 425–428 (1977).

8. B. P. Gradusov, “Assessing the Composition and Prop�erties of the Lithogenic Basis of Global Ecosystems,”Pochvovedenie, No. 2, 217–225 (1995).

9. B. P. Gradusov, A. G. Chernyakhovskii, and N. P. Chizhi�kova, “Ecological Mineralogy and Petrography ofSoils,” in Problems of Siberian Soil Science (Nauka,Novosibirsk, 1990), pp. 13–34 [in Russian].

10. I. Kostov, Mineralogy, Series Geosciences (Mir, Mos�cow, 1971) [in Russian].

11. V. Kryukov, “Sustainable Development of the AmurRiver Basin (Russian Territory) from the EcologicalPoint of View,” in Energy and Environment in SlavicEurasia: toward the Establishment of the Network ofEnvironmental Studies in the Pan�Okhotsk Region. 4.Environmental Protection – East Asia I Title, Part 2, Ed.By T. Shinichiro (Slavic Research Center, HokkaidoUniversity, Sapporo, 2008), pp. 127–156.

12. Yu. A. Liverovskii, “Lowland Landscapes of the South�ern Primor’e and Amur Regions and Their Genesis,” inProblems of Physical Geography (Akad. Nauk SSSR,Moscow, 1946), No. 12, pp. 47–60 [in Russian].

13. A. N. Makhinov, R. S. Chalov, and A. V. Chernov, “Ero�sion of Central Amur Banks,” Geomorfologiya, No. 2,72–81 (2001).

14. Yu. A. Mikhalev, S. E. Sirotskii, and G. V. Kharitonova,“X�Ray Fluorescence Determination of Heavy Metalsin Natural Water,” Lab. Novosti DV, No. 1, 18 (1999).

15. V. V. Nikol’skaya, Morphosculpture of the Amur RiverBasin (Nauka, Moscow, 1972) [in Russian].

16. B. F. Pshenichnikov and B. P. Gradusov, “Mineralogyand Chemistry of Clay Materials in the PodzolicHumus�Illuvial Soils of the Sikhote�Alin’,” in GleyProcesses and Physicochemical Properties of Soils in theSouthern Regions of the Far East (Akad. Nauk SSSR,Vladivostok, 1980), pp. 43–55 [in Russian].

17. The X�Ray Identification and Crystal Structures of ClayMinerals, Ed. by G. Brown (Mineralogical Society,London, 1961).

18. Yu. D. Tret’yakov, “Morphological Diversity in theNanosized Inorganic Substances and Materials,”Vestn. Ross. Akad. Nauk 80 (7), 591–597 (2010).

19. H. Hawkes and J. Webb, Geochemistry in MineralExploration (Harper and Row, New York, 1962).

20. N. P. Chizhikova, G. V. Kharitonova, L. A. Matyush�kina, and S. E. Sirotskii, “Mineralogical Compositionof the Clay Fraction in Soils, Bottom Sediments, andSuspended Matter in the Middle and Low Reaches ofthe Amur River,” Pochvovedenie, No. 8, 1000–1012(2004) [Eur. Soil Sci. 37 (8), 876–888 (2004)].

21. D. I. Shashko, “Agroclimatic Zoning of the USSR bythe Heat and Water Supply of Plants,” in Problems inthe Agroclimatic Zoning of the USSR (Sel’khozgiz, Mos�cow, 1958), pp. 38–97 [in Russian].

22. P. E. Biscaye, “Mineralogy and Sedimentation of theDeepsea Sediment Fine Fraction in the AtlanticOcean,” Geochem. Techn. Rept. 8, 97–105 (1964).

Page 13: Mineralogy and chemistry of finely dispersed bottom sediments in the Amur River

EURASIAN SOIL SCIENCE Vol. 44 No. 7 2011

MINERALOGY AND CHEMISTRY OF FINELY DISPERSED BOTTOM SEDIMENTS 793

23. M. A. Brzezinski, “Mining the Diatom Genome for theMechanism of Biosilification,” Proc. Natl. Acad. Sci.USA 105 (5), 1391–1392 (2008).

24. U. Förstner and G. T. W. Wittmann, Metal Pollution inthe Aquatic Environment (Springer, 1983).

25. G. V. Kharitonova, A. S. Manucharov, A. V. Kiri�chenko, and I. A. Pavlyukov, “Electron Microscopy ofClay Minerals Treated with Salt Solutions,” Eur. SoilSci. 39 (Suppl. 1), S69–S77 (2006).

26. D. A. Livingston, “Chemical Composition of Riversand Lakes: Date of Geochemistry,” in U.S. Geol. SurveyProfess., Paper 440G, p. G1–G64 (1963).

27. J. Moor and S. Ramamoorthy, Heavy Metals in NaturalWaters: Applied Monitoring and Impact Assessment(Springer, New York, 1984).

28. D. L. Sparks, “Toxic Metals in the Environment: theRole of Surfaces,” Elements 1, 193–197 (2005).

29. G. Sposito, The Surface Chemistry of Soils (OxfordUniv. Press, New York, 1984).