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FISHERIES AND MARINE -SERVICE

Translation Series No. 3536

Trace elements in bottom sediments of River reservoirs

by Ye.P. Nakhshina

•

Original title: Mikroelementy v donnykh otlozheniyakh vodokranilishch r, Dnepra

From: Gidrokhim. Mater. 57: 30-38, 1973

Translated by the Translation Bureau(NDE) Multilingual Services Division Department of the Secretary of State of Canada

Department of the Environment Fisheries and Marine Service Freshwater Institute Winnipeg, Manitoba

1975

14 pages typescript t i)7)

DEPARTMENT OF THE SECRETARY OF STATE SECRÉTARIAT D'ÉTAT

TRANSLATION BUREAU BUREAU DES TRADUCTIONS

MULTILINGUAL SERVICES DIVISION DES SERVICES CANADA DIVISION MULTILINGUES

TRANSLATED FROM — TRADUCTION DE INTO — EN ' Russian English AUTHOR — AUTEUR Ye.P, Nakhshina

TITLE IN F:NGLISH — TITRE ANGLAIS Trace elements in bottom sediments of Dnieper River reservoirs

TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS) « TITRE EN LANGUE ÉTRANGÉRE (TRANSCRIRE EN CARACTÉRES ROMAINS) Mikroelementy v donnvkh otiozhenivakh vodokhranilishch r. Dnepra

REFERENCE IN FOREIGN IANGLIAGE (NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE FOREIGN CHARACTERS. RÉFÉFIL NCE EN '_ANGUE ÉTRANCÉRE (NON', DU LIVRE OU PUBLICATION), AU COMPLET, ritANSCRIRE EN CARACTÈRES ROMAINS. Gidrokhimicheskiye materialy, Gidrokhimicheskiy Institut (Novocherkassk)

REFERENCE IN ENGLISH — RÉFÉRENCE EN ANGLAIS Hydrochemical Materials of the Hydrochemical institute (Novocherkassk)

PUBLISHER — ÉDITEUR PAGE NUMI3ERS IN ORIGINAL DATE OF PUBLICATION NUMéROS DES PAGES DANS not available DATE DE PUI3LICATION L'ORIGINAL

YEAR ISSUE NO. 30-.38 VOLUME PLACE OF PUBLICATION ANNéE NUMÉRO NumBER or TYPED PAGES LIEU DE PUBLICATION NOMBRE DE PAGES USSR DACTYLOGRAPHIÉES 1973 OM% 57 114.

REQUESTING DEPARTMENT TRANSLATION BUREAU NO. MINISTÈRE-CLIENT Environment NOTRE DOSSIER No 1101037

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PERSON REQUESTING K.E. Marshall ' DEMANDÉ PAR , y YOUR NUMBER VOTRE DOSSIER N° N

DATE OF REQUEST DATE DE LA DEMANDE August 12 1975

SOS.20040.6(HEV.2/68) 763C-2 1-020.b»3 y "»-?

• ) DEPARTMENT OF THE SECRETARY OF STATE SECRÉTARIAT D'ÉTAT TRANSLATION BUREAU BUREAU DES TRADUCTIONS

MULTILINGUAL SERVICES DIVISION DES SERVICES DIVISION MULTILINGUES

C LIENTS NO. DEPARTMENT DIVISION/BRANCH CITY N° DU CLIENT MINISTRE DIVISION/DIRECTION VILLE Environment Fisheries Service Winnipeg Man.

BUREAU NO. LANGUAGE TRANSLATOR (INITIALS) N ° DU BUREAU LANGUE TRADUCTEUR (INITIALES) 1101037 Russian N. De. SEP 1 7 11r/5

U1147-:jUD Gidrokhimicheskiye materialy, Gidrokhimicheskiy t, • Institut (Novocherkassk), 1973, vol. 57, pp. 30-38. U141,eriiZU .4une ;u1:171u

TRACE ELEMENTS IN BOTTOM SEDIMENTS OF DNIEPER RIVER RESERVOIRS. 1

by Ye. P. Nakhshina [30]*1

The distribution of heavy metals in the bottom sediments of.Dnieper River

reservoirs bad not been studied until recently, despite the fact that their role

in the trace element cycle is extremely important. They are the "accumulators"

(1) or "depots" (2) of trace elements in a body of water. It has also been es-

tablished that bottom sediments have a high potential absorptive capacity with

respect to the ions of heavy metals (3), which determines their important role. .

in the self-purification of water bodies.

Many works have been devoted to the study of heavy metal distribution in

sea and ocean sediments (4-9 and others). A study has been made on the distri-

bution of trace elements in the bottom sediments of ponds in various biogeochem-

ical provinces of the USSR (1, 10, 11), lakes of Kazakhstan (12, 13) and water

bodies of Priazovye (14-16) and the Volga (17).

* The numbers in the right-hand margin are the pages of the Russian text - translator.

00s-200-10-51 ^..:^ ^^ .,:.. +.u:.i'^;Aù:m^..k.^ .1•,G F^ ^.:... ^ .,,F.;,^_r.awhtï4 :.:,ti.;r.è..:cüs:+. 2

I The calculation of the total content of four bioelements (manganese, zinc,

copper and cobalt) in the bottom sediments of the Kiev Reservoir, carried out in

1967 in accordance with the International Biological Program (18), was the begin-

ning of investigations on the entire series of reservoirs on the Dnieper River.

During expeditions in August-September 1968, we took samples of bottom sediments

from the Kiev, Kremenchug, Dneprodzerzhinsk, Dnieper and Kakhovka reservoirs

Inunediately after taking the samples, we measured the pH level in (see Fig.).

the ground column, and then determined the hygroscopic moisture, the'losses due

to calcinationl and the content of bulk manganese, zinc, copper and cobalt in

air-dry samples in laboratory conditions.

Si02 was extracted (20) after removing the organic substance by roasting

the samples at a temperature of approximately 450-500°C; the manganese was iden-

tified using the colorimetric method developed for soils (21); zinc, copper and

cobalt were also identified colorimetrically, however, the techniques applied in

soil analysis (22) were altered somewhat - copper was identified using diethyl--

dithiocarbamate of lead, and zinc by combined staining with dithizonate and dithi--

Calculations were made in absolutely dry weight. The obtained data were zone.

processed statistically, establishing the mean values, the confidence range of

variance, the coefficients of correlation r between various indices and the de-,

gree of their reliability with the given number of samples. [31] On the basis of a granulometric analysis (23), we divided the studied

soils into three groups (for convenient comparison and calculations), group I

including slightly silty and silty sands, group II - sandy silt.s, and group III

silts and clay silts. Table 1 contains data characterizing the threshold and

mean content values of organic substance in the bottom sediments of Dnieper

reservoirs.

1 This is the most easily determined index of the total. content of organic sub- In the studied samples, it correlates quite well with the content of stance. organic carbon (r=+0.8-0.9), which has been determined by I.K. Palamarchuk (19). taiata.P.

• a •

• . s

Kiev Fiktea

■ o a ■tee

e pit a CCut Kt el N $1 1mi Chteki146/ pe m e H vi r

eD11eret Aztu-zitie flmenpo.a3eplitruicFi Arienponerposcrt

• , „anopo,R.,

Reservoirs on the Dnieper River. Reservoirs: 1 - Kiev (F=922 km2 , 16 samples taken), 2 - Kremenchug (F=2250 km 2 , 22 samples),"3 - Dneprodzerzhinsk (F=567 km 2 , 5 samples), 4 - Dnieper (F=410 kmz, 9 samples), 5 - Kakhovka (F=2150 km 2 , 46 samples).

Manganese. The content of bulk manganese in the bottom sediments of

Dnieper River reservoirs varies within a broad range - from n.10-3 to n.10-1 %;

therefore, the use of the term "trace element" in certain cases is unjustified,

manganese being a macrocomponent of the soils. The mean values lie within a

narrower range - from n.10-2 to n.10-1 %.

The entry of manganese into the soils and its distribution in them is

determined by a combination of factors - the pH level and redox conditions

(24-26), the activity of microorganisms (25), and the content of organic 4

Table 1

Content of organic substancel in bottom sediments of Dnieper River reservoirs, %

11 Group 111 Group GrouD 4 ---- Er. 1 41. N ri Q) a) (!) Q) Rèservoir I U) a, 4 U bx N ` :j ^ ^ ^ Ts ,--1 cd 4G f4 aPb c^d ^ ^ G ^ •d ^ > a^ o. m W .r^ rt N 0 a) 0 a) '. U ^l ?+ ^ O +J O 7 ^ U TJ ii +j O ^ '0

Kiev 1,0 0,8-1,2 0,2-2,8 4.9 3,8-6.0 3,0--6,6 19,2 13,3-25,1 9,8-31,8 Kr emènch.ug 1,6 1,1-2,1 0,2-2,9 6,4 -5,3---7,3 4,2-7,7 15,1 12,0-18,2 10,9--18,0 Dneprodze-r10HP.'`î-Ie He onp. 1,2-1,6 i-1 e l1-1e onp. 4,3-6,3 kl-le kFie onp. 15,8 onp. onp. I zhinsk 14.7-17,9 2,0-2,9 .. 6,8--7,7 Kakhovka 1,9 1,2-2,6 0,5-3,3 6,6 4,7-8,5 3,3-9,7 16,0 111,1-16.9 8,4--27,0

1 Based on losses during calcination Not determined

substance, which apparently affects the mobility of manganese and its transi- tion from one form to another, similarly to what occurs in soils (27).

Table 2

Content of manganese in bottom sediments of Dnieper River reservoirs, mg/kg

GrouD 1 Group 11 Group 111 ^ ^ Réservoir •^t ^ a^ 1 cn a^ u) a) 4-4 U. to (1) ;j 01 r' 0 F4 d 1-1 N W 41 Q) rz U `U ^-+ +xJ O U rd P U •d ro ^ O :> ...... ^..^-.-,..,-.. Kiev 196 182-•220 58-288 260', 72-448 60-415 I 1086 767-1405 485-1840 Kremenchug 120 89-159 43-255 510 316-70-1 389-771 504 312-696 239-727 Dneprodzer %4-1 e lie onp. 210-258 Ae ^e onp. 258-727 ^l e He onp. 1442 onp. onp. zhinsk onp. 195=-218 395-^703 485-762 Zanorozhve ,••.:_ Kakhovka • 353 163-548 143-875 486: 34i-.631' 206-800 1.135 8:84'•-1386 586--.3544

* Not determined

The pH value of the bottom sediments of Dnieper reservoirs during the

period of investigations varied from 7.2 to 7.8; only in single samples were 5 lower (6.7) or higher (8.1) pH values observed. Howeer, we were not able to establish any relationship between the pH values, and the content of bulk man- ganese.

It has been established that in soils having pH values from 5.0 to 8.0, the organic substance reduces the mobility of manganese; an increase in the con- tent of organic substance results in the accumulation of manganese (27). A sim- ilar dependence is observed in the bottom sediments of Dnieper reservoirs. In the indicated range of pH values the mean content of manganese in various types of bottom sediments correlates quite well with the content of organic substance

(r=+0.8 with a 99.2% confidence level). Besides organic substance, there un- doubtedly is a number of factors which also determine the distribution of man- ganese in soils. However, these have not been studied, and remain the subject of further investigations.

Table 2 contains data characterizing the mean and observed values of [33] manganese content in the bottom sediments of Dnieper reservoirs. It should be noted that the manganese content of various types of soils does not differ in all the reservoirs. The most abundant in manganese (according to the mean values) are the bottom sediments of the Kakhovka Reservoir.

In all the reservoirs, high concentrations of manganese are usually found in inlets (zalivs - tr.) where the bottom sediments abound in organic substance - Glebovsky zaliv in the Kiev Reservoir, Tyasminsky zaliv in the

Kremenchug Reservoir, the (upper part) and Adamovsky zalivs, zaliv in the Dneprodzerzhinsk Reservoir, and Vol t nyansky zalivs in the Dnieper

Reservoir named after Lenin, and Rogachinsky zaliv in the Kakhovka Reservoir.

Of all the types of soils, silts are the most abundant in manganese, and so it is interesting to compare them with chernozem soils which are also

the most abundant in manganese as compared with other types of soils on the

European territory of the USSR (28). Table 3 contains comparative data on the mean content of manganese in the bottom sediments of Dnieper reservoirs and 6

Table 3

Content of manganese in silts of Dnieper River reservoirs and in chernozem soils (28.32), %

Site Mean Minimum Maximum

Kiev Reservoir 1,1 • 10 4,8.10-2 .Chernozem soils of Kiev region 50.10_2 lie oup. He oup.* -2 -2 Kremenchug Reservoir 5,0.10 2,0.10 7,0.10 Chernozem soils of the — 2 -2 HCherkassy and Poltava regions 4,5.10 4,0.10 5,0.10 - -2 Dneprodzerzhinsk ReservOir He oUp.* 2,6.10 Chernozem soils of the Dnepropetrovsk region 4,2.10-2 He °up.* He oupg.` -2 -2 ZaporozhReservoir He onp.* 4,8.10 7,6.10 Chernozem soils of the Zaporozhye region , 5,4.10-2 He He onp.* -2 Kakhovka Reservoir hi. 101 3,o-10 :Chernozem soils of the 5,9.10 -2 Kherson region 0.1 0-1 4,7.10 1,5, 10-4

* Not determined

in the soils of the regions in which a given reservoir is located. Only in the

Kiev Reservoir is the Mn content of silts almost twice greater than in chernozem soils. This is apparently due to the accumulation in this reservoir of Mn brought in by the Dnieper and ' rivers (18, 29).

A comparison of our data with those for the reservoirs of Priazovye

(17) shows that the manganese content is slightly higher in the silts of the Kiev and Kakhovka reservoirs.

Zinc and copper. Zinc and copper have similar geochemical properties, and so their distribution in bottom sediments is discussed jointly. 7

Table 4

Content of zinc in bottom sediments of Dnieper River reservoirs, mg/kg

Group 111 GrJaun_ I Group II [ 34] 1 1 1 4 W 1 ..0 W Reservoir .A 0 0 -,% `cl') .r1WWW0 9-1wwww e g-iwu w 4_-,0t,o w e 4-AUW 0) W 0 0 P '1:1 *--I 'W 0 P -d H cd.w P'T111-1 . W 0 W W ,C ,---icd woww .£1,---iw w oww unzip 40> ()I:1P 4Jo› E Urd P 4-Jo›

Kiev 4,0 2,4-5,6 0,4-5,6 17,1 0,2-45,5 1,4-42,0 64,1 46,6-81,7 28,0-116,0 Kremenchug 5,0 3,4-6,6 2,8-9,2 21,8 7,7--35,9 7,6 —38,531,911,7--52,1 8,5-53,1

. DHe * He * He oup He onp. 1,2-1,7 oup. He onp. 5,3-11,2 onp ile onp. 66,1 Dneprodzershins , • Zaporozhye . . 2,6-5,4 ' , . , 12,9-33,1 . . 33,1-119,'; Kakhovka 8,0 2,7-13,3 1,3-19,3 20,0 -1,9-38,1 3,3-84,4 42,5 31,3-53,7 7,5-132,2 * Not determined

The zinc content (Table 4) varies from n.10-5 to n.10-2 %, and the mean

values from n.10-4 to n.10-3 %; the copper content (Table 5) varies from n.10-5

to n.10-3 and from n.10-4 to n.10-3 % respectively, i.e. the variance range is

slightly narrower for copper; as to its absolute values, the content of zinc is

always higher than that of copper.

The basic factor determining the zinc and copper content of reservoir

sediments is their content of organic substance, as indicated by the following

estimated correlation coefficients: Zn - organic substance r=+0.96 (confidence

level > 99.9%), Cu - organic substmce r=+0.92 (the same confidence level). The

correlation coefficient for zinc and copper is +0.9 (confidence level 99.9%).

Therefore, the content of organic substance determines the observed difference

in mean values both in the same reservoir and in soils of the same type in dif-

ferent reservoirs.

The highest concentrations of zinc and copper are also found in the [35]

silts of inlets and bays. Table 5

Content of copper in bottom sediments of Dnieper River reservoirs, mg/kg

Group Group 11 Group III Reservoir .i i Ji M -ri a) (2) M a0 0) Q) •cn m 44 0 Q) ^j G ro N ^ Q) u'd^{^° ô^ zi

Kiev...... 2,0 1,3-2,7 1 0,2-3,0 3,9 1,3-5,5 1,7-5,7 13,1 9,4--16,8 8,fi---30,8

Kreménchug...... ' 2,9 2,2-3,6 1 1,4-4,9 9,8 9,3-10,3 8,2-11,6 12,8 7,7-17,9 6,5-18,0 il-le e ;d-1 e DneprodzerzhinsL Onp. }le onp. I 1,7-2,0 onp. fie, onp. 3,3-9,0 onp. He .onp. 15,4

14,2-21,.'i Zaporozhye ..... 2,6-2,9 } 10,8-11,7 Kakhovka...... 2,5 1,6-3,4 0,6-3,7 9,4 8,9-9,5 4,1-15,9 15,2 12,3-18,1 5,0-31,2

* Not determined

A number of soil samples from the Kalr.hovka Reservoir were found to contain high concentrations of zinc and copper (as compared with the me-'an values). ITaving compared the obtained values of Zn and Cu content of bottom sediments with their maximum absorptive capacity (3), it can be concluded that the potential capacity of natural accumulators of heavy metal ions is extreme- ly high.

The mean copper content in the bottom sediments of Dnieper reservoirs

is slightly lower than in the Tsim:!_yanskaya.(14) and Staro-Beshevo (16) reser-- voi.rs, and higher than in the Volgograd (17) and Veselovskoye (15) reservoirs,

however, the order of values is identical. There are no data on the copper

content in the soils of various regions of the Ukrainian SSR; the mean copper

content in chernozem soils (after A.P. Vinogradov) amounts to 2.2.•10-3%

3% iix bottom sediments (silts) of Dnieper reservoirs). (1.3-10- 3 - 1.5-10- We have not come across any data on the zinc content of reservoir

silts in literature. In Table 6, we have compared our data on zinc content . 9

Table 6

Content of zinc In bottom sediments of Dnieper River reservoirs and in chernozem soils (28), %

Mean.IMini- Maxi- Site 1 m, um mum 11•10-: n -

..•■■■■ Kiev Reservoir 2,8 - 146 • Chernozem soils of the Kiev region 5,0 He one Heone Kremenchug Reservoir 6,4 3,2 0,8 5.3 Chernozem soils of the Cherkassy & Poltava regions 5,0 Dneprodzerzhinsk Reservoir He one 0,3 6.6 Chernozem soils of the Dnepropetrovsk region , 4,8 1,7 7,1 Dniepr Reservoir named after Lenin He onp. 3,a 149 Chernozem soils of the Zaporozhye region 6,9 . 5,0 • .7,6 . Kakhovka Reservoir 4,2 . 13,2 .Chernozem soils of the Zaporozhye & Kherson regions 5,0 16,9 .

* Not determined

with data for chernozem soils. The order of mean values for silts and soils is

almost the same; in absolute values, the zinc content in the Kremenchug and

Kakhovka reservoirs is slightly lower than in the soils. The large difference

in threshold values is apparently due to the fact that far more samples were

taken from reservoirs than of soils.

Cobalt Of all the studied metals, cobalt was found in the lowest con-

centrations in the bottom sediments of reservoirs (Table 7) - n.10-6 -- n.10-4 %

(mean values within the n.10-5 -- n.10-4% range). The content and distribution

of cobalt on the area of the reservoir beds is determined by the organic sub-

stance in the bottom sediments. The correlation coefficient is also very high

r=+0.90 (confidence level 99.9%).

The mean content of cobalt in the silts of Dnieper reservoirs amounts

to approximately 0.4.10-3%. This value is more than hall that of chernozem

soils (after A.P. Vinogradov, 0.9.10-3 %) and 3-4 times less than for the reser-

voirs of Priazovye (14-16).

Table 7

Content of cobalt in bottom sediment of Dnieper River reservoirs, mg/kg

GrOUD Group Il Group HI Reservoir 1 1 .0 CO 4 0 W W 0 0 10 •r-1 0 0 a.) o cn 0 O 4-1 OW 0 0 4-1 O 0 4-1 U W 0 • eo $4 H . 0 0 O 0 P r-i 0 0 0 W1 41H 0 0 0 0 W O 0 0 W F 4O 5 '1:$ $4 4 0 › 5 (.) '0 $4 4..) ›

Kiev 0,7 1,6 41-2,1 3,8 2,9-4,7 2,4-5,6

Kremenchug 0,9 0,5-1,3 0,2 2,9 2,0-3,8 3,7 2,1-5,3 2,2--6,2

le He eFle Dneprodzerzhinsk on p He onp. on p. He onp. 48 onp. He on p. 3,4

•Dnieper 1,5_-5,3 5,6-6,1 Kakhovka 1,3 0,2-2A 0,1-4,2 2,4 1,5-3,4 0,8-4,4 4,2 3,3-5,1 0,7-8,2

* Not determined

A possible explanation of this ma y be the fact that a considerable [361

amount of cobalt, anywhere from 5.0 to 12.5 mg/kg dry weight (30), accumulates

in the great mass of blue-green algae which winter and begin their development

on the sllty bottoms of Dnieper reservoirs. Since cobalt is hardly ever detected

in the water of Dnieper reservoirs (technique sensitivity 0.1 pg/l), up to 10

litres of water was used for determination purposes (29); this was supposed to

limit the development of blue-green algae (31). Apparently, it is the bottom

Table 8

Correlation coefficients of heavy metal content in bottom sediments of Dnieper reservoirs

Cu Zn - . Co ..E .ement r confidence r confidence. r confidence . level , % level . % leVel . % ---..--__ Zn 4-0,89 99,9 - -- — _ _ Co +0,94 99,9 1-4e0 99,9 — _ • Mn. i.0y8 . 99,9 4.0Y9 99,2 4.0j1 .97,9 11.

sediments that are the source of this element which is so important for the de" velopment of algae, Cyanophyceae being the migrants of cobalt.

As seen in Table 8, there is a positive correlation between the mean

values of all the studied elements. The closest correlation is observed for

Cu-Co, followed by Zn-Co and Zn-Cu. The confidence level for these correlations

is very high (>99%). The correlation coefficient for Mn-Cu, Mn-Zn and Mn-Co is

slightly lower.

The Co:Cu:Zn ratio of mean concentrations for Dnieper reservoirs is

1:3:6 in silt-covered sands, 1:3.5:9 in sandy silts and silty sands, and 1:4:11-

in silts.

Conclusions

1. The main factor determining the content and distribution of trace

elements in the bottom sediments of Dnieper reservoirs is their. content of organ--

ic substance, as indicated by the high correlation coefficients of their mean

[37] values. The correlation with organic substance diminishes in the series

Zn-Cu-Co-Mn.

2. In all the reservoirs, the highest concentrations of trace elements

are found in bays and inlets where the bottom sediments contain.large amounts oL

organic substance - Glebovsky zaliv in the Kiev Reservoir, Tyasminsky and

Adamovsky zalivs in the Kremenchug Reservoir, the Vorskla zaliv in the Dnepro-

dzerzhinsk Reservoir, the Samara and Vol'nyansky zalivs in the Dnieper Reser-

voir named after Lenin, and the Chertomlyksky and Rogach_i.nsky zalivs in the

Kakhbvka Reservoir.

3. The trace elements studied in bottom sediments can be arranged in

the following series based on correlativity:

Zn - Co(Cu)>Mn - Co>i`S1i - Cu(Zn).

Paper submitted Institute of Hydrobiology March 5, 1.971 of the Ukrainian Academy of Sciences, Kiev 12 I •

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