Translation Series No
167
FISHERIES RESEARCH BOARD OF CANADA Translation Series No. 1511 Hydrochemical characteristics and the pattern of the changes of surface water composition. By Michal Antonie ' Original title: Hydrochemickâ charakteristika a zâmislosti zmien zloenia povrchovçrch vôd. From: VyskumnyjJtav Vodohospodarsky Bratislava, Pràce a studie 27, : 4-161, 1964. Translated by the Translation Bureau(MK) Foreign Languages Division Department of the Secretary of State of Canada Fisheries Research Board of Canada Freshwater Institute Winnipeg, Manitoba 1970 - 165 pages typescript
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Transcript of Translation Series No
FISHERIES RESEARCH BOARD OF CANADA
Translation Series No. 1511
Hydrochemical characteristics and the pattern of the changes of surface water composition.
By Michal Antonie'
Original title: Hydrochemickâ charakteristika a zâmislosti zmien zloenia povrchovçrch vôd.
From: VyskumnyjJtav Vodohospodarsky Bratislava, Pràce a studie 27, : 4-161, 1964.
Translated by the Translation Bureau(MK) Foreign Languages Division
Department of the Secretary of State of Canada
Fisheries Research Board of Canada Freshwater Institute Winnipeg, Manitoba
1970 -
165 pages typescript
INTO - 'EN TRANSLATED FROM - TRADUCTION DE
Slovak English
SECRÉTARIAT D'ÉTAT BUREAU DES TRADUCTIONS
DIVISION DES LANGUES
1964 _165_
PUBLISH ER - ÉDITEUR
Hydrological Res. Institute
PLACE OF PUBLICATION LIEU DE PUBLICATION
DATE OF PUBLICATION DATE DE PUBLICATION
ISSUE NO. NUMÉRO
PAGE NUMBERS IN ORIGINAL NUMÉROS DES PAGES DANS
L'ORIGINAL
4- 1à NUMBER OF TYPED PAGES
NOMBRE DE PAGES DACTYLOGRAPHIEES
YEAR ANNÉE
Bratislava
VOLUME
BRAKCH OR DIVISION Freshwater Inst., Winnipeg, FRB DIRECTION OU DIVISION
TRANSLATOR (INITIALS) TRADUCTEUR (INITIALES)
MK
DATE COMPLETED DEMANDE PAR ACHEVÉ LE
July 31, 1970 Dr. G.J. Brunskill PERSON REQUESTING
YOUR NUMBER VOTRE DOSSIER N°
769-1 8-14
*ATE OF REQUEST ATE DE LA DEMAI ATE DE LA DEMANDE
March 9, 1970
Fi\-"13
DEP,-.RTMENT OF THE SECRETARY OF STATE TRANSLATION BUREAU
• FOREIGN LANGUAGES DIVISION CANADA ÉTRANGÈRES
AUTHOR - AUTEUR
M. AntoniY
TITLE IN ENGLISH - TITRE ANGLAIS Hydrochemical Characteristics and the Pattern of the Changes of Surface Water Composition
'Title in foreign language (transliterate foreign characters) Hydrochemicka charakteristika a zAvislosti zmien
zlolenia povrchovYch ve3d REF5RENCE IN FOREIGN I,ANGUAGE (NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE FOREIGN CHAftACTERS. • RÉFERENCE EN LANGUE ETRANGÉRE (NOM DU LIVRE OU PUBLICATION), AU COMPLET.TRANSCRIRE EN CARACTERES PHONETIQUES.
As above - Final report
REFERENCE IN ENGLISH - RÉFÉRENCE EN ANGLAIS
As above
REQUEeTING DEPARTMENT Fisheries & Forestry MIN 1ST ERE-CLIENT
TRANSLATION BUREAU NO. 5918
NOTRE DOSSIER NO
UNEDITED DRAFT TRANSLATION» Only for information
TRADUCTION NON REVISÉE sc..,u!cniont
SOS•200-10-6 (REV. 2/68)
•
•
•
DEPARTMENT OF THE SECRETARY OF STATE
• TRANSLATION BUREAU
FOREIGN LANGUAGES DIVISION
F-7-yç / SECRÉTARIAT D'ÉTAT
BUREAU DES TRADUCTIONS
DIVISION DES LANGUES ÉTRANGÈRES
CLIENT'S NO. . DEPARTMENT DI VISI ON/BRANCH CITY No DU CLIENT MINISTERE DIVISION/DIRECTION VILLE
Fisheries Res. Board Fresilwater Institute Winnipeg, Man.
BUREAU NO. LANGUAGE TRANSLATOR (INITIALS) DATE No DU BUREAU LANGUE TRADUCTEUR (INITIALES)
5918 Slovak MK
HYDROLOGICAL RESEARCH INSTITUTE - BRATISLAVA
Papers and Studies
27
MICHAL ANTONI, M.Sc., Ph.D.
HYDROCHEMICAL CHARACTERISTICS AND THE PATTERN OF THE CHANGES
OF SURFACE WATER COMPOSITION
BRATISLAVA
This paper, presenting the general hydrochemical character-
istics of river water in Slovakia, evaluates factors which
affect the chemical composition of water, and determines the .
pattern of the changes in the composition of water and the runoff
of ions from the river basins.
The paper represents a generalization of knowledge of the
composition of surface water in Slovakia. It is based on the
evaluation of observations made during the last few years.
SOS-200-10-31
•
-2-
The paper is designed for workers in hydrology, both in
planning and in practice, and also for hydrology scientitts and
university students.
Publisher's reader: Oleg Bogatyrev, M.Sc., Ph.D.
Copyright: Hydrological Research Institute, 1964
INTRODUCTION
Nowadays each branch of the economy is making increased
demands for high-quality water.
Water in our country is already becoming the limiting
factor for the development of industry and the national economy,
both from the quantitative and qualitiative points of view, as
Professor Madera emphasized.
Comparison of the consumption of water in Czechoslovakia
in 1939 (1700 x 106 m3 /year) with the recent consumption
(3700 x 106 m3/year) shows that it has more than doubled. By.
1965 it will have increased about four times and by 1980 about
nine times. In Slovakia the increase in the consumption of water
is even faster and in the period from 1950 to 1980 the consumption
of water will increase eight times (from 500 x 10 6 m3 to
4000 x 106 m3/year). This shows that the consumption of water
is exceptionally high and increases continually. However, at
minimum flow rates, 14,000 x 106 m3 of water leave the territory
of Czechoslovakia per annum, and 2300 x 106 m3 of water flows
off Slovakia (the Danube not includud). It means that already
in 1980 shortage of water will be evident at minimum flow rates
and that in 1990 all available sources will be exhausted.
The quality of water is of decisive importance as far as
its use is concerned - in other words it affects the design of
essential equipment needed for its conditioning. Incorrect
water management - be it froM any viewpoint - can have far-
reaching. consequences. It is natural that the properties of
water (physico-chemical and biological) are being studied, in
each case, with an eye to the use planned for this water.
Today we can no longer imagine a project without knowledge of
the basic properties of the water which will be used in it.
These fundamental data are needed especially to prevent losses
in production, damage to buildings, etc.
For this very reason the increased demands for water
quality and extensive and expensive conditioning have led and
are leading today to an intensified study of the chemistry of
water both in our country and abroad. In an era of increased
demands for water, hydrochemistry, i.e., the chemistry of natural
waters, has become a scientific discipline. Hydrochemistry came
into being not very long ago - less than fifty years - though
a great deal of attention had been paid to the problems of water
quality even earlier (especially at the end of the nineteenth
century). At that time, however, hydrochemistry was only an
auxiliary scientific discipline which served several related
branches of knowledge. In the first period factual material was
collected without being processed in detail. Laws which control
the changes of water composition were not studied and the results
• obtained were not generalized. Such an attitude to the solution
of these problems is far from being the best one and it is quite
unsuitable for future use. FILATOV (1955) said that without
learning the laws of formation of the chemical compostion of
water, and the effects of certain factors onthese changes and
processes, it is impossible to make attempts to generalize the
results with sufficient reliability. It is equally impossible
to forecast the composition of water in streams and reservoirs
from the changes in t heir natural character in spite of knowing
the principles of the hydrochemical regimes bf all rivers which
are exploited.
In the U.S.S.R., where the development of industry is
110 showing an immense growth and where the solution of the problems was approached in a planned manner, some authors ( -ALEKIN in the
U.S.S.R. and KONENKO in the Ukrainian S.S.R.) started to solve
the problems of surface water hydrochemistry from the point of
view mentioned above. Thus they laid the foundations for the
recent development of the techniques of solving complex problems
in hydrochemistry.
They have been followed by many authors who started to
solve the basic problems connected with the formation of the
chemical composition of water and with the laws controlling its
changes, problems of the equilibrium of the runoff of material,
and by authors who are studying chemical erosion. Such results
were achieved that they are being considered as factors (quantities)
gl, in hydrological calculations (27, 29, 30). Soviet specialists
•
•
•
have achieved such success in this field that their results can
be used in the prognosis of water compositon.
Recent results indicate that the composition of water is
closely related to physical, geographic, climatic or other
conditions. Therefore all findings cannot be applied equally
to all rivers, but they mUst be studied separately and in their
individual relations to actual conditions.
In our country little research has been done on the
complex problems of the hydrochemistry of surface water. Here
especially PLEISCHL, SCHULZ, HAMACKOVA, MADERA, KOHOUT, BOSKO
and others have contributed to the development of the hydro-
chemistry of surface water. In addition to characterizing water
properties these authors contributed mainly to those branches
of water chemistry which are connected with the organic pollution .
of rivers. Recent papers by CHALUPA, who studied the factors
governing water composition and changes of essential elements,
are a contribution to the solution of these problems. Also
some papers by the author of this book and in part the paper by
HAVRANEK (a preliminary Ph.D. thesis) can be considered as a
contribution to this field.
• On account of the specific problems posed by practice and
increased demands for water quality, the fact that we must
inevitably study the correlations between water composition and
the concrete natural conditions, and that we must bear in mind
that the results shouldbe generalized, we decided to process the
results accumulated.
Ile The evaluation of our own results has been focused on:
(a) The general characteristics of the composition of water,
(h) The assessment of the effects of factors which influence the composition of water,
(c) The determination of the factors on which the ' changes in water composition depend,
(d) The equilibrium of the discharge of substances dissolved in water,
(e) The possibility of predicting the composition of water.
The scope of this paper and the treatment were selected in
order to draw at least partial conclusions concerning the
hydrochemistry of surface water and the laws controlling the
formation and changes of the composition of water. Such a
paper would at least partially fill the gap existing in the
hydrochemistry of surface water and would make work for other
scientists easier in this branch of knowledge, not to mention
the need for basic data for practical purposes.
I GENERAL CHEMICAL CHARACTERISTICS OF FLOWING SURFACE WATERS
The quality of water has been the subject of study for a
long time, so that nowadays we can find data on the composition
of water from nearly all continents. Data not only on the
larger rivers or isolated locations, but in many cases on entire
rivers, the entire drainage basins of the more important rivers,
and even small creeks have been processed.
•
•
•
Various authors adopted different approaches to the
description and evaluation of chemical processes in water.
They were very often obsessed with the idea of using the results
for practical purposes. Their approach to water analyses and
their evaluation was different acèording to whether the water
was for industrial, constructional, agricultural, piscicultural
or drinking purposes. Some papers were written only from the
point of view of natural science and their authors tried to
characterize the properties of water from the widest and most
general viewpoint.
Apart from the fact that a great number of authors proceeded
and still proceed without deep generalization when evaluating
chemical processes in water, and without reference to the laws
controlling the changes of the composition of water and the
factors resultinL; from these changes, many authors are already
indicating in the conclusions of their papers that there is a
close relationship between the environment and the composition
of river water. At the same time opinions differ as to which
of the factors affecting the chemical composition are primary.
Some authors (TAKAHISHA HANYA, UNZUMASA KITANO, TSUZUMAKI MICHIJI,
NAGYAMA, SHU, NONYTA SAJDZE, FILATOV, DENISOV, DZENS-LITOVSKII,
LE GRAND, BAECKER and others) are of the opinion that the
dominating influence is exerted by the geological or hydro-
geological conditions of the drainage basin. Other authors
(VORONKOV, GIRENKO, ALEKIN, HAVRANEK) ascribe the dominating
influence to the pedological conditions of the drained terrain
and others to climatic conditions, emphasizing that the most
important role is played by the precipitation and related
hydrological conditions. A number of authors do agree that
precipitation and the hydrological regime of the river are the
factors which affect the composition of water, but some (FILATOV) /10
say that such factors bulk largest only as far as changes of the
composition of water are concerned. The basic Character of water
is determined by the parent rock material or the compostion of
the subsoil. We shall deal with these questions in the following
chapters.
Papers which deal with the • tudy of the factors governing
the composition of water and generalization of the results with
the aim of using them for predicting the composition of water
gl, in seas, lakes and reservoirs have been restricted to the
observation and characterization of several groups of components.
Analyses involving the six to eight main ions and total
mineralization* are most common, followed by papers which analyze
the regime of organic and essential elements in detail.
Recently, in addition to the regime of the main tons, a
great deal of attention is being paid to the content of trace
elements in surface waters, which has been neglected up to now.
It is especially in the U.S.S.R. that the trace elements have
lately started to be studied.
*Total mineralization (I) is the total amoun of ions present in water and is expresséd in mg/l. or mval/1 .; it is different from the suspended matter dried.
+Translator's Note: mval/litre + 11£1-.1 u.' when g. - equ. = atomic weight in gra6:
All the topics of the papers cited above are today indepen-
dent parts of the hydrochemistry of natural waters - especially
in the U.S.S.R. They cannot be included in the problems related
to the hydrochemical regime of the main ions and their prediction,
with which we wish to deal in this paper. Here we have mentioned
them only marginally to emphasize the evident progress of the
chemistry of natural water.
(A) ON THE EVALUATION OF WATERS IN GENERAL
Papers which deal only with the general characterization of
the composition of water actually present a description of water
properties either from the general point of view or as centred
on a special goal. The amounts of compounds found in water have
been listed and the ratios of the components referred to. Even /11
numerical values have been introduced as characteristic of surface
suspended matter dried waters such as — 0.75, or the ratios of electric conductivity
Mg 2+
etc. Discussed are the forms in which individual Ca 2+' e components occur in water, i.e. what salts water contains.
Also describbd are the physical properties of water (temperature,
colour, odour, turbidity, etc.), gas content in water etc. In
short, the attitudes to the evaluation of water are different
and according to papers which have already been published, can
be characterized as follows:
1. Evaluation of physical properties of water,
2. Evaluation of gases dissolved in water,
3. Evaluation of the main ions (components) in water,
• -10-
4. Evaluation of essential elements,
5. Evaluation of trace elements,
6. Evaluation of organic matter,
7. Evaluation of natural radioactivity of water,
8. Recently even evaluation of artificial radioactivity of water.
The most common evaluation of water was and is even today
based on the main ions such as Ca2+ Mg2+ , K+ , Na+ , HCO S02- , 3 ' 4 '
Cl- , and possibly also NOi. These ions practically represent the
total mineralization of water (up to 98-99%). The main Interest
of the substances listed here is that they are the most important
from a practical point of view. Trace elements and essential
elements amount only to a very small part of the total content of
salts, and they were therefore not taken into account.
Different ways of expressing concentrations and ratios of
individual ions have been used in the evaluation of the mineral
portion, such as g/kg, g/1., mg/1. 1 mval, mvallo, or coefficients
of ratios. Many ways to classify natural waters have been
devised, along with different ways of presenting results and
methods for evaluating qualitative properties.
In many cases the principle and method of evaluation has
been fairly good. Hudever, the disadvantage of all these
systems mentioned above is the statistical assessment of results,
which is no longer satisfactory demands.
We shall use FILATOVIS classification (40) for hydrochemical /12
characterization of our waters. It is a simple and clear
system which is easy to use. In principle FILATOV divided
HCO- 3 bicarbonate waters SOt- + Cl 1.9
-11 -
natural waters into 3 basic types of water according to their
anion contents: bicarbonate, sulfate and chloride types, which
form the main classes
this system are based
According to the
of the classification. The subclasses of
on the content of the main cations.
content of individual anions and the
ratio of the main anion to the other two remaining anions,
FILATOV defines 3 types of waters: pure, intermediate and
mixed.
As the pure or true type of water he considers water in
110 which the ratio of the main anion to the sum of anions in
milliequivalents is Kg--2/ 1.9. FILATOV called it "the coefficient
of the main anion" (Kp).
Waters in which 1 C.Kp l.9 he considers as belonging to
the intermediate water type.
Waters with Kp Z-1 he classes with the mixed type.
Thus, generally, FILATOV divided waters into the following
five classes:
Class I True
Subclasses:
Class II True sulfate
Subclasses:
ClassIII Ti.ue sulfate
Subclasses:
calcareous, magnesium and sodium waters.
2 SO4 -
waters _ 1.9 Cl- + HC07; "
calcareous, magnésium and sodium waters.
Cl- waters --`/ 1.9 Ho°
3 + SO2
4 calcareous, magnesium and sodium waters.
•
•
-12-
Class IV Intermediate waters Kp = 1 to 1.9 (chloride-bicarbonate,
chloride-sulfate, sulfate-bicarbonate, Sulfate-chloride,
bicarbonate-sulfate, and bicarbonate-chloride waters).
Class V Mixed waters Kp,‘1.
We shall also mention ALEKINIS suggestion (3) for the
division of surface waters into four categories according to
total mineralization. it can be used with advantage if the
degree of mineralization of the water is given. Individual
categories are characterized by the following limits of mineral
compounds:
First category: Water with low mineralization (below 200 mg/1.),
Second category: Water with medium mineralization (200-555 mg/1..),
Third category: Water with high mineralization (555-1000 mg/1.).
With the limits of the first category ALEKIN still
distinguishes waters with very low mineralization (below
100 mg/1.). ALEKIN and VORONKOV (3) (89) and other authors
adhere to this categorization when dealing with rivers, and
plot their results on maps of the individual regions and even of
the entire territory of the U.S.S.R.; at the same time they
divide waters into such types as, for example, bicarbonate,
suflate and chloride. It needs to be emphasized that only in
the U.S.S.R. have the rivers been to such an extent and so
comprehensively from the hydrochemical point of view.
•
-13-
(B) CHARACTERIZATION OF WATERS OF SLOVAK RIVERS
Before we proceed with an assessment of the pattern of
composition changes and the factors influencing the composition
of water, etc., we shall present a brief description of the
composition and hydrochemical prol;erties of the surface waters
of the whole of Slovakia.
We have selected rivers of different sizes from various
geological formations to assess the properties of waters. At
the same time we took care that the selected sampling sites
would represent the natural state of the river wherever possible.
In the case of larger rivers (Vah, Nitra, Hron, Little Danube, /14
Morava etc.) we also included sections which are already under
the influence of artificial factors (pollution with waste waters).
The results from these sections, where the natural regime of
water has been disturbed, are being cited both to reveal the
extent of such disturbances and so that the results from
economically more important regions can be used for practical
purposes.
1. Total Content of Mineral Compounds
Comparison of the content of mineral compounds or
the suspended matter dried indicates relatively large differences
between our rivers, but they are substantially smaller than for
the rivers of the U.S.S.R. or other countries. More balanced
ratios are due to more balanced climatic conditions and smaller
differences in the composition and kinds of waters feeding the
Third category:
Fourth category
•
•
-14-
rivers. Cases occur in the U.S.S.R., for example, where the
lower streams feed only the reservoirs of ground waters, or
where, during very dry seasons, the river beds get almost dry.
It is understandable then that such rivers, at low flow rates,
have a very high mineralization, which decreases considerably
during the rainy seasons, or that rivers in arid areas have a
considerably higher mineralization that the rivers in areas
of permanent swamps or permanent snow and glaciers.
In our country we have not sudh extreme conditions and
therefore we also do not observe such marked differences in
the water composition. Mineralization of our waters fluctuates
within the range of 60-600 mg/1., and only in isolated cases
have these limits been exceeded. Even in such cases the water
was affected, as a rule, by waste waters. Mineralization of
the major part of our waters lies between 200 and 400 mg/l. (cf.
Tables la, lb, le, id, le, lf). According to ALEKIN'S categor-
ization of waters there are only 3 categories in our country,
but if we accept the division of the first category into two,
there are four:
First category: Waters with very low mineralization (below 100 mg/1.),
Second category: Waters with low mineralization (below 200 mg/1.),
Waters with medium mineralization (up to 500 mg/1.),
: Waters with high mineralization (over 500 mg/1.).
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le Determination
..„.., remperature of ( war(°C) / Flow Q (m3/sec.) .. 3 rah..-..paw.5..ty cm .. q olor
• . . ._.....
.. .. .... '
•',.' -oecific condu.ctivity (L.v...cm .10-6.
at 18 ° C) - '4 tcr ;; cini y (Fhenoiphhalein ml 0.1 N Na0H/1i er :
7 Iiij:-41n.itY". (i4e-th-.4 iDrangl) ..m1 0.1 N HC1/liter . ;do
Undissolved calcinate0_ mat er...46.00°C) 'Y Undissolved dry matter ( Or . . .
-.. fLedR8gea MRt8F ÎEAïgel.e-ebooc .3 Fre e COI. ._ .. ' t`i ound COe.
4y- geressive COJ. _ it etal hardness (Gerlan. rddes)
ermanent _aardness -"- /7 emporary ,aardness -ii-
‘? Orge.nic compounds - Kubel (02-) ..?..c biochemical. consumption of' oxygen (BCO) j1 Fou_nd oxygen _
. 23 Si içic aaid SiOa. -22-0Ten differencet
2-19. 1.11 rites iwi. . --2SN1 trates 21; Phosphates 27 ee.f ates Se - .28 u iorIdes . Cl 2-9 i3 carbonates
Fe Hco3 • . ., .
2 ' irÎn cium Ca . \ .
2,2- Maunesium Ng2-1- ..?-s So ium Na .t.
.3q- Po _es-Ammonia Did:* 2_+ :e tannes A M-3) Z anlQns eis z cations _ . • ...
ri «JO 11.11
7.10
4440
1110
1111
11470 12131 1/7.12
7.24 111
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ea 177
411
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XV 117/ 94/1 111 1112 11111 111
4 31 MOO 41111 .1110 11101 11112 IX
11 111,00
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e
r
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eg.ece ; lat- Zlee/Pietee. ei• ezeove¢
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- •:- - - Dete.rraination •' ' i D. OW C) M
3/sec .)_. , •
. , ' i :z, ensperature of ,watër ( PC) •
• .•_ y »Dior . çr -u,) • 3 rif. paDep.cly t cm) . ,--r --I --I •
.. s- beeine conductivity (.cm .10 at 18 ° C) •> 4. 1.ei.nity (Méthyl Crane?) ml 0.1 N HC1/liter 16 AC1 ity (Phenolphthalein) ml 0.1 N Na0H/liter 1 Undissolved dry matter (105°C) ic, Undissolved, .calcinated. matter ( . :90°C)
. //1-tiekerideci matier 6ri*1,4t 105 8 Lus..ead.ect matter. ismitéa a -G 0,0 °C .t. ' /3 ree- uua. __._ .. _ _ _... ._ _ ..______ , - ie .riund CO .2- ,„
/4- ecressive uw..._ , tb Otal hardness (Ger au - grades - 7:7_ 1.. 1
17 Temporary Ilardness Ç_'- • fiPermanent hardness -"- _ ifgrganic.compounds - Kubel (02)
.2e; ioicnemical_ consumption of oxygen (BCO) •if Found oxygen._ . _ . „2. -..,-Oxïgen. diiferêncet . X.? Si içic ag.id SiOa
- - ,,,-iy 112. riz es .i.vt.a.- - —;.4--- Nitrates NO;
2(Phosphatés_, e... POir . . - ,../7 sulfates b07, - • ,2,5 Chlorides . Cl
' IA- Bicarbonates 3.1. HCOà" • . . . - .1 3 Fe ‘ Irgn 2.1.- .
i.3) . Calciuip Ca z-r; _ 3...-__Ma
uan
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•
•
-21-
To the first category belong waters from the regions of
early Tertiary eruptive rocks, crystalline rocks with quartz
rock formations, granite massifs and Quaternary terraces, unless
these waters have been affected by another geological base.
To the second category belong waters of rivers where the
major part of the drained land is made up of the formations
mentioned above, which, however, are already partially affected
by other formations.
It is possible to class the overwhelming majority of
rivers in the third category, be they waters from pure or mixed
geological formations. The range of mineralization in this
category is relatively wide and the differences between waters
do not exceed these limits, because in larger basins the waters
interact to such an extent that any small differences occurring
become eliminated.
The fourth category contains primarily waters of rivers
which are subject to great artificial influences and some waters
of natural character, such as the waters of Werfenian layers,
Triassic limestones and dolomites and waters from the region of
the Upper Triassic up to the Lower Cretaceous (Little Danube,
Nitra, Vernar etc.).
Hence it is evident that in our country there are first of
all geological conditions and then artificial factors which
cause the differencés in the mineral content of river waters.
It needs to be emphasized that these factors determine only the
basic state of the content of compounds in the water. Changes
in this content during the year or other periods of time are
122.
•
•
•
-22-
caused by several other factors. Marked changes in the content
of components are due principally to the hydrological conditions.
The changes are characteristic of all streams in spite of the
fact that they are not manifested to the same extent in all
rivers. However, this depends on other factors (soil conditions,
climatic conditions, feeding conditions, season of the year, etc.)
as well. The character of the changes, however, is approximately
the same.
2. The Main Ions and Their Ratios 2- - The main ions (HCO
3' SO
4' ci, 0a2+ , Mg2+ , K+ and
which practically represent the total mineralization (up to
98-99%), change due to natural as well as artificial factors.
A comparison of the changes in the content of compounds indicates /28
that the changes occur not only with respect to the total
mineralization but also in the ratios of individual components.
It is evident from Tables la, lb, lc, id, le and lf that
the greatest proportion of the mineralization consists of
bicarbonates and calcium, and only in isolated cases of sulfates.
Other components are present in much smaller quantities.
However, the ratio of the two main ions (HCO3 and Ca2+ ) and
other ions is not the same in all waters, as a rule. Yet te
changes do not depend on the content of total mineralization,
in the sense that a higher mineralization would be characterized
by higher ratios (of the two main ions mentioned above) or vice
versa. The changes in the ratio of ions to the total mineral-
ization are nearly in agreement with the origin of the water;
-23-
changes in a certain type of water are partially due to the
effect of precipitation or the season of the year.
The changes in the ratio of components due to different
types of water are relatively large. With bicarbonates, for
example, we have observed changes in the range of 54 to 90 mval%)
and in some waters which have been affected by waste waters
the bicarbonate content may even drop below 50 mval%. Similar
changes in terms of mval% can occur even in other components
(see details in Tables la, b, c, d, e, f).
The differences in mval% abundance of components are therefore
related to the origin of the waters and are determined first of
all by the geological bedrock (see Table 2).
Table 2 gives evidence of the abundance of individual
components in some more important hydrogeological regions.
As aIready mentioned earlier, the mval% abundance of
components varies with respect to the total mineralization and
also the ratios of the components.
Let us consider some characteristic ratios such as, for
„ + 2- 2- K Ca2+ + Mg 2+ Ca2+ + Mg2+ Si03
example, el:2+'e -t
2- 2-
Ca Na Na+ K+ HCO3
HCO3
+ S04
HCO3
+ S04
etc. and compare them for rivers from various hydrogeological
regions. Table 3 shows that individual coefficients of the
ratios of certain ions differ considerably from each other.
This indicates that in various hydrogeological regions the m,2+
values of such coefficients are different. The ratios of 2-- Ca2+,
for example, are very low in granite massifs and Quaternary
terraces (0.11-0.17), considerably higher (0.45-0.65) in the
•
•
•
-24-
regions of the early Tertiary, Triassic limestones and dolomites,
and different (about 0.3) in the flysch region and in the
Holocene. More pronounced differences are evident between the NCO- SO2-
coefficients of the ratios of -3 , 4 and SiO2- HCO
3 3 Sio2- 3 ; they are, however, approximately* for a specific
HCO-3 + S02- 4
hydrogeological region (cf. Table 3).
It is evident from the presented material that the values
of the ratios of water components and their mval% abundance
in the total mineralization can be used for the characterization
of water types with certain hydrogeological ratios.
3. Hydrochemical Characterization of Waters
Water types will first be characterized hydrochemically
and categorized in agreement with FILATOPS classification,
which divides waters into groups according to the three main
anions (HCO- ' S02- ' Cl-).
3 4 Processing of the data in Tables la, b, c, d, e, f,
- produced various coefficients of the ratios of ions HCO
3 SO2- + Cl 4
which were used for the classification of the corresponding
water types (cf. Table 4).
*Adjective missing - Translator's note.
•
•
Hydrogeological region Y.Trbtïtline roc
with quartz formarions ranite maes - and Quaternary terraces earIY-7-iFfn-FY eruptive rocks
T
1 / assic limesee - and Dolomites, lper Trias,
si • and Lovier -Œrétace:ous . _, Flyscli with much limestone and conglomerates Holocene Klippe:zone
Wprfenian layers and Triiassic limestone and
DoloMites
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rop/r; - He »Witted 4.3f / Nitta - Nitro (eelettr) 231 ce
/ Nitre - AoYala £01 I Tope, - Promo, 4,22
Cirocha - N e crfn 3,46 / N 21 ron - Banoke B=o )
( 2, /
Riko - Kamienka 110 / Nron - xserea 602 /
Ok no - Ramoteki Nemrs 2S0 ey Nron.
- Komonfn £97 / tee / Ist CI)C4 wet,
Jotranacke potok - Pod/wrote .e.t2 276 (3 I Nron
- Ilît PctlistEer
Pozinokf potok - Pazinok (4441-4-.) 0,07 e Hornet - Jpierkd None Far 3,/2
Porne - Orsiony (timcc,) 410 / Horned - 'park's; pore I't 3 2,60
Nara - Berotko .1,46 / Horne/ - Rofice (iltrue) £ /2
Purite . - élanpnce 411 se Horned - A'Oece (tet/egtr) 4«
* tv,zie4 zinz ; caw: 0 e eaiezee zts
intErmécliateite/frie - eiseade ooede- ileaeeores 3 Tint èrmectietd i eileexeous
eilX/241 S'eiliz7f2 — aue on de/cage° re.s
"e* ezae I-I/fete Alanufadittiee season
o
•
-28-
Table 4 shows that the coefficients fluctuate between
1.2 and 8:2, and that even in two cases (Little Danube and
Pezinsky Creek) the main ion was ilepresented by sulfates to
such an extent that one can speak about the intermediate su fate-
bicarbonate type. HenCe it is evident that the differences
among the coefficients of a particular main ion are relatively
large. It indicates that the hydrochemical properties of surface
water vary to a large extent.
The most common types are the true bicarbonate-lime
(calcareous) waters and, to a lesser extent, the intermediate
water type.
When comparing the coefficient values of the main ion,
we observe that the coefficients are approximately the same
for certain hydrogeological regions, but are essentially
different for individual formations. The lowest values are
found with crystalline rocks, early Tertiary eruptive rocks,
and neogenic volcanic rocks (rivers Cierny Hron, Rimavica,
Hron, Rika, Okna etc.). Waters from these areas belong to the
intermediate bicarbonate-calcareous type and there even exist
mixed water types with the coefficient lower than 1.0.
Relatively low coefficients mark waters from Quaternary
terraces, Upper Triassic to Lower Cretaceous, Triassic limestones
and dolomites and Werfenian layers (rivers Vah, Vernar, Revuca,
Nitrica and Lupciansky Creek, etc.).
• -29--
Considerably higher coefficients and thus a markedly
true bicarbonate-calcareous type are found in waters from the
flysch region, the "bald mountain" flysch region* and the
Klippe zone.
Hence it is evident that FILATOV'S system of classification
of surface waters reflects geological influences on water
properties. It has been shown that water types can be divided
according to the magnitude of the prevailing ion coefficient
into certain more important hydrogeological groups.
The assessment of hydrochemical properties of water
indicates that we have several characteristic groups of water.
Each differs from the other in total mineralization and the
content of the main ions.
It is evident from the division of rivers according to
hydrogeological regions that the chemical composition of waters
is.in fact affected by the bedrock of the drained territory.
(vie shall deal with this in detail in the next chapters).
Waters which belong to one particular group are characterized
by having approximately the same not only total mineralization
but also relative content of compounds. This is very important
for the total characterization of the properties of water
(cf. Table 3).
• *There is no English term for "podhôlny" Flysch; "hola" is a bald mountain, "podhôlny" means something located below a bald mountain - Translator's note.
• -30--
II EFFECTS OF IMPORTANT FACTORS ON THE COMPOSITION OF RIVER WATER /34
It is known that in addition to geological conditions the
chemical composition of water and changes of such composition
are affected by pedological and climatic conditions, by the
water source which takes part on feeding the stream, the season
of the year, etc. The effects of individual factors on the
changes in the chemical composition of water and their participa-
tion in the formation of the chemical properties of water have
not yet been evaluated with sufficient accuracy and reliability.
In most cases only a statement of a subjective assumption based
on several analyses has been dealt with. Such knowledge, even
if valuable, cannot be generalized, because the deduction was
not based on objective methods and the conclusions are not
formulated mathematically. Only the dependence of composition
changes on the flow and partly also on the geological bedrock
has already been evaluated from this aspect. Such a state of
affairs can be explained by the fact that the flow conditions
most markedly affect the changes of the composition of water
and are, therefore, most important from the practical point of
view. As far as other factors are concerned, it is more
difficult to determine and.assess their individual influence
on the chemical properties of water, though such factors basically
affect such properties. Nevertheless we do not find papers in
the literature which analyze the effect of important factors and
the conditions and processes of the formation of the chemical
composition of water.
•
of 82.9,2
/19" cl
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any gesatie
2.61;6‘
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12,2
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55,6
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300
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220
180
-31-
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trecr..fot, het' leb .-iélfà-lèhce' ,e/piee. d 26r7 ir --
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2040 /666 80,6 6;0 46;0 /1,7 7 + •5',/ 27+,6
- - 3900
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1000
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77, / letneet/ 44Mf es of Mette,e, CornreoSiWoil
in f4e, Paineee.
/— cemeice er dried- ••,- 3_-,étispendëd marter- e-d
- - - 7
mlyiniw / 11 /// y yn nil Ix ,r1271,ril
•
-32-
gl› The process of formation of the chemical composition of
surface waters is very complicated and takes a different course
under different geographical conditions (89, 92). VORONKOV
assumes that surface waters are an inseparable part of a certain
geographical zone. Chemical processes in water are genetically
connected with such a zone and reflect its peculiarities. He
ascribes the heterogeneity of chemical composition of surface
waters to the conditions of its formation in various geographical
zones and under various soil conditions of the same zone. On
these grounds VORONKOV thinks it necessary to study the laws
of formation, taking into account the conditions for the formation
of various genetic categories and also taking into account the
11› relative flow rates. He thinks that the determination of
genetic categories of waters is very difficult but at the same
time necessary for a deeper study of factors which influence
the hydrochemical regime of surface waters.
VORONKOV, as well as others, considers that precipitation
waters are the primary factor in the formation of the chemical
composition of waters of various genetic categories; the chemistry
of these waters changes as soon as they touch the earth's
surface. The chemical composition of waters affected by
precipitation gains peculiar properties depending on which layers
of soil or subsoil the formation is taking place in. Japanese
specialists (TAKAHISHA HANYA, UDZUMASA KITANO, TSUZUMAKI MICHIJI,
NAGYAMA, SHU, NONYTA SAJDZE etc.), some Soviet specialits
1110
(FILATOV, DENISOV, DZENS-LITOVSKII) as well as some others
(LE GRAND, BAECKER, WILD, BAUER and MOYLE) are of the opinion
• -33-
that the geological bedrock is the primary factor which influences
and determines chemical properties of water and that waters of
certain characteristic properties pertain to each geological
bedrock. These effects are very important because of their
character both from the theoretical and practical viewpoints.
Therefore in the next chapters we shall pay further attention
to them.
(A) EFFECTS OF SEASONS ON THE COMPOSITION OF WATER
Water composition changes considerably in the course of
a year or several years. It is the total mineralization that
changes as well as individual components and their mutual
relations. Some components change less, some more. The reason
for these changes can be seen not only in the effects of the
bedrock and hydrological conditions but also - partially - in
the changes of season. Seasons with related temperature and
soil conditions cause only gradual and slow changes in the
composition. Such changes also contribute to the occurrence of
mineralization.
From the viewpoint of practical needs it is nt.cessary to
learn the course of such changes within a year, season, months,
even individual days, because such changes may often be of
importance for the use of water. Nowaàays one cannot be
satisfied with only simple data on the mean composition, because
•
•
-34-
it changes greatly, depending on time and other factors.
Qualitative properties of water,.therefore, need to be character-
ized under various conditions and at various time intervals.
To accomplish a characterization we have accumulated
materials which we obtained from sampling sites (called
"profiles" by the author - translator's note) observed for a
long time (the Danube in Bratislava, Nitra River in Anala,
Laborec River in Michalovce and Rika River below Kamienka),
i.e. materials from drainage basins of different sizes and with
different bedrock as well.
The basic materials indicate that the composition of water
in individual years has changed to quite a considerable extent.
The same is true even to a larger extent of the composition
changes within a year.
The highest contents of components appear during the
summer and fall months in Rika River and in the fall and winter
months in the Danube, Nitra River and Laborec River. However,
not all components change vnth the same tendency. In Rika River,
for example, the highest amounts of alkali appear during the
summer months, those of calcium and magnesium in fall; in
Laborec River and Nitra River, however, the maximum amounts of
alkali appear in fall, etc. The highest alkali amounts in the
Danube occur in winter and fall (for details cf. Tables 5, 6, 7,
8 and 9 and Fig. 1, 2, 3, and 4.
•
-35-
Comparison of changes of the content of water components
with their abundance ratios (in mval%) indicates that the course
of the changes is different. We assumed that the highest
mval% abundance would correspond to the highest content of a
certain component and vice versa. It becomes evident from the
data that this is not correct, and that the changes of ion
ratios are affected rather by the_season than 10 - e- the content of
ions* (except the Danuabe), where the composition is more affected
by water sources. The lowest abundance of bicarbonates, for
example, occurs in spring, while sulfates and chlorides are
present in their maximum quantities in this season. The lowest
contents of calcium appear in spring and summer, while magnesium,
sodium and to some extent potassium contents at this time are
at their maxima.
For better orientation we present the results of our analyses
as processed according to the seasons (cf. Tables 10-13).
Hence it follows that the flow conditions have a great -
one can say dominating - influence on the composition changes.
However, from the abundance ratios of the components it follows
that even annual seasons and conditions depending on them
(precipitation, soil conditions, temperature and biological
processes) induce composition changes. These factors show less
influence during monthly and even less during daily intervals
than within a year, while the influence of the flow is far more
marked. • *The wording of the text is obscrue - Translator's note.
71,9.1)4../wit, Pratte monig(y eviden(s
-36 -
the Main lons 4,471ede anti hçeik
-àbiindâ-fiàe
7;tee. 6
• 141 -.81.4t/SUPet.1 r k/r/ /471 .. .
. „ref!' ci - col* me: + Ma+
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I
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XI/ 2136 2,94" 72,30 0,89 /46/ 0,33 8,08 2,6/ 6444 /,00 2469 433 815 0// 3. 7/ * 09 I fe 18 0, 0f + 9.82 4/3 1 /00
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MGCth. I 1
regle 7 deiken.
Nitre /.0 Arrakz.
/eeete etoeft(y de/t4À,is the main ions ,» iveuee,e e/te:i/ ege/n.
abundance
/Y a /ea; • de CI - CD 2. eg 2+ 1le* K + 2'A Zx ri
(inPi[tnyel/ 1] meled[fiere1/1][invo1 fe][myogl][inyel zi[eekel][mr01 °S]ilm61/1)[filyal Z] [1114'61/1][mr.01 %,;][/111will]l1/171•01 el [ftw1/1][/nral ,id[nee.51/11 1171Wi r]Unr.21/1)[,nrety]
/ 22,3 4, 0 66,1 400 15,0 226 /49 .9,97 192 176 248 0,90 - Y42 0,19 j 2,8 6,66 49,4* 982 fg 6 /3,48 /00
I/ 24, 2.83 eZe 0,1.3 /So 073 /7+ 3.64 59,7 1,1* 25:9 059 //,3 0,» 1 3,2 4,/8 +47 4,42 5/,3 ' e.e/ 100
dr 241 2,81 63. 4 0,71 /CC 0,73 /3. 0 2,45 60,6 402 22,8 ese /3,9 0,// j, 2,7 4,29 41 4:04' ! .985- 813 /00
/0 23.1 2,70 it 9 06'6 20,7 gm /0, 4* 2,42 ego 1, 05 256 4 f! /2,7 0,11 2,7 4,/1 50,4 4,19 49,6 826 /ea 1' /6,2 410 63.9 0,90 /48 0,81 /3. 5 2,78 55,9 1 +2 246 0,14 /2,e 0/3 2,6 485 +0+ 4, 87 sae 942 /00
17 /1,3 .7, 90 66,8 egi. /4,4 4/0 /41 4/9 56,0 170 294 ese 149 4/3 2,3 J;e+ I 50,6 570 444 /1,54 /00
ea A3. / 3,72 63,1 1,09 /43 1,19 /47 .486 80,3 /6/ 26,5 467 /1,0 419 2,! 490 I 49,3 407 507 /1,97 /00
el// 40 - .- 44.9 - 1. 00 - 3,92 - 1,84 - - - - - 2,49 - 578 - - /00
/X zs 4,13 87,2 1,0/ /6,4* 40/ /6, 4' .3:9/ 59,5 18/ 29, 8 45/ 8,4 4» 2,3 615 59: 3 607 46, 7 17. 17 /00 X 81 4,95 85,9 1,07 /4,5 1,44. /9,6 424 55,6 2,10 28,8 0,9e /2,8 0,2/ 2,1 736 +9,1 7,83 503 /4:99 /e0 X/ 9,3 445 645 1,01 / 4, 6 /,4.7 /9,9 4, 2,7 10,4. 1,99 23.9 • 1,20 /5,7 0,23 3,0 7,40 54/ 3.64. $1,8 /4, 76 /Oa
X// /to 3.95 640 47+ /2,9 1,04 /8,1 .7,59 59,3 /,37 2.3,2 0,87 /4,9 4/8 Z7 573 49,3 .090 50,7 /163 me . .
nil 1" /44 3,38 63. 4. 488 /7,8 489 /7,3 2,75 548 1,37 17.0 0,67 /3.6 0, /4' 2,8 3.14' fe 0,93 + 8,0 /0. 87 100 Meth
pe]
•
•
-37-
It needs to be emphasized that the changes of the mean
annual and monthly chemical composition of water are not in
full agreement with the flow conditions; this is due to various
conditions characteristic of the given river. This can be
observed on the Danube and partially also on Rika River. In
the Danube, e.g. the composition changes differently - on the
one hand according to the proportion of snowmelt and glacier
waters and on the other according to the contribution by small
tributaries in winter and fall, when the volume of ground and
pore water fed into the stream increases. These two sources
of different origin, which feed the stream with water, cause
different properties of water; these properties alternate twice
a year. The influence of the mentioned sources is relatively
great (cf. Table 5).
The effect of various sources of water is revealed not
only in the total content of mineral compounds but also in
their changes depending on the flow. During the season in
which the river is supplied with melt water, the curve has a
steeper slope.
Two seasons occur also with Rika River, but they are
connected rather with the subsoil and the degree of its
leaching. It is mainly a question of the season after long-
lasting elevated flow rates, especially after the melt water
runoff (i.e. April and May). In this period of time the total /41
contents of components in water are lower than at the time when
the water level is slightly elevated (especially with a
tendency to increase.
>1 .,spended
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- 39 -
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Actn 1710»7 evR7 Lee2& -the- main -10es ivede/e awe/ ieerk a btindânce in diffèrent _ _ . . _ . . _ seasons
.
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e/ 2,25 481 11,8 0,2C 25,5 . 4/3 /2,8 451 54;3 420 21,3 4/4 /4,8 409 48 1,02 540 a, 94 +50 1e6 /09
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5/ 0,82 0,8,1 19,8 0,2/ /7,7 0,15 /2, 6 0,51 546 422 22,2 0/2 /2,1 0,09 4/ 1/9 5+,6 499 4,5+ 2.18 /00
I9/ 124 0,81 144 428 221 0,/1 /2,6 0,10 52,e 0,25 21 9, 0,1.9 /54 all .9 7 /.27 I 52.7 1,/4' 474 2,4/ /00
po 4 7.1 0,90 73,2 aly /5,1 4/4 11,4 go- 52,0 0,3/ 2+4 419 /4,4 an 84 /*,23 446.. 125 s0+ 2,48 WO
/X 051 1,/0 70,7 0,11 /0,9 0,./8 4+ a 75' 16,4 0, 84' 251 0,17 /2,8 0,07 53 1,38 549 133 +9,1 2,7/ /00
• X 45+ 1,/1 7,9,3 417 /2,/ 4/2 8,9 477 60,2 0,26 243 4/7 /3,3 468 63 /, +0 52,2 1,23 478 2,69 /00
07 1,08 0,17 51,0 0,2+ /88 4/7 /3,3 ges 10,8 426 23,4 4/4 /2,6 408 2. 2 1, 28 58,1 /,// 4.4+ 2,39 /00
Xi zett 410 522 428 II,/ 0,17 /44 0,49 ea 0,2/ 21,9 4/7 /7,7 0,09 9, 4 410 04.5 0,96 455 _2.11 /00
a/Mead 1,41 417 14,4 4 24 23, 1 0,11 /2,6- 0,52 54,7 42/ 22,1 0,/4 /4,7 OW 8,4 194. 52,3 095 4.77 4 99 /00 /7leeltS
Tiabfe
[gal
• • •
Tà47c, - Mean evii i-enfs the rha.i n ions end abunciance in different seasons- -
itnngal a *ea,- 18:- et- e.g- eg,... N.- A-- 4 4 z.,
S 260I) k.%.,1 ("7,21] [mAel X] [Inrot][arefe] kiwi] Wet feJ [ewe] Peel z.j [inked kne1 y] [met] ['eel ej Well [owe! .ed [meet] [five! x
]
[,nmet] [owl ',Y.] [ere!) [elvel .1;,
]
511/2149 233f 3,/1 7133 0,88 20,11 e.37 449 2,80 62,20 403 2464 4 42 /4 01 ea .3// 4,36 51,01 4,/,2 I 449f e 5s, ma
Seine 182/ 2,73 71, 4/ 0,09 18,38 cm 429 2,3/ 82,09 ese 23,8/ 0,33 487 4/2 3,23 3,12 4031 372 50, 61 734 Am
Tall , 1410 2,74 74,4's Ceo /039 eM 474 2,30 62,19 4%98 26,09 0, 3/ 8,42 01/ 2,99 3,61 49,86 3,68 50,14 734 /00
1/44.1)tie /924 3,/5 72,41 0,84. /9,3/ 436 9,21 2,83 15,9/ 1,04 24;18 0,32 767 eye 2,32 4,35 5228 4,311 ,4472 485 e0
zes 2,49 73,65 489 /Zif 0,34 470 2,52 13,63 100 25,25 0,33 8,33 0,// 2,79 3,9/ 4.948 1,08 147,32 7,e7 /ail
TaZfe, if Cean_ coidenis of:the main ices 'd/e"abundance in different seasons
. ... . . _ ... knell e wca; .rre- • a' Coe' „ye, Me+ K 2;4 27, Z
seam [es] tmy.i] [..is] [m921] iffiral %][nnet] [oral Z] Umw1,1 krel t] [owed [met x] Unveil [mow% imred krel z] need [iv/ Z) owe] [m'2/7] [mre] ['we! X]
Speng 23,1 2,93 13,44 0,81 18,20 0,7/ /5,96 2,87 $6,16 422 28,9/ 0, .17 /2,09 4/2 2,84 441 5133 4,22 48,67 1,87 /00
StiallfeJZ 13,8 3,85 1364 1/0 /4/8 1/0 tent 2,19 54.e7 111 33,07 482 /2,42 ezi 2,6/ 005 5"4, 99 4,00 43, 20 /404 toe
Fail . 8,8 4,41 6492 0,96 /4, 3/ 42$ 4e 74 +,0! 542/ 1,8$ eft 407 /4,92 0,24, 3,35 e7/ le14* 7,17 I 14 68 /3,8 ea
White 15:9 4,22' 13,75 1,02 /5,41 134 10,91 4,48 60,43 471 25, . 406 /4,1e 0,11 4 76 4 62 ̀/7 29 zse 52,71 Ataa ea
frieete m,4 3,37 65, 44 415 ./7 28 049 /Z28 2,75 13,74 482 2779 0,12 /3,59 0/4 2114 3,te 5409 4, 91 i 449/ /909 /00
7,4 te, /02 eeae coe`edn's eithe ma -in-ions smai , a-bund.anc e in the different /*pen ___. _ „... _ .... .....
Ma': of"' 2, 1 , IA. 9 CC Cee*
Mg,. . _
2i efoollal 0 eV; .ra t-
f&r..rer Ws] [e», a t] new, 1.,1 [mra1][//1,01%] [eyed [faro! fd [mead krol :4] [mr,;(][favel ',',;] [ftwol] [meal ;,i [meal] [/nr.pl5d [mvoll[nival "4] [nved l[nh.ol e;] [e wad i[.'rea/ %.]
f Rifle 2848 2,/a 72, 6 1 417 /8, 66 423 Zes 480 69 77 0, 48 18,99 421 81.9 407 2,7/ 2,90 i 17,92 1,58 i 4708 j; ,,,,s
ee 496 2,62 , 74,69 412 /766 417 3, 69 2,9/ 63,65 4 e0 1 /7,3s. gm 867 4/1 4,33 3,51 10,36 3,46 : 4969 697 '00
LI«
I Fait, 442 2,97 77, 11 466 /en 0,22 474' 2,71 64,83 492 1 2440 0,6/ 9,8/ 0,/ 3,35 3,83 j 47,82 4,18 1 52,40 3, 0/ : .104
Viki,,e, 10,19 3, 91 77,4/ 46/ /5,48 429 4/1 2,66 74,09 4 67 I 18 66 4 20 457 0,96 4 67 3,94,1 1432 3,5gi. 4749 7. 01 ' /00
hem 2,13 7435 411 /9,01 e es 7,67 1,94 64 11 452 1 19 6+ 029 468 449 2,13 3,of 12» 2,7g .k7,0 3;82 . /ea
,^ffle_A.,• ■
Cean ctidemis of-àje nià in . Jim's and ffieigiti . .a...bundanc-é in t he different sea son e . _ even
Xamienk,
btee..
_ etnal liras- far er - Cat' . ee 449 A" . ,94
, 2-,
ediel r0,5's1 [mral] kwelkl[mv.21] [eye/ f4,][mvall ("lye! f4] Pnyoll [meal ['rived [,,?r,615;][mra1] mrel •,;][,nvol] [mral%][al] limr.9/%1[e»..9e] [[,,A91 3 ) [,,metli it,,,e/5•":
I I Siewhe 2,23 455 6/, /1 413 2456 4/2 /333, 4+1 13,17 4/8 21,68 4/2 /448 488 3,51 4 90 1/72 484 1 44 26 1, 74 /00
Slimy« 481 418 6,9, 29 4 2y fese 4/1 /1,3/ am 53,33 427 12,50 4/8 /3, 00 ell 9,v7 /,27 11,42 1.20 ; 4858 2 47 faa
I Fee, ,,e,. 478 63,4/ 419 13,59 4/6 /3,00 460 16,60 424 12,19 4/6 /38/ 0,48 3,51 /,13 53,71 1,06 I 4429 229 . va t
leinfea /.22 471 67,1'9 42/ /4 4+ 4/4 12,96- 414 18,74 4,21 12,93 410 /0,97 407 3, 61 1, 09 54, 04 0,92 Ï.___«9, 46 00 2, 90 180
Tétar r 1,e2 6;67 66,34; 42/ 1479 0,13 /2,87 0,12 .1-4;,74. 4 2/ 24/1 4/4 /5•,74. 409 8, ,,2 /,‘,/ 5/.5.7 4 95 1 , 47 1,96 ma mute i
•
O
-42-
For comparison the accompanying tables give the values of
the arithmetic means and weight means (the values are related to
the water volume) as well as estimated differences (in percentage)
between such data.
For rivers with a higher mineralization (the Danube,
Laborec, Nitra) the weighted means are lower, as a rule, than the
arithmetic means, though the differences are very low for the
Danube. In cases where the flow and precipitation have more
marked effects on the changes of compound contents (a decrease),
.as happens with the waters of low mineralization (Rika River), /44
where the weighted means in many cases are even higher than the
arithmetic means; the flow or precipitation changes show
different effects in sites where the mineralization of water is
low (incomprehensible in Slovak - translator's note). Also
remarkable is the fact that the differences between the two
means are lower in individual months than if average annual
values are taken into consideration. It is caused by the fact
that the flow ratios are better balcanced in individual months
than within a year. Errors which can arise due to incorrect
processing of the basic materials, can also be seen from these
data. Assuming that the basic materials mentioned here stem
from about 150-350 analyses, there is a great probability
that the effects of accidental atypical data will cancel
themselves. Obviously even greater errors can occur when
processing a smaller number of samples.
-43-
•
IUNN e 71-4
Fig. 4. Annual alterations of water composition in Rika River
1. Specific conductivity 2. Suspended matter dried 3. Suspended matter ignited 4..
5 . Flow Q
(B) PRECIPITATION CONDITIONS AND THEIR EFFECT /47
ON THE COMPOSITION OF RIVER WATER
Despite different opinions, bibliographic reviews indicate
that precipitation exerts a great influence on the final compos-
ition of water. It exercises a double effect:
a) Physical - due to diluting more mineralized river water, and
h) Chemical - supply and direct supplementation of water with chemical components.
•
•
-44.- •
•
00
7,e. 5 ee, emmua/ peeeiloifa7/1 Jletebek, (ftei Me/we/0d «o/- /950)
7a-ee, efizet-de,e2 ea. eeMpoS /Won of filegaijoiietWon ceteleS
(a mozolieg jdo
'é w 5 et zeM ets)
ebt2/24.019-12- 1st, e... acdpitet-Tfs=i475- r..e.mx-des
dent, n en f Burk.rer necogra /I? . 10-
6irenku Me104e zteth °es ( eid-h) minimum moximum minimum merimum eean• Nelel In I M morimum mean,
eftetddn- cdd2 460 81,06 0,60 3600 5,e 420 21,00 1,00
Iirenesiite Mg r • 0,30' 8,30 eta nort • 460 0,00 /zoo 0,10 -- too
/4kedi ode + e ) 0,60 30,80 4/0 3300 2,70 0,10 15400 410 .. 15,00
at' e;tki 0 We; A I CO; 3,05 .90,28 3,00 +1,00 14,20 3,10 62,00 4,00
lc/M5-304, - 3,01 90,28 0,60 7800 11,4.0 0,10 9700 2.00 - 74 00
Chlaridtg- cc 1,08 255,60 0,20 34,00 0,50 0,10 260,00 400 - .M.. 00
4liteales -NO; • 0,39 402 2,0 0,22 0,00 .9,0 .0,01 -.- 490
Afruncilig- bye 0,17 0,06 2,0 0,26 0,03 12,00 0,10 "'. 480
3devdedhe- &d. 40008 4- 4010 - - - - , - -
.101:11./70 -7,2_ 0,0015 * - - - - -
Maitik'm e, ag.eq 5 o. 2o - 0,,e0 Je_ Pitee
•
Ut 93
-45-
It is sufficient for the assessment of the physical effect
on river water composition to have more detailed data on the
flow conditions or on the total precipitation in a typical
season and at the profile under study. It is sufficient to
know the flow conditions, because they are actually the result
of precipitation conditions and other climitic factors.
Precipitation conditions in Slovakia (totals and the
terrirtorial distribution) are schematically shown in Fig. 5.
This basic material is sufficient to give a rough idea of the
balance of the discharge of compounds from the river basin.
To judge the other, i.e. chemical influence, it is necessary
to learn about the composition of precipitation waters. As a
matter of fact the chemical influence consists in enriching
water with compounds present in the precipitation and in the
atmosphere in general, i.e..in the direct supply of chemical
components to river water.
Precipitation waters are characterized by certain contents
of mineral and organic compounds. As compared to river waters,
they are characterized by a higher content of dissolved gases
and also by different abundances of the main ions.
It follows from bibliographic references that the composition
of precipitation waters is relatively diverse (cf. Table 14).
The difference in these data is caused by various factors,
which can have various effects on the final composition of
water. From the existing knowledge it emerges that in arid,
flat, industrial and maritime areas precipitation waters contain /49
more salt than precipitation waters in mountainous and humid
• -46-
areas. In maritime areas there are increased contents of
chlorides, potassium, magnesium and iodine (82, 32). In more
distant sites their ratios change together with the salt contents.
The changes of precipitation water composition are different
and dependent on weather, season, landscape, etc.
Precipitation waters on our territory are characterized
by relatively high Mineralization (about 40-60 mg/1.) and
suspended matter (about 30-40 mg/1.). In some cases bicarbonates
or sulfates are the main anions. It is evident from our data
(cf. Table 15) that sulfates are a very variable component of
precipitation waters. Their contents'fluctuate between 1 and
36 mg/1., and, therefore, in many cases the rain-water is of
the sulfate type. Calcium, and in some cases sodium and
potassium, are the main cations. Rain-water contains relatively
more alkali and ammonia than river Water, and therefore
their abundance ratios are also different.
Hence it follows that most mineralized waters occur in the
vicinity of industrial centres and that in the mountains the
precipitation is somewhat less mineralized. On observing the
composition of precipitation water, we find that the mineraliza-
tion is lower at the beginning than at the end of the rain; it
is in agreement with GIRENKOIS finding on the effect of the
duration of rain on the chemical composition but not with the
opinion of TAKASIMA.
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•
•
•
The opinons of authors concerning the effects of precipit-
ation on the composition of river water are not in agreement.
VORONKOV asserts that in the northern parts of the U.S.S.R.
the effects of precipitation are considerable and that they
diminish in the southward direction (toward lowlands); HAVRÂNEK
is of a similar opinion. This phenomenon is ascribed to a
gradual pollution of the atmosphere. On the other hand
DZENS-LITOVSKII asserts that the northern sections of rivers
in the U.S.S.R. are subject to geological effects and southern
river sections to climatic effects.
GAaMONOV estimates that climatic conditions affect the
changes of chemical composition of water in such a way that in
areas where precipitation predominates over evaporation of
water (northern part of the U.S.S.R.), bicarbonates are the
main anions. In areas with low precipitation the sulfate and
chloride contents are rising. The author is of the opinion
that ground waters, like surface waters, respond to the climatic
conditions; in areas of high precipitation the waters are of
the bicarbonate type, in areas of low precipitation of the
sulfate type, and in arid areas, where evaporation shows a
great predominance over precipitation, the waters are of the
chloride type. This opinion can be considered basically correct,
but changes of the composition of river water cannot be ascribed
precipitation only, or to a complex of climatic factors, because
the composition of water is affected by other factors . also,
as we shall see later.
19_
•
-49 -
As evident, climatic conditions and especially precipitation
conditions exert a great influence on the chemical composition.
However no dominating influence should be ascribed to them.
We know about cases of a higher total water runoff per square
unit in which the mineralization is higher than would have
been expected. The mineralization of the Amazon River, for
example, is 37 mg/l. at a total runoff of 100 cm, but river
waters on the island of Java (Serajo River and Meravo River)
have mineralization of 122 and 107 mg/1., respectively, and a
runoff as high as 150 cm. Even under our conditions there are
completely different properties of river waters (Rika River,
Sobranecky Creek, Topla River etc.) while the precipitation and
runoff conditions are the same. Hence it follows that there do
exist still other factors which affect the composition of water
remarkably.
To estimate the effect of precipitation on the changes of
the composition of river water, it is sufficient to draw up-
a balance of the rain-fall, record the flow changes in the river
and analyze the chemical composition of the water. Differences
which result from the balance of the composition of river water
should be ascribed to other effects (soil, general climate,
temperature, etc.). It means practically that when observing
the laws controlling the composition of river water, the precipit-
ation in a certain case must be analyzed from the viewpoint of
heterogeneity under local conditions, and only then they can it
be used for the proper purposes.
•
•
-50-
As far as our own conditions are concerned, it can be
stated that many of the factors listed above 5peed and direction
of winds, various localities etc..(such factors were not listed
above - translator/snotel7 will not affect the composition of
precipitation to the same extent as in countries in which the
conditions are often completely different.. It can be assumed
that in our country it will be industry, the season and
duration of rains which will exert the greatest influence on
the composition of precipitation.
(C) SUBSOIL AND ITS EFFECTS ON THE COMPOSITION OF SURFACE WATERS
There are no doubts any more than the composition of
surface water is seriously affected by the subsoil, though
there is no uniformity of opinion on the effect of g eological
and soil conditions on the final composition. Some authors
are of the opinion that geological conditions are the main
primary factor, but other authors have the idea that it is
primarily the soil conditions which exert the main influence
on the composition of surface water. The study and substantiation
of the influence of geological conditions should be considered
•
•
•
•
-51-
more opposite because the geological conditions produce the
parent rock, from which the soils and substrates originate
(due to decomposition and weathering of the base .rock).*
It is impossible to exclude the effects of other factors
on the composition of water. On the contrary they may be very
strong. In spite of this, the subsoil remains the main factor
determining the qualitative properties of surface waters. The
author came to these conclusions on the grounds of his own
experience; these conclusions can be confirmed by data which
he has already reported when analyzing the effects of precipita-
tion. The waters of the Amazon River (South America) and Serajo
and Meravo rivers (on the island of Java) have low mineralization,
which is usually ascribed to the precipitation conditions.
Although the runoff on the island of Java is about 50 cm, i.e.
50%, higher than the runoff in South America in the area of
the Amazon, where the runoff is 100 cm, the mineralization of
of the Amazon waters is approximately three times lower.
Mineralization of water in our rivers is different (Rika River,
Sobranecky Creek, Topla River etc.) although the runoff is
practically the same. In view of all this, it is possible that
*The style of this book is unusually poor. There are many paragraphs which do not make sense even in Slovak. The sentences are extremely long and branched. The main verbs, nouns or adjectives are often missing. On the other hand the author has used excessive words, often in a wrong sense. An accumulation of nouns is very common in this paper. The book is full of awkward passages in Slovak and the translator did not know how to cope with them. The principles of the book could be presented briefly in several pages of an abstract. - Translator's note.
•
•
-52-
11, the difference in mineralization has been caused by another
factor, and that factor is the subsoil in our opinion.
1. The Composition of River Water as Related to Soil Conditions
It becomes evident from our general knowledge of the
effects of the subsoil on the composition of surface waters
that the subsoil has a great influence, and actually determines
the basic character of surface waters. The main effect is
exercised by the bedrock. Soil conditions in the drained
territory have a great influence on the formation of the
chemical composition of river water and sometimes they affect
its composition to a great extent. However, they cannot be
considered to possess a unique influence as far as the deter-
mination of basic qualitative properties is concerned. Although
the influence of soil conditions is immense, the author did
not succeed in finding a relationship between characteristic
properties of water and various types of soil even after he
had processed a great quantity of material on the quality of
water, which had been collected from the entire territory of
Slovakia. On the other hand he discovered distinct qualitative
properties, i.e. the dependence of the content of total
mineralization on hydrogeological conditions.
On the basis of his own knowledge and the opinions of
other specialists the author arrived at the conclusion that for
the formation of basic properties of surface water the bedrock
is of the greatest importance. For the processes associated
with the leaching and dissolving of individual components the
•
•
-53-
primary factor is the soil with its sorption complex, which
pertafns to the bedrock. This opinion is considered by the
author to be correct also because the geological conditions,
i.e. the parent materials together with the climatic conditions
and the vegetation, are the main factors which determine the
character of the surface soil strata, or in other words, the
character of the soil type, which possesses (in addition to
other properties) also the properties of a sorption complex.
The state of the sorption complex and the quality and quantity
of individual sorbed cations determine many other important
properties in addition to the soil reaction. Due to various
climatic conditions the properties of the surface part may
indeed change, but the principal properties continue to be
shared.
Thus the soil and its influence on the composition of
water can be characterized rather as a certain active factor,
i.e. a factor in which the compounds change and are prepared in
a form which then enters water easily; the quality of the water,
however, depends on that of the parent rock.
There was no success in finding how the composition of
waters could be related to and depend on pedological conditions,
though the effects of pedological conditions cannot be denied
and there are many papers and essays on their effects.
Therefore in the next chapters we shall not deal with a detailed
analysis of the relations between water and soil. Instead we
present a map of soil types (Fig. 6) by means of which it is
possible to compare the conclusions, i.e. the relation between
qualitative properties of waters of individual rivers and soil
types.
•
• •
Meenozems and "Weed. soils [7:7 Rene/elm/5 3u.eozems L j Ave mounietin
wz.tzzed,sods - • et' es (ekele
(
al)
end pod2of s ils
Ataceete Soils
Aar of /floes egavale-ieu
-.55-- •
•
2. Dependence of the Composition of River Water on the Bedrock
The preceding chapter showed clearly that a relation
exists between the soil conditions and the composition of
water. After we divided (the results of*) chemical analyses of
individual rivers according to the more marked geological
regions, it was found that certain relations do exist.
A great number of authors dealing with analyses of surface
waters and the conditions under which the basic chemical
properties of water had formed, relate the chemical processes
in water to the bedrock of the drained area. First of all
the Japanese specialists confidently assert that the composition
of river waters results from the effects of the bedrock. They
arrived at this conclusion on the grounds of observations in
nature and laboratories.
Also in the Soviet Union, where hydrochemistry of surface
waters has been studied in considerable depth, many authors
hold the opinion that the bedrock is the primary factor
affecting the processes in water.
Even those Soviet authors who ascribe a great importance
to the upper part of the subsoil, or, properly speaking, to
soil conditions in the formation of the composition of water,
do not exclude the effects of rocks on the basic porperties of
surface waters.
*Added by translator.
•
•
-56-
To emphasize that the bedrock gives the main_characteristic /56
properties to water we shall present another set of data on
heavy or rare metals (Table 16), which are exclusively under
the effects of the bedrock and not external (climatic) factors.
The presence of a certain amount of such components in
water proves the effect of the bedrock on the composition of
water.
Also LE GRAND and MOYLE (59, 64) are among the authors who
are of the opinion that geological conditions determine the
properties of surface waters.
BAEGKER (24) and WILD and BAUER (65) are also convinced
of the influence of bedrock on the composition of water.
They have already discovered salt deposits from the composition
of water.
As far as our conditions are concerned, the author
processed the basic materials on the chemical composition of
waters of Slovak rivers (23) and correlated them to hydro-
geological conditions in Slovakia. It is evident from the
materials that the river waters have various compositions,
but they are in agreement with defined regions.
When analyzing the dependence of water composition on
geological conditions, it is necessary to refer to data published
by BEHOUNEK (33). Although these data deal with ground waters,
the effects of rocks on the composition of water are clearly
evident (Table 17).
/57
• 77z4te, /6"
-57-
•
ealfames of heavy edecuzeinglaisin waiv ( /net)
ificulece. •o »nee,. CU , Z/7, Cd, I'd, Li Ce Rd Ti 4.4> Ze Ou a, riyika
evens la- Bohemia.. a015 fib - - - - - q 0.+ 0, 0/2
/. ,..... Buchtormo e; eee., 0,02 - - - - _ _ _
lienchi (71 Zueeniséayaleerek 407 - - - - - - -
ieteellns oeiqienelo In- aa,eas of •i,ae miribie 41 _ _ _ _ _ ._
teGt£M9 C(/224/ 435/ .
ZelVa1/475k4reti e/ rate e f _ - - - - _ _
eyzeams clelh),...!filq. 44, «as of ce: mefehy 2,85 - - - - - _ -
A evilq ...e4 the eitea.., - 3, of del-Jos/1-s of Z', _ - _ _ _ 24/0 9
/1 speeiny-in ..ni.isk..._ 4.e. - _ _ _ eeepn ( K4rzakh...sfan)
, - - - - 4,0 0;06 - - thleoaa's ..5/2/eilys
cletrhin Is Ri Pen 5 - 4001 40002 0,00+ - - - -
cligeneee sl'beh'ef beerns/4/ng:)5 »ofe)
Titee, /7 e01rep0S70/7 Runninf ozei Pez+el'ouS
Semi- Com/totimc,i . dion, elitnitz. ey4yt -4‘45,z-b` 'elate- usign-p- ,WYP5=0»
eeectnbeczWon or essoived cqmp,?(Ails en„ 2'n /€.
Pay nesiolue, 2540 24,0 --2/40 /60,0 /10,0 /20,0 125,0 2 265,0
cep. eonguais. 1) 2,e 3,1 8,0 «3 i;eetca_s /, f Yle..4Ces
On 0 78,0 e7 - 450 62,0 5, 2 10,0 /28,0 76¢2.0
A180 50 25 ..... 210 12,0 3,0 ZO 2.9,0 128,0
le- ea 84,0 -IMO /7, 0 45 2f,0 /4,0 1 /04 0
/0, 8 ao - 40 ao - 40 ao - 4 0 0,0 __140 0,5 iitaces
Oh/orio'es-CI - 40 e2 - /40 40 *goes 5,0 4,0 /40
•
-5E-
This brief review gives clear evidence that geological
conditions have 'a great influence on the composition of surface
waters. One can even say that geological conditions with the
adhering overburden (soil) determine the principal and charac-
teristic properties of water, which change, more or less, under
the effects of other factors. A majority of authors is of
such an opinion, which can be considered to be correct, though
there do exist also other opinions that the composition of water
is not always related to the geological environment (65, 42).
Evaluation of Results
We shall briefly characterize the chemical composition of
waters of Slovakia with respect to the bedrock in agreement with
the hydrogeological divisions of the territory (cf. Fig. 7).
We have selected the following categories as processed in
agreement with the State Hydrological Plan (1954):
1. Crystalline rocks with quartz formations,
2. Granite massifs and Quaternary terraces,
3. Eruptive rocks of the Early Tertiary,
4. Triassic limestone and dolomites,
5. Triassic limestone and dolomites and the Upper Triassic to the Lower Cretaceous,
6. Werfenian layers and Triassic limestone and dolomites,
7. Bald mountain flysch,
E. Flysch with ample occurrence of sandstone and conglomerates,
9. Pyroclasts,
10. Holocene.
/58
•
frj 8 # Et1 8 Ile Fig. 7.
"
nydrogeological map - oi'Sroliakià Tas based on data of the Ystatny vodohospodarsky plan (State HydrologiCal Plan).
1. Alluvium with horizons of phreatic water;
2. Neogene with horizons of ground water in aquiferous layers - there are usually Artesian waters in the lowlands and basins;
gl, 3. Neogenic pyroclasts with fissure waters; .
4. Oligocene without water sources as a rule, Upper Oligocene with water horizons in gravel, sand and conglomerates;
5. Bald mountain flysch with fissure waters of negligible yield, conglomerates of the bald mountain flysch with fissure-semikarst waters;
6. Flysch with fissure-stratiform waters of negligible yield, flysch zone with prevailing sandstone and conglomerates with fissure waters;
7. Klippe zone with fissure waters of lower yield;
E. Upper Triassic to Lower Cretaceous, mostly impermeable, sporadically with fissure-stratiform waters of negligible yield;
9. Triassic limestone and dolomites with fissure-semikarst waters of great yield;
10. Werfenian layers, impermeable as a rule, in limestone and melaphyric strata with fissure waters of low yield;
11. Crystalline and quartz rocks with fissure waters of a negligible yield, larger lenses of Carboniferous limestone with semikarst waters;
12. Granite massifs in upper strata and surface zones with fissure waters of low yield.
•
•
-6o-
We have divided our rivers under study according to the
preceding classification so that the chemical composition of the
section assessed corresponds more or less to a pure geological
type. It turned out that in some cases (especially in crystalline
rocks and granite massifs) only a small amount of other formations
was sufficient to affect the chemical composition of water
considerably. According to such a selection of rivers one can
speak about the composition of surface waters typical of
certain bedrocks.
Tables 2, 3 and 18 present composition of water, abundance
ratios of components and ratios of componerits which correspond
to a certain geological bedrock. They show clearly that the
least mineralized waters occur in the area of granite massifs,
crystalline rocks and eruptive rocks of the Early Tertiary.
Total mineralization of waters flowing from these geological
formations is most frequently between 50 and 80 mg/l. As far
as the chemical composition of these low-mineralized waters is
concerned, it is most remarkable that waters flowing out from
granite massifs have higher bicarbonate contents than waters from
Early Tertiary eruptive rocks and especially from crystalline
rocks.
•
• •
nilc /8
6Mi oSilioe ts/crien, estxtioeS
uspendeç déoree4y/eal eeyiees
Tri i
Tri
Wel Tri
r.. ----I rota/ /frebecietios7iecz/ even., ez tic/ . . .. i a id te c. hand.; samfifine_ e, _ i at_40,9e j7e6s,.,- NCO; 80:- el- ce Ng' //a+ A' + i102
/tee icq, Ye
(mg/Il [. 1 , •
elZySlid7/1 177 G. g-oCée-S Élecck 1/ron4• 6,"ellron ice, 740 1,7 2e1 /4'o e, 1 ea 24 2, 1 3,.;" 50 le I /17 q « adel
, Z. kimevice 640 46 21,4 /1,0 4,0 /2,0 1,7 2,7 8,3 3,1
,Zrenetices ..- lean/ fe Maseives Perade. e. e.ve.-foNt. 84 0 12 443 4,1 3,3 /OA, 1,1 6,2 54 -
anal eduate/enevey Prieb»D de PribiNize.e 540 2,0 449 94 1,3 /14 1,2 2,0 2,2 4,0 tedeezees
eaidy re,- eliadey Okne 1./1 750 48 ea li,.e 3,7 es 2,2 82 8,2 /45 Remetrki , lifmre, egeloWee. eociess A'ike Wad Kemienka, 770 11 37,0 45 3,8 4+ 2,3 17 4,4- 152
. SiC" limeeiree end Reerca ei a/Ate/peke,/ Crecie, 2/50 /0,0 184,7 35,0 2,0 41,0 /2,0 - - 40
/OW/P.-S. e A/Nrka ii,Bie/iciach, 4/4,0 /2,2 2257 780 35,7 5e - - - - .3:à SIC ern »wee, zu,agioneki.Ceedi+,1upècr, 210,0 9,3 2fe 6 cso 4,1 740 /40 1,0 II -
eilea.dtet itS •
freed) h/i//1 71i1a70417171. reAl; l/ant/Zan • é• .. 263,0 11,0 289,0 .121 5,0 59,0 Me es 4: 2 Z2 AM•e5f7177e 4r7Ci _1 Labarge A Kerekorce . 238, 0 e7 /e,a .1.3;6 44' 11,4 57 6:1 e7 42
cony/cm:Aar-es
#04 cen e- /10//./20 4./.9kelb0y 2950 /1,0 20/,3 42,0 Mg 80,0 11,0 9,6 '4, 0 /8,0
Ael_f_e, .zon-e, ,Tobreneck, &Lek, 2740 - /47 2440 /es .Z 9 14,1 19,1 4,0 .zel 14,1
•f e nian Al gee 5
ass iC'-iirrYeSaiteal- Pernaï- in 1/ern42' 414,0 142 261,1 /149 2,5 - - - - - - '
cm c:/ Poi0e) ifeS •
•
•
•
-62-
While there is about 70-75 mval% HCO- in waters from 3
granite massifs, only 45-55 mval% appears in waters from
crystalline rocks and 55-65 mval%.from Early Tertiary eruptive
rocks. On the contrary waters from crystalline rocks have a
higher abundance ratio of sulfates than the waters from granite
massifs and Early Teriary eruptive rocks. Similar differences
can be observed with the contents of calcium and magnesium.
The highest calcium abundance in mval% is found in waters from
granite massifs, then from crystalline rocks and finally in
waters from Early Tertiary eruptive rocks. Magnesium abundance
is the reverse - the lowest percentage occurs in waters from
granite massifs and a higher percentage in waters from crystalline
and Early Tertiary eruptive rocks. It should be noted that the
SiO2 contents are very high in waters from crystalline and
Early Tertiary eruptive rocks and low in waters from granite
massifs.
Another more marked group is formed by waters from Triassic
limestone and dolomites with about 200-250 mg/l. of suspended
matter. The main anion HCO - represents about 79-83 mval% and 3
sulfates approximately 15 mval%. Very similar to the waters
from Triassic limestone and dolomites are waters in the
East Slovakia Flysch region, especially as far as mineralization
and the abundance of the main ions are concerned.
Waters with higher mineralization pertain to another
group of waters, i.e. waters flowing from the bald mountain
flysch, Werfenian layers, Triassic limestone and dolomites,
Neogene and alluvium. Plain characterization according to
•
•
-63-
total mineralization is insufficient as far as waters from these
bedrocks are concerned, and the contents of individual components
must be compared with one another. Considerable differences,
which are characteristic of a certain bedrock, become evident
when comparing the abundance of the main ions.
Waters flowing from bald mountain flysch are characterized
by an exceptionally high HCO; abundance of 85-88 mval% (the
highest under our conditions), but they contain approximately
10 mval% sulfates, 2.5 mval% chlorides, 68-77 mval% calcium
and 22-32 mval% magnesium.
Waters flowing from Werfenian limestone and dolomites have
completely different hydrochemical properties. These waters
are highly mineralized, but of the main prevailing anions
bicarbonates form only 62-65 mval%, while sulfates reach up to
32-33 mval%, and chlorides only 2-3 mval%. Cations in these
waters are present in quantities similar to those in waters
from bald mountain flysch with the difference that waters from
Werfenian limestone and dolomites have a higher mval% abundance
of magnesium.
A higher abundance of HCO3 and calcium can be observed
in waters from the alluvium.
Chemical composition of waters in other Slovak rivers
fluctuates within the limits set for the types described. It
cannot be assessed so unequivocally, because there always takes
place a sort of mixing of several water types pertaining to a
certain bedrock.
-64-
III FACTORS GOVERNING RIVER WATER COMPOSITION CHANGES /62,
Changes of the composition of water as related to other
factors do not affect only the total mineralization or individual
components but also the abundance ratios of individual components
of the total mineralization and the ratios of the components.
This relates to the changes within a year (season), when the
abundance ratio of a certain component changes at the expense of
another component. The change of abundance, however, does not
need to be in agreement with the change of the total content of
components (for details cf. Tables 6-13). The changes of the
composition of water are affected by climatic factors, sources
feeding the river, soil conditions etc. Since the conditions
or the intensity of the influence of individual factors are
not the same everywhere, the changes of the composition of
surface waters in individual rivers are not the same.
Changes of the abundance ratios of water components are
severely affected by the subsoil of the drained territory. The
effects of the subsoil of the drained territory are so extensive
that on the grounds of some ratios of components it was possible
to determine to what subsoil certain water belonged. Table 3
presents the coefficients of ratios of the main ions. Hence
it is evident how different are the coefficients of certain
groups with respect to the subsoil, while the coefficients are
only slightly different from èach other in a certain subsoil.
Various classification systems of surface water quality
have been designed on the basis of the ratios of components.
çe'
100 200
ion.51mg/1] _
250
200
150
'
1
: • • 1 • • • • . • •
• ' . • •
• •
J.. «
é a
e • , •• , • • • • • • • % •• de •
• • • • • • Y.
• . It 2. ••
: • • .
• • .
i
I 250 300 350 -450
-65-
The content and abundance of components determine utilization
of water and must, therefore, be evaluated. Evidently, the
assessment of relations between the components of water is of
great importance. The evaluation relations is also important
from our point of view; in the next parts we shall be able tc5
use them as the basic and auxiliary meterials for the prediction
of the composition of water.
•
Fig. 8. Dependence of the HCO - content change on 27d_ of the 3 water of the Danube
(A)- RELATIONS OF COMPONENTS TO TOTAL MINERALIZATION /63
As we have already mentioned, the relations between the
various water components and to the total mineralization are of
great practical importance, because first of all they determine
the qualitative properties of water. On these grounds, as well
-66-
as in order to collect basic and auxiliary materials for the
prediction of the composition of water, we shall evaluate the
relations of the main ions to total minei.alization and specific
conductivity in detail. The relations obtained in this way can
be used in conjunction with the dependence of total mineralization
on the flow in a river to forecast how the composition of water
will change.
Graphical processing of the materials indicates that a
linear relation exists between the majority of cmmponents and
total mineralization. Dispersion of experimental points is
relatively small (cf. Fig. 8, 9, 10 and 11). With some components
(SO4 ' Na, K, and partially also C1 - ) the dispersion is
111› considerably higher (Fig. 12a, b).
It is evident from the calculations of the degree of
dependence (correlation coefficients) that the coefficients are
relatively high and that the correlation is very close (cf.
Tables 19-22a).
The values of correlation coefficients calculated from the
formula
x,y (x- k") (Y. - 7)
t (xi _ 5-02 (yi _7)2 fluctuate most frequently within the limits of 0.7 to 0.95. The
degrees of dependence are lower for magnesium and even lower for
alkalis, chlorides and sulfates, but still they lie above the
limits of significance. In some cases they are so small that
one cannot speak about any dependence.
•
•
• 21i
s
I 13
310 270 290 330 350 370
-67-
eq./
120 a
a
VO
0
60
.---•"""e''''»elr'e!"--"e '
MO 1M 720 « 280 _700 .740 MO +20 MO MO MO MO Me MO 7L
Zilenefi l
eyeencieec-e, of Me aree'i-coofeeet 'c4ezesfe-oe 2j of the kveden, af Nibect;
!
1 o
• o o
? -t-- 1 o 0
o o
1
o
1 0 °
r o
• o •
230 250 irrng /1]
F/e, /0- D9 , 3,,./e,,,,,e 0/ the hieeà- content cAderiya,
• o„ 4. eV /he kveden, .Leîo,gec
•
I
150 170 190 210
54
Si
1 31
oe, 11
/65
-6e-
8 / 00
0
0
) n
0
?
• 0 0
0
? -
•
0 7 •
•
0 u
0 , 0 .
•
,
30 410 50 80 Xi[men]
70. 80 90 100 HO /20 130 /40 • •
Fig. 11. Dependence of the HCO content changes on of the water of the Rika Ri1er 1
The dispersion of experimental points is affected by various
factors (precipitation, soil conditions, water source etc.) which
act in varying degrees and invarious time intervals. But as a
rule they are not the same as those which affect the mineral
ization, which depends to the greatest extent on the two main
ions (IWO - and Ca - ). This means that in Waters of the bicarbonate-
lime type with a high mval% abundance of these components there
will be a good dependence. The functional dependence which
should exist between total mineralization and the components
which participate on the mineralization, will be disturbed only
to a small extent. •
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'x) /ce2+
(Y) 248 49 /1,8 2e6 ,es >2,17 2461 3e7/ e92 4.11 476 ee..7 8,0141 40,4e• y- .4'12#x +7.40
4x) / ,i 2 24 7 As 2,8 27. 7 42 17. 71 2478 47.1! 40'7 4 42 eef 4 690 48221 4‘74100 y =Café 2 x -488
(e) S.
I(x) /ive+(Y) 24e 849 22 241 48 19,09 2481 17,27 ye 409 ...eq- 44es 10111 41196' y-0,02.gx +417
Delebafeece; Vectee4.04ç0/S gle eieniee of ions De icia./ en:AedeePz494;en 220
ee4 event'« iMmeecieee 6Wie/ lineae, /ta45, . v de.getalion etfotesricn eet&?,s'en:
n ' I - 4 de .rx . 7.'84.1- . 35, ■ f:y 184,.ry My ±1 E 4e xtX/4'
. ( etect,4J-
£ (x) - - 21 390 272 eee „ref 22,// .16,26 69470 /4 78 2752 8416 +4759 48873 42200 se=esex + 48e / -(b )
4.(x) 7 s0+2- re) 25 190 07.2 fed? 9,9 42,46 84 11 293;3 8, +3 1497 46,e1 +ercze e /220 4+990 e=40fex + 1417
Z. 25 290 254/ 5/9 es;a /999 29,84 71,82 1449 /7. 76 56,29 +4958 40/1/ 90999 e=c,7se x - e8,21
(Y) .
'x) / Ce2(e+) 1.9 .190 646 57.9 8,2 .1623 59+2 /78,26 6,67 8, 95 2965 +47/e 80258 e420/8 y =4 ea x - /1,28
•
-73-
To find out whether the dependence does exist between /70
individual components and total mineralization, and of what -
kind it is, we calculated the probable errors of correlation
coefficients from the formula r
E = 0.6745 1 -x,y
We then verified whether the condition of reliability of
the correlation coefficients 4E.:4jx,y had been fulfilled. It
can be found from the materials at hand that this condition has
been fulfilled in a majority of cases, though the correlation
coefficients are different for individual components and various
rivers.
How individual components fulfill this condition can, and
only in a few cases are they within the limits of significance
(p = 0.05). Only in isolated cases are these values below the
limits of significance.
(B) RELATIONSHIP BETWEEN SPECIFIC CONDUCTIVITY AND OTHER MAIN i71
COMPONENTS OF WATER
Nowadays determination of the specific conductivity of
water is generally used when analyzing water. Many authors
ascribe great importance to the specific conductivity, especially
because it gives an idea of the total content of the compounds
dissociated in the water. On these grounds it is recommended
for checking changes in the composition of water.
2
•
• •
l eeeSçie/les" ce 14.e €eafio of spee.eeddligeivity 1
(a) ,(10) f/co; cpt. le* - 21/ oo, x/ x/ X/
0/ leafee_.
uncj
Lab ore c Topic RikQ Nitre Hron
0 777 0,5/5 0,767 1,056
a, ,26Z 0,524
0632 0,515
0 Bi-
o; 160
/19 a/25 0/06 e 1 •1 0,115 0,166
0,022 0,027
4022 0,060 0056
0,037
a/76 8/71 0116
0,112 0,127
4044. 025.
0,052 0033 004.6 0,040
0,057 0015
01'1 0,039 0,042 0,042
0,015 4016 0,01+ 0,022
015/ 9, 019
046,
1,082 toes 0,971 1,232 Za00
4 se 0,6/3 8, 66! 0,527
0,566 0,546
• ----- - -- Suspended matter dried B = Suspended matter ignited _
-)F A
doeek/mYs Rah.° of reeSè. coeirizeeikily (7e) am/ mote. impoeileet Psealeie, eomponees
(a) Suspended matter dried (b) Suspended matter ignited
*Suspended matter
4e-ea-ien715 e. geg-Wo eye ree0" e.. coeciteeiSy a.bey dome
Corn/Jo/le/71"S t7e hIcrAteee ;viz% ites,e,e74 el. ereeittecele. O7 G.
23
7721.P-• 24
&zee. Coefficient el /he Rai% iFt.-Cede/teell. zee !row en -teed/a-1s e.,..„.....„ ean._
0 44 7,1 z.1 44 44 37.541 .5,44 /10 41141/15 /1,144111 11145177 le1-,714 leers 77.5 117e740114417.117741.71017444,71, 71.744V 1404174f 777+4444 #414441 417.3e1 f0.4•77 #474e711
7
4757 4700 4751 4701 4457 41(4 4472 7.?17 4I01 4477 4104 4 171 170 4711 4117 1,114 4111 0,711 4112 4711
, 4+75 e5,,, 4100 4533 gel gait 17/4 45zi 447, 400, 4701 4141 ,15.11 4117 4111 427/ 4001 0,111 11/1 1157 I ol, er0e
I, / x • 1,011 1,011 1.071 IOU 1117 ell , 4)77 4557 144S 4174 1150 en - gas au - - - - -
et 4110 4111 WS gas gas gas gas gs» gat gas gas 4711 4715 4506 gm - - gas - -
/l e/ X. - - gas 0,101 WI gad de+ dad 1144 407 lei 40# . use WI 4111 4/a - 4747 - 4717
-N, .. . - - 0.114 Itist «$71 0,13.21 41/4 • 4521410043» gas 41174+11 1,01 4111 4101 - 4111
-Ili .ii /ee. - - 4007 gas es» , 1,505 gas . tra me gas ee4e eeee ae« «et, «01, - -- - •- -.
HCO,yee -. en, gees Isi. 0,141 4M gas gar 44a . gal 4 1» 4774 404 , 4571" - - - - -
, 4 3Vet. - 401 em /,/#7 Iillf 1,111 11+2 1,015 4110 1/40 1,111 1101 4/44 - 4001 .-411/ zed), du+ um 1042
.8ify 0.e., . _ .. 4174 goy dag 47,4 4775 41f7 gas gas 0,047 MIS 47+1 4177 ea/ sae gas 4517 4114 4771 105 Riko
le /7,:e - pur ear 1,405 gogir gifir 40ee egkr dad ye um VW gm tar dad 4115 4171 401 1111 . end
Neer / pé.", • - WI 4541 : • enr gas deilf 4114 is* a« e+a ma 041 • 4+07 4444 4411 1,441 1+17 Off 1111 100 I
•
•
-75-
A coefficient of 0.75 is suggested for surface waters to
convert specific conductivity into the total amounts of
compounds dissolved in water.
While carrying out our studies we arrived at the conclusion
that such a conversion factor related to the total content of
compounds dissolved in water cannot be generally used for all
types of surface waters, though it is more or less suitable for
a great number of waters (cf. Table 23). We have found that
this coefficient is different for different rivers. In the
case of waters from the Early Tertiary eruptive rocks, i.e. of
waters with low ineralization, with a different abundance of
ions than is usual in common water and with elevated SiO2 contents, the coefficient exceeds even the value of 1.0. It
may even occur with these waters that the coefficient reaches
values around 1.5. An elevated coefficient indicates that the
contents of dissolved compounds are relatively higher than
specific conductivity (would show)*. This means that the solution
contains nonconducting compounds which increase the total
content of dissolved compounds, but do not take part in
conductivity. According to the preliminary results it is most
probably the content of 8i02 and tts abundance in the total
mineralization. Such an assumption has been confirmed not only /72
by the Sio2 content in the waters of individual rivers or types
waters, but also by the changes of the Si02 content in one
*Words in brackets added by translator.
•
-76-
and the same river. Such content changes depend on flow changes.
We have divided our materials into several intervals according
to increasing flows and have found that the coefficient of the
ratio changes quite significantly.
The coefficient value increases (i.e. the content of a
certain component and especially the content of suspended matter
decreases slower than specific conductivity) with increasing
flow rate. It reaches maximum values within intervals close
to the mean annual flow rates. At higher flows it decreases
again but there is no longer such a regularity as at lower
flaws (up to the mean flow rate - cf. Table 24). Hence it
fallows that the coefficient which is generally referred to
11› cannot be used for all surface waters, but must be calculated
separately for various types of rivers. When the coefficient
is to be expressed with higher accuracy or used for more
exacting purposes, the change depending on changes in the flow
rate must be taken into account.
We have evaluated the relation of specific conductivity
to the total content of compounds dissolved in water or the
relation of specific conductivity and total mineralization or
of other compounds to the flow rates. We have found how the
changes of a certain component depend on specific conductivity.
With a relatively high probability we can use, therefore,
specific conductivity as checking a given kind of water.
We shall.now turn to the relations and their main character-
.,
istics for the main components of water in sonie rivers. The
correlations between individual components are not equal. They
•
•
•
-77-
are closest as far as the suspended matter, total mineralization,
bicarbonate and calcium are concerned. They are looser for
other components, and in some cases one cannot speak about
correlations any more.
It becomes evedent from the graphs that the dependence is
linear, and we let ourselves be guided by this when calculating
the correlations which are presented in the following tables
(Tables 25-28).
From these data it can be concluded that the regressions
of a certain component are different for different rivers.
Before they can be generalized, further research is needed
even with respect to the subsoil.
(C). DEPENDECE OF CHANGES OF THE COMPOSITION OF WATER ON THE FLOW /76
When we characterized the chemical composition of water
with respect to various time intervals, we saw that the changes
of the composition of water are affected by the seasons. In
addition to the effects of the seasons following more important
and longer lasting climatic conditions and the effects of sources
feeding the river, the amount of flowing water has a great, one
can even say a dominating, influence. To be able to say that
there is a correlation between the flow volume and chemical
composition of water, we must prove this by using the materials
obtained. If a correlation does exist, the nature of it needs
to be determined.
kiellate4CE. /4e, Sfedecviees Ivelee/t eaittfraitereiS o4 Sreee./1/*e era4cietc,f/i/ify (bia/Atee/t..(fetese/;v1)
C7/17
Sum,
eiirloyra t kin /87/
leieneeictite ./V, preefsiin etrarahark; e e 2 g dx d, .fx 464.4 S ,f, .15, 1,64.1:y 31 , ..t PA., y F 4..e-
e/x
90 299 224+ 14,4 22,9 1402 2411 14,06 /7, 37 24+1 Mil 49+9 401+20 4087/6 3, - 0,60613' x - 46 fr, 1 ecv &wit. let) //CO, jeleceeir
/23 283 /74:7 23.9 /z.., 2481 I4, /2 02,41 . /0, 91 /7,4/ 1486 tree" *72217 408048 g-0,+0494 x +90,9 1 efeter7"Y;i
co yeedeter emieutfy.,.. 78 Ate +9,7 2t2 6,2 tee. 3423 See 1,6-/ e net 482+ 402162 .4/1240 y .0,14612 x + 72 ',ley (x) - -
Peertienee. et alkeets sedee- dent,e19/7e-471S 04 se•-cfyie. co/totee://i,ily (;friel//ineet .eeze (ssiew) Tadte- 28 Rime.
• Nitre 4 A/To/a. /1e. fee5.7,,w
/2 ji 0: d .s.,
,ezilgiien Étetteelete2/) :y' „ 46 4. ,I4 . 7 Sx J 1,144 3 19 ± tl.,4, E 4•E d
/ use.Ald.ed e e
Y 'erx,yi(x-R)+.47
/
ee..,e-yee/", P. it,ec./.98 4147 2149 127 92,8 6445 1/8,0 209,31 1497 14/0 /12,0/ + 480 0, 0/49 40672 y-46/2 x + gem
e...
gîPii-lii.:2 115,2 /2/ 91,1 7+,90 /22,94 224,70 97,79 6,91 115,29 +47«, earn 40J21 ,y-tZ.399 ec + .49,5/ (., (ye ... ...,..
,gp ft. e d fereern-s /15 +442 2312 /21 «a 74;90 ag 84 224;70 37,70 41,93 1.19, /0 • 4 zei 40287 40129 sy a. 0,891x + Seer
(,, (9) -
o a/ e 0
(x f (v) /9/ 419,7 46,2 /28 /9,3 /13,10 04/4 344.10 /1,79 /9,32 911+ +0,464, a -tet , 112 y - , +8 x + 29,19
eteive .e/ el - /98 +/47 SU /27 /Z9 9599 /4491 25758 «as /9, fet ..gwe 4- 0,719 0 019/ 407e4 y -4/02 x - 8,70
(x) (9)
grefece/ e02+ /99 42‘4. AB /26 /48 .99,01 /37,84 212,11 /2,1,9 19,99. 86,57 +47+9 402/7 40880 g0,/09 x + /429
(x) (9)
*eider 1/92+ /87 +42 /40 /25 ef £'8,80 18072 29400 4;0.9 4/9 »,87 + 4027 40299 4/1X y.40,7/9x +18,62
(x (9)
(Zee1 mil.CY) /59 ++2,2 /437 /2+ /4,0 104 0+ /7163 212,12 /471 /el 1476 + 414,1 40174. 4/499 y - 408/9 x - 7,87 i
eeeee. e" i CO /59 ++2,2 49 /2+ 4,2 /01,09 /0473. 304/9 2,41 SW 142! 4' ere 4 0114 4/41! ,y-401•97 x - 8,7/
. • . . _ _ • •
jtlateq(e/Ice al 14e aleled7.4.40//S of th. eeeeieweeeS. SAec/)4è ea,74e4C7iii.« (7i7k/ /Moe?, eft, eS9/;ey)
even , Leborec echo/one,
TaXte...27 [75-] ,
emite4kPnReresse fteetion... .
•n 2 , dx dy ■rx /, 6# 1,,„ 3 ..t;,, ..rs, eess, 8 sy ±I f . hr
x./.9 .9-±,4
all • n.c. e d ma t,te r 2/9 260,2 206,6 ,s0-„5 ,g2 3974 6-8,12 118,22 24,57 40,29 7.7,7/ 47/6 0,0829 413/9 y -445+ x +.9.9,1
yge,•8 12;71-e, e „ -; - 21,+ +6;28 74;26 /31;94. 2143 44,71 76,29 45.09 0,020/ 0,/204 y- 4120 x + 14 5.1 kezze -rem •r fe it. f .";. -(9) =.,e I/CO; 206 274+ /71,9 478 249 1427 5449 /08,8/ 22,02 341/ 66,09 4647 4027! 41492 y-0,892 x + 944
-trek/ 092+ ey) 22/ 2140 +78 55,3 49 41,9/ 9417 /25,42 46'S /49/ /9,01 4888 40239 40819 y... 4109 x + /9,57
y 278 259,e 4. eV 2,4 4718 7754, 14484 2,05 e38 6,15 0:s/0 0,832 4/829 y- 0, 022 x + 2,4 Po (e)
slyenCifenCe 4thieleer 6oi'S t Wedelew demlepeteis evt .
eandeceliviiy ( izeAtigfression)
4. 21
,- f ea.4■7›../
etunda 1 e i r h, .
.1;‹ 464. Ix 3 Sy Sy 1,64 # 3 S Ey I. r.ye #E entefiegrei.,) . . -
dx err x/y . Se' (r-9) •i*
u.spmIded matter e qi 2ga e0 83,9 23,9 .10,6 21,27 29,22 84,11 /5,35 23,/7 46,05 4568 90268 0,/066 y. 44'08x + eie
- -sf . l • m- er 1 ni e.
, .1-5,8 21,7 /4,3 21,07 34,55 87,21 .. /1,73 1924 lee 9173 9020 91056 y ■ 4319 x + tee . . hi CO, 48,3 2.e8 /3,3 14,9/ 23,47 +2,93 .499 14,59 26.67 4828' 90124 0,0492 y -0,51+8 s + e, 58
(e)
293 93,4 /1,7 2.e9 1,2 447 28,65 12,4/ 217 2,56 6,ef 4750 40222 40888 y - 4 093 x +9,78
/y.9 2+230 83,6 2,9 28,0 /,2 2403 .7+,&9 63,09 0,97 1,94 24/ 4187 40280 0,1044 y - 4,427x • es-9
(.9)
4/e t 292 13,1 3, 2 2e. 1 4 2 23,99 33, 16 71,61. 4/0 e.90 8,40 4+05 4 0210 4/120 j... 0,011 x *1,11 i*el(x) (Y)
.Defreinience- .71 etee1VelS'oes 7itgeeziee, diereoeenfs e fiew egidee)
77,1 4 n pen «le teeeeession) 3rQ1.:r4ome , k,n /6'71 7;a/ei.27.
41-1,4..adec:it, n' Mg 9 /ay/ k
. . gef-.2e5Slon 0 "on
log o non /og ± r, r yé- etapided apt Ale (e ,,,./..r ) . (ems)
e (4 123 429672 2,ea /2 -4/72 40/5.1.6. more -9171 etheff 916516 . tu - exiled nrat,t,i.- (, 80 3,2340 2,15698 -9281 1, /2228 /se e - 0, 612 4 0411e 4/8er 3(4) . 4/824,9 x -" Y1
e (x) / eco; 153 427567 2,2;203 74178 2,854e 683,7 -9683 902905 41/616 e ■ 653,6 fee'
le)
47(x)/ .1*0!- 78 429729 95066/ -928t 441708 279, 6 -9147 401319 921152 ye ,. 273,6 f gee ' • (g)
e / , (4 / c,- (*.y) 91 3, 2951/ /,69945 -9/6/ 2,22995 /698 - 9 55.t 905/91 8, 20792 e. -1648 x-ate/
79 429152 2,47268 -9190 3,0986/ /241/ -9618 4, 04500 418000 ,9,t =/24.9,/ .i."" i
;6 de.44,-ewv/5
ete ,i_Su,spnded matter r-7
t-J
-80-
We have plotted some components on graphs and found that a
relatively good correlation exists with respect to some of them
(suspended matter ) HCO3' Ca2+ ), though quite large dispersoons
appear for some values. A detailed analysis showed that the
dispersions are caused both by the flow trends and seasons
(especially withthe river Laborec), and by characteristic
seasons (especially with the Danube and Rika), i.e. the
seasons which are related by water levels, climatic conditions
and time.
The division of the material is based on certain trends
during characteristic seasons mentioned above and subjected to
detailed analysis.
1. General Correlation of the Chan • es of the Compostion of Water
(Entire Complexes of Observations)
Graphical representation of the materials and knowledge of
the dependence of changes of the composition of water on the
flow indicates that the dependence is hyperbolic. Using the
method of least squares we have established the degree of
dependence, which we have expressed in a correlation coefficient.
This correlation coefficient obeys the formula
2(log x.-log x)(log Yi .-log Y. ) x,y
V2 uogx._10„0 2 (logyi - log y) 2
where x. is the flow in individual determinations and y. the
individually measured water component ( HCO3' Ca2+ etc.).
on/,nez/t, tata/ Req4eSsio
• ., 4c/7c/en ee, et irif-eieaAees- lvajett eampoeenis o,, ee,t,w (4- ei'Vete) Ta-Wei()
eortnetzh'on_ . /cg Fr • /4947 efitessioo eeect25.04.
n k log Q • num. kg g t rx,y E. 4. F Y1/10/1/i/leae.) • -,: . x/e (4 m'Ys) (e/e79 r
- , x-"s* ' x
44;eacleik/Vy /.94 4/9306 2,60839 -4294. 2,95037 8/3,2 -46/4 40299 41/96 si .9/82 ()
e :bus na e d matte -424+
2,34254 -4254 Z952.39 7//,4 -499+ 40253 41082 8M: - 7//4j Dei
47 • il, - u e d matte:- -42" 2/4 4/7543 2,3504+ -4214 2,69403 4,93,1 -46z9 0,02.90 4/121) yza, 4,93,1 x
..J. • _ -- :Ce) .0i
a
CO; /fg /,/e9/9 2,39420 -0,31/ 2,72714 .334,4 - 0,6+7 4431/ 4/24-4 yene 574,4 X-0,311
19 (y) ( X) /
0,- 19
42 (4/ fo . (y) 209 /,16/60 /,‘5614' - 4/90 /47746 7.5,./5 -4.427 40312 4 /52,9 yje - 7.5",1.5 x ‘,2-
e ci - 2/5 4/74es 452759 -0,49+ Z/0713 tee/ -dese2 40239 40556' y,, /24/ ,r-ee•e*
( ) ( y)
Q 2+ -0,202 205 4/7971 1 10033 -0,297 2,Ieeco /4' /, 4 4609 40290 4/M4
(X) (Y)
e I+ /99 /, /6730 1/77/7 +0,03/ I,14090 /343 4409 40474 4/9/2 8,,+ .• /343 x*et03/
(X) (y)
e -0,0fS
• Me .' 159 1,1559* 4/8359 -4sse 412493 664 - 4540 40979 4/5/9
( x) (9)
Q e 4 /0•9 tese. 4. 75324, -0,372 1,/1261 /3;23 - 0,5/4 40898 4/172 9,+ - /5,23 x-4.372
(x) (Y)
° (X)/ 2 /G/ 4/5234 2,62649 -0,3+9 9,02901 /096,7 -4709 40204' 4/816 yE,
(x) ( y)
Oeteemeeeme atfee.ezies me7reif,evierpanen13 0/1 Me 'eh/ 1./4ee) zwe, . ,.
/47?'ch44vae rtaidieea 7teeie ,eeet essie
gette46.011 /1 • / y 1 lof .57 k
/031 a num. log a ± /; f 4,e- nessien frete,, .1
• r eier,4- ) , - ••,. y (e?
a ,7,373-) (.9,,,w) y ...),
3/9 490320 2,41249 1 -4/32 2,312/8 340,9 - 0,660 4025/ 0,1004, y - 9+46 Peen ,i,,./_:_42,
42 . Sus '
pend- ,4--e rnaeuÊr -4,0z ..' dfl.aot . 13/247 I -0,082 I 2,39799 249,1 -0,642 4025/ 4/004 s'Ai, - 2+9F x °'
- 4; .:tuspenciL447mq2-4r. -0,013
,) 2,06/29 , -404's 1/3799 /3Z4 - 4861 0,0372 41489 yrre ' %ni twit) _ k
i )/ M-03.- (y) 100 40356/ 2,23232 - 4/40 2,3493/ 233,5 -4719 0,0202 80809 y,,,,,,i . 223,1x-4
0 -1
/ J'Of- 21,6- 4 9391/ 1,49974 - 4043 I,5/887 32,39 - 14,s, 404/7 4/609 9r; - ' 3246 X ()•
-40+3
x ' (y)
-- 260 4 92719 4924/0 - 4/04 1,02063 /0,89 - 0,337 0,037/ 4/494 „gr,- - /0,39 x 410+
(4) 0 '
''. 219 0,929/0 1,07353 - a /2/ /,79199 6/,/ -0,674 0,8329 409/8 »il* ,.. 641 x-4/2/
/ Ca',
(x) (g)
0 „,,,,2+ -0,166
(x)/ "' (0 159 0,929/8 49/29/ - a, ae 1, 09676 /1,96 - 461f 40393 4/172 y,,,, -. .. 14 66 x
-4292 (x) / Mg + /96 0,81011 0,8253+ -0292 1,07393 /1,89 - 0,509 487941 0,1+72 9,,,,Q * - /4/9 5 (9)
Mi 0,81286 0,47057 +41/9 436993 2,34 + 0,088 0,04.89 4/992 et.. . 2,34 x-4//.9
(X) / •• (Y)
/ -4/2e ' (y) ; 2-, (8) 166 , 4 8343/ 2,41411 - 4128 2,56077 363,7 - 4796 802/7 0,0994 ezi -363,7 x
• • • eudedions ihe aeaca•i4kws. ielviere do«peeenie ,t4.01 me flow «31-dee) ?Via «4/mean eereessio#1
eke 41 ("einianka..-
Zi‘le. 32o
belittle:eon ' /09 ji /09 1 ee62Non df/helepecee,
n k /ay e num. /ay a ± re,1 4.E e/..q (4 /es) (y/m3) eefeesebil .9' ek e
/Spe
e (x) f.,,„1„ àdi, sac 0,01+7790 492922 -42er 49,2220 ne, -‘9,5-24« . 40242 0, ff20? „4 ■ e
".f
(2 Suspen.e ed. matter s e A:41"
ex) / T;ieti iy) 311 0:0190070 1,94779 -414.0 1, 91040 89,21 -0,123 40179 411/8 _ye - e ,
Q 4 ,x) , • • s.Ped1:15,Le d.e2;teaor 73681 -0/.92 Z73907 etee .-0,172 48295- 4/180 Fez,. - F 94 x
' el •,._
e-0,381 - '
/ fiC'0 - 292 0,0225630 167102 - 480fe 487790 4.7,6.1 -0,701 4828/ 0,0804. g,,,.. - 47,03 x
[,k) 2 (4)
.i.' C
-0,171
x)/ ' ' r 94. (e)
.32/ 0,0118480 49595/ +0,175 495(189,01 + 0 284. (1,084.8 0,/284 gai. ... 9,01x
e 0,- 778 e1 33.5* 40071792 464125 -4,778 • 484,483 44.5 - 4 led 488610 4/4+0 yci_ - 4,40 x
(x)/ - (91
Q ,2 / CD 337 40652468 1,01138 -4219 105642 Mee -8,184 8,0242 48906 y„•• -11..eqx
( x), (g)
Q I ii, Z . 3p, 00.34.760 041826 -0202 0,4.1937 2,83 -0,272 46,318 4/272 ' .9,7,8• - 2,03;4'72 (X) /
e , No * 292 i 40818100 4+68/2 -4102 440870 2,94 -4180 4088/ 0,1524. ye , . - 2,94. x-4/02 (.9)
193 90.011888 0,44420-6 -8,/414 44,4813- .9,44. -4895 48..194. 41578 ye . - 2,09 5 / 141
(7) ,
_ 0
/ E ' 24,9 40295920 1,91491 -0,10'8 f, 92012 88,28 -0,4" 00327 0,1304 yzi - 88,28 x-4 me
x) t (e)
7.;a11.e. 316 4Itgght. h.0/1 aie,, etheekleth-ClIS serif/de-9Z Amtle011eek adhy
vmz,z_ 14e-fiev m3Atee) bed non h:eevt, !feu ssidm
411«/475en n /09 .0 1 09 1 ePeek Cl /,,e num. log rk, 4*E. . Ref,t0.1S1 '
(a ',rib') (ems) e o - .y.cx
7Surri„ bpended matter ,,, . • _..1 21 080744 44.8112 -0,121 41e72/ 20g7 -4720 40171 44312 y,,...266)7x-."" -.7
eoly) .
(4/ 1800; 21 460344 2,31/94 -0203 2,30301 2042 -0,810 9.0/02 4008 4,„..,;. -2042x-el"
- C9)
(7) ..10:- (0 25 460744 1„55611 - 8)115 1,41442 241 - 0,287 4000 0,1956 .9,e - 241
x ce" 2+ 460013 1,77021 -0,0014 1,719/1 if, - 0,541 One 4250+ .9' ra t. ••■
( Y)
20 0,51201 2,6120! -4e2 410789 1249 -47901 0,01/6 01204 . ..37/,..0 k - e fee
-83-
From the calculations of the degree of dependence for the
entire complex it can be concluded that not all water components
depend equally on flow changes (cf. Tables 29-32a). This shows
that the components which are not related to the flow are affected
to a larger extent by other factors (soil, climatic conditions
etc.).
For the river Nitra all components except SO2- depend on 4 flow changes. The explanation is as follows. Because there
are high concentrations of such'components (chlorides and alkalis)
as are affected in other rivers by precipitation, the mecipit-
ation exercises a small effect as far as the increase is
concerned. Due to this, the changes of increased concentrations
depend mostly on flow changes. (This paragraph makes no
sense in Slovka - translator's note).
.In other rivers we observe that flow changes depend on
specific conductivity, suspended matter, bicarbonates, calcium
and total mineralization) In the river Laborec they also
depend on sodium, and in the Danube on magnesium and sulfates
in addition. Magnesium and especially sulfates, chlorides,
potassium and sodium (the river Rika) do not depend.on flow
changes. Relatively high and at the same time fluctuating
contents of these components in precipitation waters are the
reason why there is no relation between the contents of such
components and the amount of flowing water. The content of
such components except sulfates is generally low in river
waters. Their high content in precipitation waters affects the
variability of certain components all the more. It is especially
O
-84-
evident in waters with low mineralization (Rika). Here even the
content of components (sulfates and potassium) increases with a
certain flow increase; however, it decreases with an additional
flow increase. On the one hand this is related to precipitation
(intensity and duration of rains, intervals between rains,
direction of winds etc.) and on the other hand to the season
and soil conditions. Relatively speaking the highest contents
of such components occur in spring at relatively high flows;
they are lowest in winter.
The values have relatively large dispersions under the
influence of the factors mentioned. Correlation coefficients
are quite low (especially in the river Rika), but they meet the
conditions for the probable error of correlation coefficients
(cf. Tables 29-32a, where 4E )
After we established the degree of correlation, we calc ated
the nonlinear regression. In the given case it was a hyperbolic
function. Its general formulais y = a.xk and "k" obeys the
relation
k =, 2: (log x . - log x) (log y. - log y) i
L (log x . - log x) 2 i
and for "a" there is another formula
log y. - k log . log a = xi
We have calculated the parameters of the hyperbola and
devised equations for individual components as well as for •
•
-5-
total mineralization. The equations show the dependence of
changes of the contents of components on flow changes for
individual rivers (cf. Tables 29-32a).
2. Partial Correlation of the Changes of the Composition of Water
Graphical presentation of results showed a relatively
large dispersion of individual points, as we have already shown
earlier. We searched for the reason for this. We classified
our results in accordance with the seasons and calculated the
degree of correlation. It became apparent that the large
dispersion is not caused by the seasons, because partial complexes
have even lower degrees of correlation. Exceptions were found
in fall, when the correlations were closer than for the complete
complexes. We classified . our materiàls according to the flow
trends (in the river Laborec, where we had limnographic
records of water level changes) and according to characteristic
seasons.
The following seasons are characteristic of the Danube:
a) A season with prevailing participation of glacier and
Alpine melt waters (end of spring and summer). This season
is characterized by a lower mineralization (decrease of
50-60 mg/1.).
b) A season with prevailing participation of pore water and
increased participation of ground waters (from end of fall
and winter to beginning of spring) - and increased mineral-
ization.
-86-
The following seasons are characteristic of the river Rika:
a) A season with moderately increased water levels which have
an increasing trend. Total mineralization is elevated in
this 'season.
h) A season following prolonged high water levels (April and
May) after the melt runoff.
With other rivers which have a higher mineralization we
do not observe such differences as concerns water composition
during certain intervals of time and dependence on the source
of feeding water. Here the differences manifest themselves
rather in the trend of the flow. Distribution of the material
11› according to seasons did not yield positive results even in /83
this case. Selections had large dispersions and looser cor-
relations than the entire sets.
Fig. 13 and 14 present both the distribution of values
belonging to a certain selection and curves which show the
dependence of changes of the components mentioned above on
flow changes.
Thus we observe two patterns with the Danube. The upper
part of the material (the first set) comprises data from late
fall, winter and partially also from spring, and only a few
data from the summer and fall - and those primarily data which
were strongly influenced by pore water. A slow decrease is
evident in the first set of individual values (the set of higher
gl, values) with respect to the flow increase.
390
370
350
330
310
290
230 800 1200 1600 2000 2900 2800 3200 3600 9000 9900 9800 5200 1142W 0 [nee]
270
250
•• 1R
•
lie h.w. • ora
.mil .
iimagi: iii • ---• ma: • ,
. . 0
/83
-87-
Fig..13. Dependence of the 2:1 content change on Q of water of the Danube
I Season with prevailing pore water with partial regression,
II Total regression
III Season with prevailing Alpine waters with partial regression
Already greater differences as depending on flow changes /84
are evident from the other set; the correlation is quite good
(cf. Tables 33 and 34 and Fig. 13).
The tables show that the partial correlations are substanti- /86
ally better than the total correlation and that the regressions
differ from each other. The curves of the first set of data have
only a slight curvature and in several cases they almost
gl, approximate linear correlations. The curves of the other set have
steeper slopes.
ee. a .
to 18
(..
,...„. . ,....
m .
.
littim% En is
/ —
e') 120 — 0 20 40 60 80 100
row. e [ ep] 160 200 /80 120 14-0
380
360
340
320
300
280
• esie
24-0
220
288
/80
160
-88-
Fre. 14 - Deffencie/We 0, Me 2.-1. e-42/274eePeS c6a./27e, en a of tverfett Leae,,tec
- eleclinia5 inenci
/7, - rising trend
///, - siagd;zed t‘nencef 0///011/
- eth cemrdex ey‘ oÉSeeva7Lio/25
-89-
•
Apeeleece eillete61es_e_metdee1t comfiemem'S Pe Sreei:rlavo r km /cm (egutits..tAten‘rwan1A.e102.44irm1 irrv )
7.-tee- 33
?1/4i7hl (a eyded) •
y- - /0
d i i _
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n k /088 a Pam. logo ± iky f 4. Le /
xty (4 mYs) (gier') vureatem) y- g • x *
Q Msite42-', ,,) y *3 3,2873.5. 2,49096 -0,/64' 5,03110 /071,0 -4701 48+219ese a ease y- /071x 41'4' , 4 ..rdit,
--a . - --Züspen-Cee (x ) Jett er ( 9) 8.25909 2,40710 -4/00 2,92790 84,70 -4713 404•94.0 4/9760 ,y = 847 x
a - (X) / Nee; 7/ 47+129 2,2978:1 - 0,1+0 8,0(964'e 2,7+14.8 117,4 -48708,0(964'8,0(964' 0,23916 y - se, e i °'
(y)
12(x) / re
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e Z .,:, 33 3,2124.8 2,1/748 - 0,1+7 2,981+1 989, 8 -0,801 407.1-29 4201/2 y -, 889,6 x
(X)/
(9)
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ezik:
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) I/CO; 8/ 9,30/93 2,22/92 -a/77 2,801/2 438,4. -4719 0,03/71 9,/2701 y- on,* ;4/77 e(x / (9)
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e / , (x) / , a (9) 4,5 .!e074.7 468271 - 0,/27 2,22941 /69,6 - 0,680 . 404'84.g 4M1e y -
Q ,, / znm, . (.9) +1 3,3/849 2,41810 - 4/4.2 3,04q73 m90,9 - a 738 0,04170 4/8304, y - /ma ..,<
•
•
•
•
-90-
Following the division of the data into the two sets
mentioned above, we note a better degree of correlation in the case
of the river Rika. This is especially true of the other set,
which characterizes the season following prolonged high water
levels and the melt water runoff.
Since the selection according to seasons was not successful
and a serious dispersion of data occurred in the, basic material,
we made a selection according to flow trends in the river
Laborec, where we had detailed limnographic records of flows.
Both Figure 14 and. Table 15 show that in the river Laborec
both the mineralization and the content of the individual
components are highest at the time when the flow has ân -
increasing trend, although the mean flow in the case of such
selections is highest, i.e. the mineralization should be lowest.
This can be explained by the ihct that sufficient amoumt of
dissolved compounds always accumulate in the subsoil during the
season between rains. On contact with precipitation waters
these compounds enter into solution instantly, which increases
the mineralization in the initial masses of water. Mineralization
of water which feeds the river with a certain delay, i.e.
mainly with a decreasing trend and later, is relatively lower
with respect to the flow volume of water. Lower mineralization
of water with decreasing flow trends can be explained by the
fact that the soil is already partially leached and is not
capable of supplying a relatively large amount of water with
soluble compounds to such an extent.
•
«9,2-fie/Wei/ce - alketah'pes gyi ri/Sen, eooponents oe fzele(a e3/.4ee,) _ -
evue, /ficha/arc ki lek /Mectit, 'tee; IteSSf
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etee.424.7`lon i• ,fr' P.24/8e2Ssigen, geq4Cleet.
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alezeac
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iii+ .7ey
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atter te -0,07:7
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71 4020/2 2241,/7 -4/19 2,36610 222,1 -4738 44291 41/84 y - 212," x-41"
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Q (x) zi 3+ 4/1129 2,39052 -0,142 2,55428 2543 -4770 0,0164 0,0640 y : 118, 8
(e) -0,0eté 67 0, 18116 2,47044. -4022+ 25/887 $341 - 0, 437 4061/ 0,218+ y * e14/ x
•
O
-92-
As far as the dependence of the changes of mineralization
and its components on the flow is concerned, Table 35 shows that the
highest degree of dependence is for a decreasing trend of flow,
then for an increasing tend, and lowest at stabilized water
levels, although one would expect the correlation to be closest
at stabilized water levels. VORONKOV (93) arrived at similar
conclustions but for the season of low water levels. He even
asserts that there is no cortielation between the.composition of
water and the flow in that season.
At stabilized water levels the correlation is weakest
because various magnitudes of flows apply to the stabilized
water levels and, in addition, during various annual seasons
and various trends of flows etc. (This sentence makes no sense
in Slovak and a verb is missing - translator's note). Under
such different conditions the conditions under which water is
enriched with mineral compounds are also different. One time
it is a long-lasting dry season, when ground waters with
higher mineralization participate in the flows, another time
it is a season following long-lasting leaching of the subsoil,
when the waters have a lower mineralization.
On the other hand with both increasing and decreasing
trends the changes last a short time, so that such differences
do not occur. In addition to this there is another fact,
namely that precipitation immediately after contact with the
soil is enriched with mineral compounds. This decreases the
variability of the concentrations of a certain component. At
higher precipitation intensities leaching of soil is decreased
•
•
-93--
proportionally to the amount of water. This causes a more
frequent concentration decrease although the absolute amount
of leached compounds is higher.
There are relatively good correlations between the
composition of water and flow rates in rivers (cf. Fig. 15-18
and Tables 29-35). Components which are more strongly influenced
by precipitation do not change in dependence on flow changes.
This is especially 'evident in waters which have a low mineral-
ization. The dependence of changes of:mineralization and some of
the main ions is lower in waters with a low mineralization
than in waters with a higher mineralization.
The degree of correlation is relatively low because
various factors affect the disturbances of the dependence of
composition changes, e.g. the trends of flows, the sources of
water which feed the river, seasons following long-lasting
different climatic'conditons, etc. Such factors cause dispersion
of values. Partial correlations are better as was shown with
those selections which correspond to one of the factors listed
above. This means in practice that it will be necessary to
evaluate the effect of a certain factor on composition changes
when analyzing the dependence of composition changes in detail.
•
—94 — 700 • 600
500
eno
300
ek e1* , 200
tO SO f0
a[m3xp] 20 50
Fhe, 15 - Dependence of the chareles e', 6-1,7£5 Pie a of h/a/71-e-,Z
of Me ivied ml`n enet//ze,,
or /Wing, R/reit,
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29
251
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o o o
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'Fig. 18 - Pepe/We/Ice f /he heco,- cenierit eanje- ve a oit ekiz, devet
-96-
IV THE BALANCE OF THE DISCHARGE OF COMPOUNDS DISSOLVED IN WATER /91
General chemical characteristics and the description of
the properties of river water are not sufficient for the
elucidation of processes which take place in nature and
especially of processes which take place on the surface of the
earth and which are strongly influenced by water. It is necessary
to know the detailed balance of the discharge of compounds
soluble in water as well as the balance of compounds which fall
on the surface of the earth in the form of precipitation.
Such balances should be used for the elucidation of denudation
and erosion processes in which a great role is played by these
very compounds dissolved in water, which form the main componant
of chemical erosion. A detailed balance and the investigation
of chemical erosion are important With respect to the history
of the development of the Earth in addition to their practical
values.
It needs to be noted that our study will be focused only
on compounds dissolved in water, i.e. on the balance of the
discharge of chemical compounds dissolved in water. Some more
precisely defined considerations will be focused on the balance
of discharge of ions and of total mineralization, i.e. on the
main part of chemical erosion, which according to BRAZHNIKOVA .(30)
represents an important part of total erosion: E = N + Ch,
where N represerts the deposits of soil and minerals in the form
of alluvial and drifted deposits, i.e. mechanical erosion, and
-97-
Ch represehts dissolved chemical compounds (by drifting off
soil and minerals in the form of soluabe compounds, i.e, chemcial
erosion.
When drawing up the balance, it is ricessary to keep in
mind the purposes for which the results will be used and to
proceed to process the results from such an aspect. At the same
time the peculiarities of the river basin must be evaluated.
On the Third All-Union Hydrological Meeting in 1957 KHOBKOV
said that it is necessary to observe and evaluate the peculiar-
ities of the stream in more detail, because such peculiarities
can have a great importance for the balance of the total discharge
of compounds. He noted that the peculiarities of individual
regions or stream sections are neglected even in cases of
'detailed statistical generalization of the ion discharge in
rivers. Data originating from a small amount of basic data
offer an even more distorted image of the discharge.
We know that the concentration of compounds changes with .
the flow changes and that such changes are different for various
compounds, i.e, for various groups of compounds and different
types of rivers. Hence it follows that balances which do not
originate from detailed knowledge of such properties of the
stream can be only considered a rough guide.
It is evident from available sources that more detailed
balances of the discharge, which take into consideration also
the knowledge of annual changes and areas into which the landscape
is divided, appeared around 1947 and are the domain of Soviet
authors (3, 4, 5, 7, 10, 29, 30).
• eischaief of /OeS from Me
eye the vis,s,n, 7ciefe, 87
-9 8-
,ei:seAcedefe. 07e sail's fRorn con14>m/elS eznel 78i/e.. 36 ee572p0S/.74 .0n or eibee.41, Pt/a/eit (CC-Peg/4e ajleit),
݈-ofieeoefficienr pischeefe 0/ ices [mye %] eolYneill`5'5'01 eitee.ce;d 1011 tikint 01 'se' Arc+ x+ cor se ci wo;
Argth tiMeRker, +74. 30,4 22,9 11,4 9,4 1,3 19,5 44 ey es Jena% Iteseeéa. 200 19,4 32,1 Z! Z7 1,7 344' 1,7 4 6 43 Elzeope . 300 347 349 6,1 1,3 2,2 . 39,4 Z3 2,9 44.
•
leaskv Weten Dischaeqe of ionS fat e 15,:ept geea.. f/oie ,oe fea■ - waieie, sys/em . [kdial [km'] ci," ne" ,vei-A, co; Jr cr 4 [emnfiej
azneids czeof 4/hi/e. Seas 1000 3+1 1,94 1,30 453 e19 5, 10 402 24/3 25,1
ea lea" 5ee4) 6100 1166' 1443' 3,45 en Z476 /470 42+ 72,53 ms
ZI:407.`ec..fiee4141,l ûmko7 Se«, 4600 322 14, 75 4 22 /1,/s 25,76' 14+1 /465 87,92 19,1
Aveett . J'eumnaglied - 11700 2393 37,18 8,97 20,58 64,06 91,21 488 134 53 45,9
an. (fie. cSect, 600 Ise 207 6,79 6,43 435 4 11 4 68 1443 24 7
alaCked feet of /1zo v 1200 158 en 1,36' 2,32 /0,76 455 2, 61 3406 24 9
It7Li52,179•e. OCecrry sunpthebliheae 14100 314 ese 4 15 3,40 1311 7,68 .eze 4449 24,2
Beeinq Sect., Sea o elehotet, 3200 810 6,60 1,7+ 2,92 /2,91 4 94 2,12 8423 9, 3' ' Se. of Tcf4I/7 /e, " j'ecimva,q/zed 3200 810 460 1,7+ 2,82 /2,91 4,94 2,12 3423 8,3 7a c:1 (kerb
Ca51
piczn Sect/ zoo 305 1480 3,0/ 404 2413 18,94 4 22 sgeg 21, 8
/1-feal Seq.) +55 e° 1,27 4 00 3,14 5,18 .9,23 4,12 28,72 ee,s
0115C4 svSleme WI Moe pale /en es - -- - ('-'9 _
Sysierns evithouil outlet 4841 #09 2457 401 9,48 25,69 24 17 469 es/ 29,2
Sammaieizec( (10781) (22,3)
erne/etc ferveii-ort. q of 21545 3968 74,28 /6;87 36,30119,77 7498 38,33 35411 /7,9
Me 44S,S, 'it (seem (um
ewe, meneens in ieetckeis Mciiectie. ofh&R, Sinag syseeenS pid/e7e Jecrzedc.hSn and Cenbecti fleet 62n/y? -eree/e eaid the betSin
1elMol3-71 •
-99-
The discharge of chemical compounds at the present time has
not yet been sufficiently investigated even in the U.S.S.R.,
not to mention other countries.
Of foreign papers we refer to the balance of the discharge
of water components as presented by CLARK (3) (cf. Table 36).
The table indicates that the ratios of water components
in Europe and South America are very similar with each other,
although the discharge per 1 mm2 is twice as high in Europe as
in South America. The 'ratios of ions in North American waters
are different from those for the two continents mentioned above
and according to ALEKIN (3) they are very similar to waters
running off in the U.S.S.R. However, the waters in the U.S.S.R.
have an even higher rival% abundance of magnesium, sulfates and
chlorides than North American waters.
The discharge of the main ions from the territory of the
U.S.S.R. has been divided according to individual seas into
which the waters flow. If Table 36 presented the differences
between the discharge of ions on different continents, the
differences are even more marked as regards certain regions of
river basins in the U.S.S.R., pertaining to individual seas
(cf. Table 37).
Even more marked differences in the ion discharge are
evident from data for individual rivers of the U.S.S.R. (Table 38).
The indexes of ion discharge fluctuate within very wide
limits of 2.8-161 t/km2/annum and accOrding to BRAZH-NIKOVA (30)
the maximum values of the discharge are even 250 t/km2/annum.
-100-
Most rivers have values below 50 t/km2/annum. In our country
the situation is the reverse. Our rivers discharge as a rule
/ / more than 50 tfkm2 /annum.
Based on a large quantity of basic material - 15,000 analyses
of 550 rivers - the discharges of ions from the territcry of
the U.S.S.R. were processed by BRAZHNIKOVA (30) and plotted on
a map. She has divided the discharges into six categories
according to their magnitude:
1. Discharge of ions from 0 to 10 t/km2/annum,
2. Discharge of ions from 10 to 20 t/km2/annum,
3. Discharge of ions from 20 to 30 t/km2/annum
4.. Discharge of ions from 30 to 40 t/km2/annum,
5. Discharge of ions from 40 to 50 t/km2/annum,
6. Discharge of ions above 50 t/km2/annun.
When calculating the balance of discharge of ions or of
other compounds dissolved in water, many authors proceeded to
characterise the distribution of the discharge in individual
seasons, in months or as depending on hydrological conditions.
Hence it follows that each river or type of river (lowland,
mountain and other rivers) has a different distribution of ion
discharge. The highest figures usually occur in the spring and
summer seasons (cf. Table 39). We can see from the table that in
spring the Dnepr discharges 42% of the total annual amount of
ions, the Don up to 51.5% and Sumgait River even as much as 7%,
while the Danube discharges only 30.5% and Amudarya River about
111, 37% (2, 3, 7, 10).
• -101-
Jere enej c4eadeeich'es ‘7t loti cesc4erAye.....
iit eet/eita/ eifre4s ot e _.
T 'en,' fit 104 e icienieea4t/e Ion :s- even,
Yisofebeye 1 44 ce...,25,,_ 11e4ye o theejef [W e ifr..1 Eii.rmei..) [t/.s. en') [we te [erne r [1/.r Xml
The Amu& a- 59,380 72,7 - Hero 2,870 10,2 .9,2
Dnepr 41/0 16,2 3, / 8/on: 2,160 161,0 $0,0
Don 6,220 14,7 2,1 Kilôeilr 1,950 31,7 5:9
rego 46,500 33,7 5; 8 Jonc 0,950 3,9 4,0 .
Zeno 41,300 17,0 8,4 Se4 811e 0,630 1,8
0,570 13,7
Ob 34200 12,2 5, 0 Tojmiro 7,9 9,0
Jem:rej 29,00 11, 4 6.,7 1999 0,260 20,4 8,0
Julok /WM eino
17200 48,0 9,8
1,560 11.9,0 Avorskoje Kojeu 0,470 61,4 . -
Chotonge 9,500 . 2,8 9,3 Anclijeoje Kea 0,740 160,0
Amu-Dorjo 17,700 78,1 5,9 Achty - 0,130 133,0 Jyr-Dwio 6,050 27,8 2,0 :femur 0,180 81,1 _
Peeoro 5, 470 /8,5 12' 5 Koro -Zroj 0,015 58,8 - Pjerina 3,600 fee /3' 3 e(eQr-ekl. 0,025 .99,8 . - Inv/ 3,320 16, 1 1,6 Sumgolt 0,055 34,1 - 1nelt:qirik2 3,280 .9,1 5:0
Trek 3,090 747 8,0
7à4/0 38
* elms pee, anmen
** tons Ani pee a/mum
feezsond e5leeietzefivi cie Ion diS44ezie_9Pe,
'y SIP/he izi vets iseteeelevej Tr24/.e3.9
• ,feasen-
even, henten., 4c+ring Pift1/11,e/L -rid/ /14,7ise.-
xi - f. e. - Fi ri - /X. X.- X/.
74e- Panuee. 29,4 30,5 26,0 /7 1 lee./ aeeentio/ished the- disbelétation erdify Dnepr /9,9 42,0 21,4 1+,7
Den 144 11,1 244 /1,7 fre, a# piyedzei.4,
Amy - Porjo /8, 4- 27,2 es 4- Me otsceeve, io eolnloezéte-•
.111/ek 14,9 37,9 471 Me gestes
Arcrekee Kea 4 3 19,4 548
Andirkoje Kopu /I, I 34,7 S4,2
Ach If - éci el 49,9 +69
A-cry - At /8,1 +4.3 $7 8
Jumsreit • /4,4 779 7,7
7;11/e m Yelleilufion of de disc aeee cf 4%, 0. -esente eirees ezen42,e449, Met/i .e./4(J menths eiir>eleèenece.)
_
• X2/1/C.12. / .1/ .111 Ii, b' VI kW nil /X X XI XII
ThZ., DanzeZe- 1,5 41 /0,1 /42 142 9/ 9,1 78 6,2 45 8, 4 64
Dnepr 2,0 • 7, 3' 9,5 172 193 146 6,9 54 5,7 4,8 48 5,1
Don 5,4 5,9 10,1 /9,3 21,6 9,6 54 5,0 4 4 41 4,8 5,1
Amu -119rjo 5,0 69 6,2 72 49 /2,2 1+2 13,1 8,1 5,6 5,4. 5.,,e
•
-102-
Distribution of the ion discharge during the course of
a year in individual months is presented in Table 40.
Hence it follows that the intensity of leaching of dissolved
compounds is different. It depends on geological, pedological
and climatic conditions and the profile of the river basin.
The magnitude of the discharge of ions from the river basin
depends on the discharge conditions in the river basin. The
greater the water flow, the greater the discharge of ions
(spring, summer). The discharge of ions is greater in rivers
which have a more humid climate than in rivers with a dry
climate.
Such differences can be observed on the basis of the
gl›
indexedischargeofions(P ) . ALEKIN (3) and BRAZHNIKOVA (29)
related the discharge of ions to the specific discharge and
stated that the index of discharge of ions is directly propor-
tional to the product of specific discharge and mean .
mineralization, as expressed by the formula Pi = A M C, where
C = mineralization of water, M = specific discharge, and
A = coefficient of proportionality.
It is assumed that mineralization of water decreases
with increasing specific discharge and that the mineralizatdon
is inversely proportional to the specific discharge for the
majority of rivers.
It is not possible to agree completely and unconditionally /96
with such conclusions. It can be true only on condition that all
factors affecting the composition of water are more or less the
same (the subsoil, composition of precipitation waters, etc.).
• -103-
Under our conditions we have cases where even the mineralization
of water is higher at a higher specific discharge than at lower
specific discharge, or we have very different mineralization of
water at the same specific discharges.
In practice this means, according to the authors, that
the highest discharge of ions will be in rivers which will have
a relatively hgh mineralization at a high specific discharge,
or t hat at a very high mineralization the specific discharge is
not very small (incomprehensible - translatorts note).
Concluding this very short review of balancing the
discharge of ions it needs to be noted that much work has
already been done, especially in the U.S.S.R., that tables and
maps are available with respect to discharge of ions for important
rivers, and in some regions even for smaller rivers and complete
river basins. However, the results have not yet been sufficiently
based on statistics. From this viewpoint, in our country
CHALUPAIS papers can be characterized as the only papers based
on a deeper theoretical analysis and statistical characterization
of results.
Total Discharge of Compounds in Our Rivers
For the calculations of ion discharge we have chosen five
drainage basins (the Danube, Nitra, Laborec, Topla and Rika)
with different areas of drained territory. Since the areas of
the river basins are of different magnitude, the flow conditions
are different as well. Consequently we obtain various amounts
-104-
of discharged compounds. The amounts of discharged compounds,
i.e. of the individual main ions, total mineralization and the
suspended matter from the entire drained territory are evident
from Table 41.
Table 41 presents also the amounts of compounds discharged
from an area of 1 km2 , i.e. so-called specific discharge of
compounds. Such amounts are relatively very high as compared
with the data given by CLARK (3) in Table 36 and with the data
from ALEKIN (5) in Tables 37 and 38 • According to the classifi-
cation by BRAZHNIKOVA (30) they pertain to the sixth (last)
category of ion discharge. As compared with these data, it is • /98.
remarkable that a high discharge of ions occurs also from the
territory of Early Tertiary eruptive rocks (the Rika), i.e. from
a territory in which the total mineralization of waters is
very low. It could be assumed that the discarge of ions will
be considerably lower, at least in these waters, and that it
will pertain to the middle categories of such classification.
To be able to judge the extent of leaching of compounds
from the subsoil, we must include in our balance also the
precipitation waters and their contents of dissolved compounds.
The author made a balance of compounds deposited on the drained
territory or on 1 km2 (cf. Table 41) based on analyses of
precipitation waters and precipitation conditions in the river
basins.
•
1-177cal Waece,eompozeeds foe some. e/Vees
Ri'Ve../f., 11/itrQ Zgeorec Rika
, ken to‘ecin 8414/7re
site A nirei o frlichalamce Karniereka
845in .aeete [km'] - 3/11,230 /401, /27 -82,562 'noun ,..74 • en 7 Wei emea 2 204661 1 0.50, 841 ..ro, 370
freecijai, r „ ,, begh..5 L i
,
t/ /1774194 1 ker? 0,700 4 750 T 0,800
lieu, awl off 'it e eze 580,262 see; 719 44,781
[iee 073/a4n um 1 kn7 2 0, me 0,421 4 7/1
, r ,
Bela/ice ei $i/eviele, eemPoneetS 1. Lrons pee an/,am]
roves-, rake die- Thia/ ells- e0/hp9b in htn ce 4 chic/tie-fee A iq geefa. fete 3 acatelien 3 e-- ilice4.et tielasin
175.e„
eirSin the
iesin ..e elezect, /10433 1/0 692 100 259 38038 104 244 55286' ' /552 37/3 2/61 .Suspended_ en*
latter dried ikme 3400 61,71 3/78 2714 74, 40 4Z26 2484 5457 3* 33 ediee ea=
; 26 eae //9 24+ 92 740 70 801 79 976 18/7/ /352 M47 +95
NCO 1 Ave 8,40 3Z79 29,39 1486 57,08 42,23 2/,48 29,33 7,81
(eke «ea_ 39 756 24154 /5502 8127 /6 35/ 712+ 67,96 5/6,30 45434 dee.
I km i /2,60 7,69 4, 9/ 429 /1,69 538 0,99 8,20 7, 11
et - enege a.«4, 7 780 /8222 /0 492 mg a +962 -3 a he 259,70 2/8,50 - 4490
1 kire t 2,44 478 2, 34 562 3,+7 -2,/1 4/2 3,47 - 405
Co" edek, eleeit, 1214<9 31 971 /9823 4 938 22 978 /80+0 302,20 47460 /74,40
1 Ice' s 341 /418 429 3 53 /6,40 /2,87 4,80 Z57 Z77
M •l+ Mee agegv 2 650 <9681 69,91 /576' 353/ /955 4427 1/960 79,33 e 1 km' 04.3 3,05 2,22 I/1 2,52 /,39 es+ 1,90 t,e
+ -etigeeteeer, 814 7 9 987 2090 2206' 3096' 890 1059 139,/0 58,50
A/9 1 km' 2,I7 2,83 0,66' 1,50 2,2/ 8, 64 1,28 2,21 493
25„ 20 +
ediiete aeecz, 4+17 3 772 -654 4098 -1,6494 /33,50 /5<9 70 K
/ km s . 1, ee 1,20 - 0,20 2,92 -7,34. 2,/2 2,52 - 0,e
E effee cheaz, ma 052 25647G /59 424 927+7 2 342 3396 /054
i 1 km 2 31,77 91,29 4.g SÉ 37,12 eem 54 06 3720 53,93 1473
componeniss ft/k1 4 f4e /17,vey of Imee,;(elieteew
B ceschaefe freief ee kachby q subsoil si
• -41
7200
1000
800
f 600
1100
200
0
■ - 1r il
soil
luarm•I mu Jr 10 U 70
Wf)
/6'000
14 000
/2080
10 000
8 000
6 000
4 000
• 2 000
-106-
o
• °
0 0 o o
o o
o p
_ 900 1200 Enn ?DOD 2400 PROD 3200 U170 417170 imn el» r;
pipit. a un3/s)
- 2),9enctieece of Me olisalaege, of .7/4:s-solved eofteounels -: dried_susnended matter - on the Danube water
flow
seo
fri]
78/p1v e unm
Dyeeedence e c4cutie 2 anal
F/4. 20- Zecfct, /seitete.reaole ki/ e:iffice •
•
•
-107-
We see from the able that the amounts of compounds brought
to the surface of the earth are relatively high. If we compare
them with the total discharge of compounds, we find that with
the respect to some components the discharge is only a little
higher than the influx of the compounds into the river basin.
With some compounds it is even lower, which means that compounds
(such as chlorine or potassium) are absorbed in the soil. With
other compounds (bicarbonate and calcium) on the other hand,
especially in the flysch area, very intensive leaching takes
place. Table 41 shows to what extent individual compounds
are extracted from the subsoil.
The table shows that about four times as many mineral
compounds have been leached in the flysch area per km2 as in
the area of Early Tertiary eruptive rocks; the greatest fraction
is represented by bicarbonates and calcium, which were about
5.5 times as high as from the Early Tertiary eruptive rocks.
On the other hand, from the Early Tertiary eruptive rocks more
potassium, sodium and sulfates have been leached out and a
considerably lower amount of chlorides has been absorbed by the
soil from precipitation waters than in the flysch area. Hence
it can be deduced that the subsoil has a great influence on the
enriching of surface waters with mineral compounds; the influence
is even so great that it dominates over the effect of precipita-
tion. Precipitation, and thus the water flow as well, depresses
the concentration of total mineralization, but not to such an
extent as one would assume. This is evident from the fact that
•
•
-10 8--
there is a linear increase of the discharge of ions when the
flow increases (a direct linear relation between the discharge
of ions and the flow - translator's note).
It is evident from Fig. 19-22 that the correlation between /100
the discharge of ions and the flow is so close that it almost
reaches a functional dependence, because the correlation
coefficients approach the value of 1.0 (cf. Tables 42-45). The
changes of the discharge of ions are linear with respect to the
flow and they obey the equations listed in Tables 42-45.
Hence it follows that the subsoil also has a great
capacity for being leached out; a brief contact with water
(fallen precipitation) is sufficient to supplement water
sufficiently with compounds present in the soil. At the same
time it is evident from the degree of correlation that it is
not affected to a considerable extent even by the intensity
of precipitation (very confusing in Slovak - translator's note).
The degree of leaching or the degree of the enrichment of /101'
water with mineral compounds depends on the kind and character
of the subsoil. Many more compounds are leached from the subsoil
in the flysch area than in the area of Early Tertiary eruptive
rocks or in other areas.
•
/0000
.9 000
69 000
7 000
8000
5 000
+ 000
o 000
2 000
I 000
0 • 0 10 20 30 eat/. e [eye]
-109--
+0 50 60
•
• •
•
o O ee e8 62 Poly Q finPl
66' 2,0 2* 2,9 *Î2 i0 *0 J;2 ea
[Ice]
14, 21- D9eendence. oi£ clischez4e. Zs' oe of Lez,ep/tee even, Jvcdeor,
F/9. 22 - Pepeatieflce, of the cliseizzzefe of come zeme/s evedee, flew in, ei../(41, eiveit
1. - Hee3- 1/1. - sor
21,
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1 4. =Ire, «ecitivi, . 1/x 1 [ y•lr,,,y -`11.-., (x-,7)..9.
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74 eil 77111 1.111 Ifni 514 « 41 10401 Me 19,41 43-127,2/ 4741/01 •0,117 4001709140/18.71 y• 73,-14.x •/970/ PO '• (y) I
Q /fee 71 1071 713411 MI !die ,J419 1040+ +0491 9217.1 /047409 3.140414 .e018 leoeoxoli aaeles y . 41,47+ +1730 tx) (Y)
a /lee (x) (r)
Q
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ill,Yee 14 10/4, Sfel 1071 ISO AMP 1441: ID«, CM42 11144,1 és.iff,4.1.4,170 40,7;001401441f y- 7. 05. • 700 (x) (Y) I - I e (Xlee,
(Y) !I 21/1 :00/1 .V71 +942 11471 ,017,31191437 11044 379433 1/307,111•4070 0,0/717411007/41i y-37,144- 70
e A e 71 /90f 917073 MU 210.713 14917 me Wei .110741 01114x /11.7.74011•401/ 400/290 4X14+4 y•1099++101194.
.en f/ow (7i€41151a7‘,e)5 hofe)
f. Suspendeçl matter Q
•
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/10 li • 1114.7 N;$ /04.1 el( 1411 1,411 /MS 11441 9/419 .4m 0,0110 0,071 y- 1.09+ • /tee
e (x)fre. 04) ire 77,C 1141 74,1 /J74* 449 its( 19,07 94/9 1+7,71 27427 •4111 0,0140 g/71 Y. 421+ * 117,2
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e (+)/'(V)
110 17,1 91144 /4;4 +7743 440 47,10 144* m2,1 stir,x, 4+0,41.94/1 0,0100 4070 y.2149. • /Mr
t Suspended matter Q
Rive& ,
glerer elYirine/or
•
-111-
, 41/ [roa] Afiemieace. 51 44. esliS14a/egeto51.5 «nd 115571ed 51e.eah'z4344sol
in /1'e. /ow /ire /l7 5/d 42.43545.5sien )
Pefietriener Of, ieffiteS_Si0/1 A/ scnem
ire_ c54114.014Pr3 n _ A ea.s. 34 204. 4 ..9.1y, ±4,, 3 F E
on, 44
251 19,5" 21.241 37/ 79547 723 11,80 2499 19419 27413 10437 •4111 400/9 0,0004 y• /99,4 x • 3147
am 417709-1;} 700 110 1909,4 791 27771 917 1477 /47/ 05400 1537,20 207400 .4909 4 002.9 40/70 y« /049,4 • 1.70.9
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e(x) AC/-. Q)(y 990 /0,7 a1,9 sz : 1114 es+ /422 1402 74 77 114 74 71811 .0. et 4 0771 97104 ..Y et7. • 4°
e , ,
‘4‘5".71 4 259 445 7427 37,5 1014,3 10,41" /75+ 81,31 30750 X130 91470 0,910 goon 0,0/12 9, 94249 •1191 (x) (y)
e ,
i„n, •.(2) 219 ter /141 371 171,1 1471 49,22 3411 34 24 eslo 192,53 . 4 040 40024 0.0014 y. 439,, • 39,9
(x) CY Q
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7-ert4 445
•
4e1.0e1e
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x/( a')' se 444 11930 1,11 11440 9,220 488+ 40/7 +1,91' 18,91 /2411 *e 9r gem 40345 y. 75,19 .142
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•
-16 • 14
12
10
8
23 .— kic4ezdefe iee.
?Ye eemouni 471 eonepiengés
anel eernieer-e-)14 leached -by ibeee)ei{e14 .o» jntoyi4blet dere.04 .
4 id ges:c4adeje 447 bithesieet./i2.46 .p4
- zrabethed&a:ze 4.o.t 4.eve_qe,, diie to pre- -
e-fee'A 7ifee ,
Dol. .3
0 10 a[m3Arj
10 000
9 000
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7 000
6 000
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000
3 000
2000
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VA v
ova °
0 0 10
[m3/el 20 30 40 50 80
70 60 eo SO 20 30 pm-
-112-
000 410 0
70i, 0
000
000 0.
0 . 000 0
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1 000 °
-------- --------- - a000
0
Dos]
• Fite - esthaieare aye Me bin/et/Moue of eent_POUtigiS
eé/Or (74 61freteiriu(s leached by precipitation into -7
_ idatee, ekze . €-eiai .etitreXaisfe, /v7' 7 mi- 4.mq4.24eon • .2- AP/La/ ei/1-e■tali2erhon WiScherlre
_due .t o "eeeerecnoe .
900 • 0
280 111111re
350 320
i
2, i Iledirdiall
E0 4 An 11111111111111 °
I -.14111111111Preer& el illieleelP"-
0 0 Of a[mois
04 1,2 1,6 2,0 2,9 2,8 3,2 9,8 3,5 f,0
»era
Z 06ore c
Ri
0,613
8788
a, 4«..25
0;717
0,772
-0,078
0, 324.
0,628
0, eta
0, 129
8,79.9
0,/68
0,160
0,804-
0, 964-
•
-113-
pq, 25. Fume of Me iefed emezenis • . eo,y,e,unel.s aed ee»,/ee, ze.ls leached by
•, free e/ev'îLeiliee . 42- ek.a., /Pli)efe.
f Wed eueoe Zi• • f/. 'etc I off _clue to
of -freec%eliczeon • 2 = iohd criefe. ee037 cesci4cziesfe, pie eev -
•3 .
.cine t o
Tiak,
•
4 eoeieie een 74 of teed eeeie ion::: ei....ee, ee2+ me 2+
mat t_er ile.93- eue o,
0,701
0,/08
•
-114-
Leaching of compounds (chemical erosion) from the subsoil
can be expressed by the following equation:
yo = (a - al )x + (h - to), where
a = The slope of the line which represents the dependence of the total discharge of compounds from the river basin,
a' - Tue angle of the line with axis x which represents the dependence of the discharge of compounds due to precipitation for average evaporation;
= The free term of the equation of the line for the total discharge of compounds;
b' .= The free term of the equation of the line of the discharge of compounds due to precipitation.
The e.quation can be rewritten in a simpler form:
yo = aox + 130 .
Such an equation can be used for calculations of the
discharge of compounds due to chemical erosion.
It is evident from Figures 23, 24 and 25 that the true •
ddscharge of ions from the river basin in the flysch area is
very close to the discharge of ions provided the water concen-
tration (in the original text "water concentration", but
according to the sense rather "the concentration of ions in
water" - translator's note) does not change, i.e. that the
subsoil at each Q saturated water with the amount of compounds
which appears in water at minimum flows. This means that the
subsoil has a much greater effect than the precipitation. The
influence of precipitation is manifested mainly on waters from
Early Tertiary eruptive rocks.
For a more general characterization of the leaching
capacity of a certain subsoil the author suggests a so-called
coefficient of leaching of subsoil, i.e. coefficient of chemical
eriosion; by means of such a coefficient it would be easier to -
•
•
-115--
calculate the discharge of compounds from the subsoil as a
portion of the total discharge of compounds from the river
basin, i.e, that portion of the discharge which is due to
chemical erosion. The coefficient of chemical erosion is a
number which represents the ratio of the total dishcarge of
compounds to the discharge of compounds due to leaching of the
subsoil: ax+by = 0 o +
ax + b y •
where y is the total discharge of compounds and yo
the discharge /106
of compounds due to leaching of the subsoil.
For our . conditions (the rivers Nitra, Laborec and Rika)
we have calculated coefficients of chemical erosion for some
more important components (Table 46).
The table indicates that the coefficients of chemical /107
erosion are low for areas of Early Tertiary eruptive rocks
(Rika), where the subsoil has small amounts of soluble mineral
compounds. High coefficients are found for such components as
occur in the subsoil in elevated amounts.
By introducing such a coefficient we are able to compare
the effect of subsoil on the discharge of compounds in relation
to the total discharge or to the discharge due to precipitation.
Hence we see that the ion discharge coefficients of water are
considerably higher in the flysch area than in areas of Early
Tertiary eruptive rocks. •
-116-
1. Distribution of the Discharge of Compounds
We have shown the total balance of the discharge of
compounds, the balance of compounds falling on the drained
territory in the form of precipitation and the proportion of
such compounds and compounds leached from the subsoil of the
total balance in the foregoing chapter. Now we shall briefly
deal with the volume of the discharge during a year, i.e, the
volume of the discharge according to individual months and
seasons.
The evaluation of the dependence of the changes of the
discharge of compounds on the flow showed a very close correlation
and in some cases one can even speak about a functional
dependence. Therefore we do not have to think about other
factors which could affect the discharge of ions and, therefore,
also its distribution during the year. It will be sufficient
if we confine ourselves to balancing only the flow conditions.
The differences in the discharge of compounds during the
year are very large and, as a matter of fact, they result from
flow changes. If we make a balance of the discharge in the•
course of individual months (cf. Tables 47-50), we observe
very large differences on the Laborec (flysch area), where,
e.g., the difference is about 17-fold with respect to the disbharge
of total mineralization and 19-fold with respect to the
suspended matter; the differences in sulfates and chlorides are
even larger. With the Rika (the area of Early Tertiary eruptive
rocks) the differences are considerably smaller. With total
mineralization and suspended matter the maximum difference is
-117-
3.5-fold and with cÉlorides and potassium up to 5-fold. We see
that fluctuations in the Rika are 5-6 times smaller than in
the Laborec, while the differences in flow fluctuations are
about 4.5 times as large. With some components, e.g. sulfates, /112
the difference is only 2.3 fold. Hence it follows that the
variability of discharge of compounds is affected both by flow
fluctuations and subsoil.
As far as the distribution of the discharge of compounds
within a year is concerned, we observe the greatest portion to
occur in spring and winter months. There is an extremely
high discharge from the river Laborec in winter months.
Several times we have recorded high levels at snow melting and
simultaneous increase of flow due to rains (we have classed
such cases with the spring season). The smallest portion of
the total discharge of compounds appears in the summer and fall
months.. It is evident from Tables 51-54 that 72.4% of the total
discharge of ions runs off the river Laborec in the winter and
spring seasons, and only 27.6% in summer and fall; this is
roughly in agreement with flow conditions. In the Rika the
discharge of compounds is distributed a little differently. In
winter and spring only 56.3% of ions of the total disbhârge
runs off. There are certain stall differences as far as the
distribution of the discharge of individual components (ions)
is concerned, but this is in connection with the èffect
mentioned above.
•
• 4 leek, +7 mone4 escherieee.. cy ions anal 74,4/
1% ]
/0,3
9,1
46
.07
II.'
46
42
0:4
J;4'
10 0
ea
kg/4 W.]
400,1 5,7
744,6 /0,
470,4 45
1032 41
1699 /t 4.
, •
I 7191 /as 1976 42
5543 7.9
393.2 96
sae 57
1147 3;6
861,7 9,6"
40,3,3
EI091
4'
(kei5)1 11(34's11-
tz, 140
21,1 71.*
19,1 I/O,'.
/35 9.1
\ es , 12,4
/es 14 0
146 , ea /4,4, I 78
•8,9 1 M
47 i 4.7
9,0
14,9
107
4,3 4:0
te 2 /2,4.
94 48
8,3 Zd
/4,1 mg
/4/ 13. 2
/31 /0.4
8,9 43
47 44
4,4 4,1
47 44
89 1 4 2
el I 4 1 8,5
a- _
Utsvil [ % 1.
14,3 43
347 10,3 ,
27,6 9,2
243 41
31,9 12,0
271 9,1
24.,5- 92
244 44
16,0 44.
16,6 44
/M. 4,8
91,2 10,5
**
[ keel
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112,5
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1049
143,5
1241
1019
85,1
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445
199,0
25o i 44. 25, 9 45- 1040
• es '.
ref 30,0
249
24,1
3.3.1
330
240
23,4.
141
16,7
149
32,5
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8,5
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12,4
10,5
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ff,6"
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/277
79,7
45,2
935
712
41,7
50,3
40,1
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543
102,1
72,0
1 •41
14,0
71
146
41
7.0
44
1,s
9,B
/1,7
uspencied matter
ri9in
-118-
The Arntc4e,
. Bratwoeci-Akin /871
awl% 1 a egiéd
(-ei) Py/s1 7,1
/ /see 44.1,7 7.41
1512 154,1 1,4'
Al 2991 401,1 /0,5
/Y 1190 474* 4 $
Y • 150/ 4511 11,
Y/ MU 14.4,2 9,5
17/ 2301 4447 40
YI/ 1177 4.294 7,5
/X 2013 3141 es
•X 1477 821,6 41
X/ 1601 2941 42
X4 /44.3 548,9 9,5
177n142 2010 485,7 mean
ie-Suspended matter . _
7.9 I 2771
nited [kg/e] [71 [.91/11
181,1 7.0 ates
le: II, 413,2
046 /1,1 3639
1107 4 3+43
170,2 11, 2 3540
211,7 49 447,9
1+1,9 Z 6 eei
211,7 70 329,0
5,2 2+49
1991 60 2147
1737 5,* 2/e•I
317,4 46 +048
421 3148
NCO;
./euen nlonihly 04..sc469.4e9e, 07e ..0.75 erne' 7eteW/77/e-efecilizzzAct7 lei ken v 'Vitro b7,4/7eia. (Agee 4nigi1/5423ktn2
TQZ/e,
e 1 a . PR-14de: Igniteçt*. //co; Jo:- CI -
011 417 .. [me] [9/3 ] [ % ] [gis] [7.1 [es] [7. ] [97s] [7.] [gAr]' [7.] [9P- ] 1- [7.] WM' [7.] [91 [7,1 ['s][ ['/,] Wei r [%3
4. / 22,3 95/5, /41 3 - date 143 59.974 15,6 1 070,4 13,2 9090 15,8 f771,1 ' 14 0 + 77 2 1+,8 4633 164 165,0 16.6 f0 9343-1 /0, 7 // 24,0 7531,4 131 5251,2 12,8 " 204,1 /1,0 7248 :49 e3e2 l4 0 /267,2 10,7 333,4 /0,3 2760 9,8 1272 12,8 7353,4 1/2 /// 248 8021,7 12,4 4993,1 11,9 50142 13,1 9838 1 /5,2 7+1,9 118 /4/4,1 . /1, 9 322,6 /0 0 369, 6 13, 1 124 7 12,8 8905,0 / 3. 4 Ze* itt 584:49 9,3 37561 9,2 3404,4 9,6 yeed I /2,1 4834. 7,7 /129,4 ' 9 4. 295:7 9.1 777, 2 0 8 Ma 10. 2 7176. 8 /1. 4 e /6,2 +9/4/ 77 3066,7 . zs 8044,7 zs 704.5 .17 4876 7.7 .9040 7.6 2002 47 239,5 45 34 2 4,1 1736,4' 8,7
• r/ /1,3 4334,7 ea 24748 45 24841 30 557/ 6,9 440,7 7,0 722,1 1 6,1 233,9 . 7,2 /77,4 6,3 548 49 1034+ 77 P// 16,1 5734,1 ea 3641 49 1656,9 es 8801 10,2 . 426,3 8, 9 /181,7 ■ 9,9 3146 .9,8 249,6 .9,8 83,7 8,4 63843 07 Pe' 40 3193 6 40 /852,0 45 - • - 373,6 Z/ 2840 45 6240 43 /7e2 55 -- - - - - - a 71 2102,0 44 1854,0 4,1 19915 4,9 364.5 4,5 2493 4, 3 542,3 46 /450 51 97,8 4/ 413 42 - - X es 29044 4,1 2/6g/ .3,3 1 921, 4. 5,0.. 8341 4/ 112,3 .43 5548 . 47 /73,4 44 /443 42 52,7 .3,3 2733,3 4,2 Al et 4 /10. 0 69 2 9744 es 1715,1 72 +41,6 6,0 483, 1 Z7 787,7 ' 46 224,1 6,9 257,6 9,1 828 8,3 4933.7 7 e- Xl/ 14,0 4792,2 7,5 8 3432 42 33749 48 459,4 4,/ 514,6 ; 42 9534 , .9,3 233,5 32 2744 ee 142 8,9 51746 9.1
/11niet be+ 5149,4 .er 18142 9,3 17472 9. 9 760,1 9,5 .5778 9.2 /015,9 45 3044 9,4 283,4 /0,0 /032 /0,2 8 /32,8 /2,4' Mean
a •,
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1+8,1
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-119-
1101
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R/442.4 196Ortc li7Hich91011C2. . . i .4145 in ,4f-14 ea/ 1 rut m ,cm i
y c Je t ' el- Cot* • Mai - 4 /19" X" . Ze•
pimith , a
7'/2/eet -x. gnitect //o-
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/ $eg scam 14.9 $ 2147 14, 2 15742 240 1 0143 17,1 4547 1+,1 /M40 let zee/ les se7 .9,9 sae ea to SI*4 129
// $9.1 nee,' 240 S$11,1 182 1731.4 At /194,3 " 12,1 sear zee 2083,0 2411 302$ 211 $44 1 32,0 279,1 MI F5 924,1 17,8
*0+ /41 eggs 11,1 stay . Its was 12,0 1891 9,4 954. 7 11,1 119,3 /41 121.0 11,1 80,9 140 4 2085 es
1Y , 144 5244? LI 2/242 41 11110 9,1 se1,4. 9,9 /181 81 7181 81 /417 /40 92,0 84 142 Zi +1441 8,7
bli /0,9 11187 4,7 /2247 4,5 14144 43 31(0 47 74. 2 3,7 4147 .4,1 111 48 140 4,9 348 4, 1 27147 4+
In es /74.44. 4.,4 1/247 kJ / +MS 41 tsgs 3,2 ez 1,4 14,Z, 4,7 180 4,8 54 1 41 13,1 ZS 2 1140 4,1
I XX MI 19741 8,1 2474+ 88 110) 7 9,9 1241 49 2940 11,0 912/ 14i /740 /2,0 /181 /0,7 84/ /1,2 * 511,1 9,9
. ex ee .1144 2,1 1471 41 7149 2,1 124,0 - 2,1 121 14 205.9 2,4 351 2,1 *1.3 3,1 /87 41 1 MI 2,4
Ix 40 917,9 1,7 3$89 1,1 4742 1,7 1017 › 18 144 12 /14,1 1,8 14 2 2,4 2+,9 2,1 11,2 48 901. 0 1,8
f X 4,0 1244 2,! 1180 2,1 $egs 2, 4' /081 1,8 344 /7 1112 2,4 +12 3.3 41 1 41 /4 4 41 F123,4 4 4'
XI 49 /522.1 418 / 024 / 40 /1141 4,1 2/40 49 $18 1,9 399, 2 4 0 69,1 4.1 14 7 4,9 141 4.1 / 793,0 41
XII 14 9041 1, • - - 47Z7 1,7 de+ 1,4 30,0 1,1 /443 1,7 /71 1,2 +40 3,7 /4/ 2,1 - 1010 41
eltrited $47 310.22 43 2/141 81 23171 es 1180 ed Ides z7 721,1 81 //Zd 43 102,9 9,4 141 49 19 312,5 84
11121111
*.Suspended mater
...■
_
ekan Money oliSc4q/2,7e oic l'Ons czec;/ 7407id Mii7e/e,ea'zaiioo 7aWe e
Pi:to Komienkci léagin ergerz,ge 4.er
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X# 2,01 /MI /1,4 /042 /2,5 71,1 /40 37,4 /9,7 /2,1 /1,8 244 /47 42 /49 8/ /S, 2 "fornte _
mea ' 1+1 1/1,1 4+ MI 4+ 111 41 me e 4 ec .0. 4 /4, 7 44 3,7 4 4 4 4 Bs'
buspended matter
-120-
2. Specific Discharge of Ions and of Total Mineralization
From the viewpoint of submitting parameters and meeting
ecomomic requirements, the results should be generalized;
therefore it is necessary to give a basic unit which would
serve as the starting point in various calculations. We have
decided, therefore, to calculate specific discharge of individual
ions and of total mineralization (as in hydrological practice),
which means the amount of compounds discharged from a square unit
(km2 ) in a time unit (one second): g/sec/km2 .
We are presenting the specific discharge of compounds and
its simultaneous distribution in the course of a year.
It is evident from the basic materials that there are
differences between the specific discharges of individual ions,
total mineralization and suspended matter. Specific discharge
of total mineralization, of suspended matter and of a major
part of the ions is higher in the flysch area than in the area
of Early Tertiary. eruptive rocks, which is again different from
other regions. Specific discharge of chlorides and alkalis are,
however, the same, and specific discharge of potassium is
even higher in the area of Early Tertiary eruptive rocks.
As far as the distribution Of specific discharge is
concerned, it is in agreement with the distribution of the
discharge of compounds (cf. Tables 47-54) and the same applies
to the former as to the distribution of compounds.
•
• •
Télle elee4eidihiee keitvee4 Me- Wisc4 ,e_ .7 1 ions eznef 747-4t/
7ht Panuee- and annuel season. -47 seizeshve,r p km 12771 , _ ,,,J.'.g lit...40. lel,er in19,_ hnuel a g
ln Qià 30,1- CI - Ce t `
me I. /,/ * K * le
kewl >es] [kg;s] %ria [keel /e. J0 keirl 17°)0 [9/s1 [%10 [kes] 13/4.1 0 [ker] v410 tkeirl [1,2f [kg4] (r.:1e4 [A-a/el
2511 104 9 29,2 3/3,2 241 3840 149 76,3 36. 2 29,1 29,2 /256 29,0 314 21/ 19,9 32, 4 /2, 4 144 7349i 11,1
filming«, 2 266 901 / 209 2/68 /9,7 107,2 22,9 18,7 hte 240 22,/ i6,0 /94 213 21,6 /1,8 216 82 23,0 04,9 I 249
Fee /576 3844 20,3 291, / 210 2102 249 67,0 23.0 20,7 248 1/1 9 23.8 214 212 /1,2 /2,2 6,0 /0,9 486, 5 247
Wi'alre /ces sec 296 1323 347 1644. 223 99,3 32,4 227 228 //a,/ 244 fee' 26,2 /2/ 228 90 28:3 6049! 25.8
I 2010 412,7 23,6 27/,6 " 9,7 fee 241 72,0 24,7 Ka 25 1 /09, e 24', ! e9 23.6 13.7 25,8 9. 1 214 403.3i
e7 creams
raPe, z elkee
/Vitro ;ye lie kv
cf eieee,4›..4.0a as ale#Ced/%1e P/L annual -reason
4etwil e, 5 s e e d . ma; _ - r //co,- • 20 1- 4*
01 -- eoz-* me.r. me + x * Ze
114,Solt,
re« res 1 ' .0 [57;s I .0 [ es ] 4 [i/s) 4 0 [ er] 4 ee ] .0 [es] 410 [es] r• [es .1 (4. 10 [es] if. 1".:. ) 0
e/ e s8e2 30,8 4 1448 29,1 4 /25;7 297 eatz 22,1 194,4 ee /û 3 J9.1 e49 248 tei 244 /064 311 71864 341
leynfen /34 49246 22,4 8/443 22,4 1 MS 23.8 72.7.3 es 119, 4 exa 7143 /9,7 2740 24,1 /960 /42 714 211 1120 219
/
fed/ ed scc49 /44 z420 /23 24/42 /7,9 40e,e /9,4 Jett /24 7/1,9 19$ /944 /20 2/7,4 202 de 24:0 43+9,0 /7,2
Villite 1679 68950 3/2 4 lie 9 349 48958 29,5 772( 226 779,1 S4 / /101,9 20+ 183,9 24/ 1e40 1e,/ 729 23.1 77648 108
0916 ' area 2' 4' 6881.-8 21." 3724,2 26,1 373/,: 228 769,1 27,8 577,1 248 /8/48 229 891,4. 346 213,4 20,* 1/48 15.1 0/124 12,3
ultif]
less
-122- _
CiSr.4eztey.e, 74>A7 1eqo in ccordancewith the season
even, rec int-1/c/7Qloyct...•
(2 Pilied.de.".1 ite -- lic°:- eel' el - cot* /.19 34 . No K + El
Je-as e4 tml/sl [ 9/s1 r.- 779. 0 [9/si L'1•10 [es ] [Ye.. 10 [vs) ci../25 [g/s1 i‘tefl Ls/el r [gis] 1 % 10 re41,-; 191311 Teeflo [ ws ] f % 2s I
ifAginor 2448 41072 54/ 3/24,8 4Z 7 81444 44,9 7771 11,9 2278 -4-0,1 /0241 43.3 /70,9 493 /42,41 49,1 74,0 I 42,0 1 906,4I 142 ! ! I Jimmie eV 1770,2 /42 /174:7 /40 /424,0 /8,3 2644 /7,1 163 te2 429,9 /92 e0 /ze 641 I 248 144 I .941 2413.0 i /7.7
FallA. 442 10042 /44 14.2,7 94 8042 /0,8 /33.7 9,2 .941 2, 7 289,9 /47. 49,1 13,4 441 /4,1 23,4 ; /3,3 1$219 II .9, 1
WM/ex /4 19 20748 21,4 /103. 9 24,1 /9941 24;4 100,9 20,4 99,9 22,1 142,/ 242 etc 22,7 43.9 /j;,g 21,1 : 14., l' je784,1 27, 4.
77 1470 3306,2 34,0 2/83.1 82,9 2144,3 .32,7 smo 83. 1 /18,3 34,1 723.9 12,4 /17,8 31,9 /02,0 33, 4 63.1 ..772 42740i 341 /MAAS I I
buspencted matter
Teibb--
PA) e Pek eischaefe. de. e /oils qed fvfeil eilhe1/2eibe7according_to the season Tie fe.
'ke Xe/nieek.
Anual a eiereci*-Tgai.t er, 4, W001 ./0:- CI" cell' e924 No+
Sé4:i Lm/s]9/J] 1 % 0 1[es l!r`Y:f.'0 Is/s1' 0 Is/el /'Ø 1 es ] .0 [ es] ' 0 let] " 0 [es ] • [ es] .• ]0 [ils] [ Y• 10
Sparno 2,23 171,3 93.7 /e/,7 ; 870 71:2 37. 1 24, 1 Jes 43 37,4 241 11:2 4:9 ses es see 7/ 4.1, 0 /474 I 344 I
Siimmee2 411 749 /40 40,9 I /9,1 43. 7 20,3 9,9 /02 4.4 /7,1 /49 /0/ 2,8 24/ .3,1 241 .1,1 242 740 ; /42 ' I
404 91,0 241 90,11 22,0 +9,7 22,/ '14, 4 28,6 3,1 22,1 12,6. '!•22,1 10 21,6 e+ 249 -3, 4. 707 7006 1 21,0
Wioltg1,22/00,222763.0;72,956,224,//2, 0 247492e0 rne02, 9 /7. 8 4 3 /9, 191.7! 24 9 I ri, - 44.2 //6,6 24;4 72,1 1 26,2 142 23,9 11, 26,2 6,7 24/ /49 241 3,7 296 f,4; '. 2Z0 4, 7 27. 2 /02,1 21,0
1,124/7.5 • i - ,
_*puspended matter 4, uq/ esteve.-
- elt-Inkez/ eesiniteze.,79oe ffie -s-Ateteitie- eile-hcrefe., /lees gee, 4/12/ leitte.e'reze75'es,
Palieuee
Bretir/ore ,km 1.971 cé4i:»7 aieez /31331.2 k," 2 ,
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-125-
V FORECAST OF THE COMPOSITION OF RIVER 'WATER
In connection with the increased demand for the quality
of water used in various branches of the economy, the problems
of suitable basic material on the composition of water and its
prompt use arise. Nowadays with such a high and extensive
demand it is impossible to provide basic material for the
requested case when the need is urgent. Collection of the
materials which would reflect composition changes during a
year would last too long and the realization of planned actions
would be postponed. It is therefore necessary to generalize
the knowledge of the composition of the water, which can then
be used for required purposes.
Final conclusions based on the generalized knowledge
shouid make it possible to predict water quality. This is
what we are trying to do. Forecasting the quality of river
water has not been sufficiently elaborated in our country or
abroad. Only in isolated papers do we meet references to
forecasting the composition of water, but even this is marginal.
Eventually the authors, who refer to a relation which expresses
the dependence of the change on the flow or the change of compon-
ents on total mineralization indicate that these data could be
used for forecasting composition changes. Existing knowledge
can be summed up as follows:
Since 1901, when KUNDSEN for the first time elaborated
hydrographic tables for the calculation of salinity and density
of sea water based on the chloride contents according to the
•
the formula 1
Qn = k (c)
-126-
, III formula S% = 0.030 + 1.805 Cl - , and which tables are used with
great success in oceanography, this relation has been applied by /120
MUSINA and MIKEJ to river water as well, namely to the river Don.
They accomplished the calculations by the method of least
• squares and the error was less than 0.02%.
PIVARELIS (69) recommended using the dependence which he
obtained on the Volga (Saratov profile) and Moscow River
(Rublev profile) when observing the dependence of the composition
of water on the flow with the aim of determining the flow.
The author thinks it possible to use some step function for
the expression of the dependence in spite of large dispersion
of points. To express the dependence he uses the reciprocal
value and dried suspended matter, for which he gives the following
relation
1
dried suspended matter
For a concrete case it is
Q = 11.9 x 10125x
where X)/ 0.007.
Like ALEKIN (2) the author recommends constructing two
curves, namely for the rising and declining trends. 2- BLINOV (28) states that the changes of 8
04
and Cl- content
as rélated to the flow of the Volga in the profile Saratov obey
Q=
and he gives the following concrete relation for C1 - :
•-0.63 - Q = 0.035 Cl
-127-
It needs to be noted as far as such evaluation of the
correlation is concerned as well as the evaluation of the
correlation derived by MUSINA and MIKEJ for Don River that the
selection of components used for the expression of the dependence
was not chosen advantageously. This was proved both under our
own as well as Japanese conditioris, where very weak correlations
exist between the components mentioned. In many cases one
cannot even speak about correlations.
Weak correlation between such components in waters with
low mineralization result from a greater influence of climatic
factors and soil processes on the content of such compounds in
water.
Also ALMAZ°V (8) can be blamed for such insufficiency.
He also used chlorides for characterizing correlations between
the composition of water and the flow in the Dnepr and stated
that this relation in addition to the relation for salinity "S"
can be used for prognostic purposes. He expresses both
relations by general formulas: n1 S = A1Q 2
CI- A2(4
The attitude is basically correct but the water components were
not chosen correctly.
BOCKOV (27) investigated the formation of the chemical
composition of water and the runoff regime in river basins
(i.e. the so-called external runoff stage) and arrived at the
conclusion that such a stage can be characterized on the basis
of hydrological conditions and the corresponding composition of
water.
-12g-
The author stated that a good correlation exists between
the content of water components, total mineralization and flows.
The correlation is expressed by a curvilinear function:
C = f(Q)
and is similar to the flow plot from which the flow of salinity
can be calculated. This relation is not the same during the
entire year according to BOCKOV and can also be different for a
defined runoff phase. He stated that the curves can have
various characteristics for the ascending and descending
branches as well as for the intensity of flooding.
VORONKOV (89) also states that the composition of water is
different for certain runoff stages and that the changes of the
composition of water as related to flow changes are different
for various rivers. He refers to several types of curves for
various rivers in the U.S.S.R. In addition to these relations
thè author evaluates in detail the relation between the content
of water components and total mineralization. The relations can
be used for the forecast.
Also MAKIMOTO HIRONARI (62) and TAKAKURA (81) mentioned
that correlations exist for the changes of water componants
among themselves and with respect to flow conditions. Both
consider it possible to use such correlations for the forecast.
On the other hand LARSEN (57) does not recommend using
for prediction of composition any relations between the components
of total mineralization and flow conditions in spite of the fact
that he found very good correlations.
-129-
Hence it follows that many authors who found certain
relations between the composition of water or some water
components and flow conditions in the river or, possibly,
relations between water components and total mineralizatiôn,
tried to use such relations for forecasting the composition of
water. Any success in this direction cannot be considered as
satisfactory. The fact that the forecasting technique has not
been elaborated to a sufficient extent should be ascribed to
the fact that even individual relations have not been sufficiently
elaborated, not to mention the fact that the influence of
individual factors on composition changes has not been accurately
determined, which obviously has a great effect on the formulation
of the forecasting technique.
The greatest success in forecasting water quality was
achieved by Soviet authors and by CHALUPA in our country.
In our papers we have evaluated in more detail the dependence
of the changes of water components on total mineralization as
well as on the flows, we have characterized the qualitative
properties .of water from various hydrogeological areas and we
have evaluated the effect of precipitation on the composition
of water. We can, therefore, proceed to the problem of fore-
casting from a wide'r viewpoint.
It follows from our results that the most useful items for the
elaboration of the forecase are the relations showing dependence
of the changes of the suspended matter, specific conductivity,
bicarbonates, calcium and total mineralization on flow changes
•
•
-130-
as well as relations showing the dependence of the components
mentioned above on total mineralization and specific conductivity.
Other water components which do not show good correlations
(sulfates, chlorides, potassium, sodium, etc.) cannot be used
as basic indicators of changes. They can be calculated by
using some other characteristics.
For the evaluation of chemical erosion of the drained
territory, we can use the relations cited for the balance of
the discharge of ions and the total mineralization as related
to the flows.
The relations which we have d. rived and which express the /12)
dependence of the changes of components on the total mineral-
ization of components, total mineralization, suspended matter
and specific conductivity on the flow as well as relations
between the discharge of compounds and the flow can be used not
only for short-term but also long-term forecasting of the
composition of water. However, with long-term forecasts,
especially with respect to water in reservoirs, it will be
necessary to donsider other factors as well (such as, e.g., the
presence of biological life, biochemical processes in water and
in bottom sediments, evaporation, infiltration, dwelling time,
etc.) to which no attention was paid in this paper because of
their exceptional character.
In our case we focus our attention on forecasting changes
of the composition of water as related to the flow during the
year, i.e. on the conditions of natural changes in flowing water.
without impounding it.
• -131-
If we calculate the content of the main ions, we assume
that we know:
1. The flow in the river (Q in m3/sec), - 2. Specific conductivity f.itin .cm .10 6 (18°07
3. Alkalinity of the water (in mval/l. or, like the content of bicarbonates, in mg/l.
We have chosen these known values because they can easily
be obtained by simple masurements and their relations are
relatively good, so that the calculations of the content of
components would notbe full of major errors.
To be able to calculate other components also (the main
ions) based on the components mentioned above, we should learn
the relations between the total mineralization and the components
mentioned above (sic: - translator). We can calculate any of
the components mentioned before if we know the relations
between the various main ions and total mineralization.
Relations between mineralization and the three selected
components for rivers which we have observed are listed in
Table 59.
From these relations and from relations among individual
components listed in Tables 19-22 and 25-28 we can calculate .
the composition of water if we know (measure) one of the three
quantities mentioned.
•
•
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weic/e riews eeleiion. , ett-
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O
-133 -
• /124-
•
The mathematical procedure is basically as follows:
firstly we calculate total mineralization () and then using
it and substituting in equations for individual components we
calculate the real values of certain components. Thus on the
basis of relations known we can calculate the content of certain
components at various values of the flow; in addition, we can
define them in more detail for various characteristic seasons,
various trends of flow, etc.
Similarly we can calculate and predict also the magnitude
of the discharge of compounds (ions) from the :river basin.
This can be used with advantage in drawing up the hydrological
balance, in judging chemical erosion, in evaluating the quality
of water impounded in resenpoirs, etc. In this case it is
sufficient to use the relation for a certain component and to
calculate data from a real case.
Such procedures for calculating both the concentrations
(content) of the compounds in water and the discharge of
compounds from the river basin is sufficient for a rough
prediction of water composition and the discharge of ions.
To simplify work and ac elerate calculation of the
content of compo s e author constructed nomograms on the
basis of the obtained equations (Fig. 26 and 27).
•
y=0 X
ek—peteenetw acueve
X-0
now d'afiecim
•
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• e
% s2. c
• 2
2fre °2 1 ••• 40 tO
9-• a
7 . 7
- S - S
# ' #
1,014 10 7 3 ,'
li
1,0 10 1 • 9 9
8 r 8 7 7
-:--: 5
45 3 -r• 0,5 3
2 1
£10 log x #,0 0,00
•••••••• ••• ■•••
num. log x
025
0,50
0.75
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eitAeldiee leî,
- 5E) + 7
-135-
In both cases associated nomograms are shown. The first
nomogram represents the equations of linear regressions
and the other the equation of a nonlinear regression for the
dependence of the change of components on the flow
y = a.x
We present the necessary characteristics for the use of
both nomograms in a tabular form (Tables 60 and 61).
To calculate the first nomogram we proceed as follows:
1. We search for "y" (i.e. one of the water components) for
a certain assumed "x" i ) at a known "z" (regression
coefficient) and "u" (free term of equation).
Procedure:
Draw a line from scale "a" (for a known "a") through
scale "x" (for ) and on scale "y" read the magnitude of
the desired component.
2. The other procedure can be reversed - for an assumed "y"
we find "x" while "z" and "u" are the same for the given
component and river as in Example 1.
Procedure:
Connect the know value on scale "y" with the known value for
the given relation on scale "b"; read on scale flax" and
connect this value with the known value (on scale "a" - added
by translator) and read 7, on scale "x" (English formulation
by translator, because Slovak explanation is incomprehensible
and inaccurate, cf. the original paper, Page 133, line 9).
•
-136 -
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C1 - - - /29 / - 449', /0,39 - 0,/04 4,45 -4778 _ . _
Ca f + 169,8 -0,161 1+1,4. -0,297 641 -0,/21 /1,39 - 0,584 52,4. -0,093
He 2. - - - - 11, 66 - 0,166 2,63 -0,372 - -
N a * - - 66,8 -0,555 /1,86 - 0,292 2,94. -0,102 - : -
N + - - /5,23 -4272 2,34. ... 0,//9 3,04 - 4 /89 - -
ri /24,4/ - 0./30 - - 3637 -0,128 83,28 -0,1/98 321,9 -0.152
Nolte : 49,4 e7L-eies q eteieve- rhypededeila)
•
• -137-
The procedure for the use of the other nomogram, which
represents the dependence of the changes of the components on
Q, is as follows:
1. We search for "y" (i.e. for one of water components) at
known "Q." and we know the parameters "a" and "k" on the curve
(a hyperbola).
Procedure:
Draw a line from the scale for the known
scale "x(Q)". Draw another line between the intercept
obtained on the scale "Qk" and the value "a" on scale
"num.log a" and read the desired value on scale "y"
(reformulated by the translator).
2. We know "y" and search for "Q".
Procedure:
Draw a line through the known value on scale "y" and the
known value "a" for the given relation on scale "a";
connect the resulting intercept on scale "Qk t with the .
known value on scale "k" and read the searched "Q" on
scale "x" (origninal text incomprehensible - translator's
note).
The procedures for reading (flow diagrams) are presented
graphically for both nomograms.
We cannot perform more thorough and detailed predictions
yet, because we have not enough observations (several years -
minimum 15 years) to be able to characterize, e.g., the
probability of repeating and exceeding high discharges of ions.
•
"k" through the
-138-
Relations such as these can be solved as they are solved in
hydrology, but we need additional observations to be able to
generalize.
Based on our basic materials we can construct lines indicat-
ing how long the discharge of compounds (ions) lasts and lines
indicating how long certain concentrations of individual
components or of total mineralization last. Because there are /134
very close correlations between the discharge of ions and flows,
and in some cases there are even functional correlations, on
the basis of hydrological material we could calculate predictions
of repetition or exceeding of discharges with a certain
probability.
Calculations of the probability of repetition could be
accomplished by one of the methods used, either graphically or
by means of some equations for empirical probability distribution,
or by means of equations for binomial or logarithmically normal
distribution, or by means of some simplified methods (e.g. after
ALEKSEEV - 1960).
Calculations based on the equations mentioned, which hold
true for entire complexes of random quantities, yield values
which characterize the mean composition. If we wish to character-
ize the composition of water under various conditions (various
seasons, various levels etc.) and make the results more accurate
and decrease the errors between actually found and calculated
data, we can make the calculations on the basis of the equations
for partial correlations of characteristic selections of random
quantities.
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-141-
The question of how precisely we shall succeed in determining
the composition of water depends on how close the relation is and
what way that particular relation is used. Errors between
values found and calculated are lower where partial nonlinear
regressions are used; most results fluctuate within limits of
-5% error and only isolated cases have a higher error.
Somewhat greater errors occur due to the use of specific
conditions, but they are still within acceptable limits
(except sulfates and potassium - cf. Tables 62 and 63).
It becomes apparent from those tables that though the
differences (in percentage) for individual components and ways
of calculations are different, they lie within acceptable
limits.
•
•
-142-
BIBLIOGRAPHY
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•
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•
111••
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• THE CHARACTERISTIC OF THE COMPOSITION AND OF THE LAW 01P THE SLOVAK SURFACE WATER COMPOSITION CHANGES •
Ing. Miami A ntonië, C. Se.
In the work presented the general hydrochemical characteristics
of river water (according to prevailing ions) is given and the
dependencies of water composition and their changes are evaluated
by means of statistico—mathematical methods and as far as the data
have alloyed it the factors, influencing the water quality are
evaluated as well. The balance of ion discharge and of the total
mineralization was elaborated and the derived relations for the
forecasting of water composition were used in the conclusion of
the work.
The results and knowledge obtained can be summarized as follows:
The general characteristieof Slovak waters: According to the content of minerals we classify our waters into four categories:
1. Only very slightly mineralized water
2. Water with a small mineralization
3. Water with a medium mineralization
4. Water with an increased mineralization above
up to 100 mg/e,
up to 200 mg/I,
up to 500 mg/Z,
500 mg/i.
Water originating from crystallinicum, from granite massives and
young tertiary formations pertain to the first category.
Waters originating chiefly from regions mentioned above with occu.;-
rence of other formations pertain to the second category.
The prevailing part of our waters, originating from different
geologiéal formations pertain to the third category. Waters from
zones of Werfen layers, Tries limestone and Dolomites as well as
•
-157 -
waters, considerably influenced by industrial waste waters pertain
to the fourth category.
The basic formation of water composition is influenced by geologic
conditions and the variations of composition are influenced also
by other factors (hydrologic conditions, soil conditions, seasons
of the year, climatic conditions etc.). Under the effect of factors
mentioned above not only the °vex. all mineralization, but also
the mval % substitution of components on the overall mineralization
are changed. The over all mineralization varies in a considerable
range according to the origin of water and under the effect of
other factors (compare tables la, b, c, d, e, f). The changes
take place not only in the mval % substitution of components but
also in the relative mutual occueence of the more important compo- A
nents. The coefficient variations in some groups of ions are very
pronounced and they show the response of hydrogeological conditions of the drainage area.
•
As far as hydrochemistry is concerned bicarbonate-lime waters with a coefficient 1.9 to 8.2 and with a most frequent occurenne
of about 3 - 3.5 are prevailing.
In the regions of slightly mineralized waters (the region of young- .
tertiary eruptive rocks, crystalline granite massives) there
' are waters of intermediate type and even of mixed type below 1.0.
Performing hydrochemical classification it spears also, the types
of waters and namely the coefficients of the prevailini ion are
connected with hydrogeological conditions. :
From the practical point of view it is also important to know the _ seasonal variation of water composition, that means the effect of
the seasons and of temperature conditions connected *ith them, the
effect of soil condition etc. From the evaluation it follows these
effects are substantially lower than for instance the effect of
hydrological conditions, and they make felt themselves gradually
and slowly thus influencing the variations of water composition.
Even though the effect of discharges on the composition variations
is very expressive, it is not possible to assume, the influencing
of all components is identical. Even at the Rika River and namely
-158-
at ta Danube River neither the total composition nor the over all
mineralization are in the full agreement with the discharge con-
ditions. These disagreements are caused in actual cases by diffe-
rent sources of stream eupPly (the case of the Danube) and the
subsoil, poor in minerals and its degree of leaching (the case
of the Rika).
In both oases these variations are influenced temporarily.
The occurence of minimum or maximum contents of components do not
fall into the same space of time, because in every case make felt
themselves more or less pronounced also other factors. The maximum
contents of components occur in autumn and in winter eventually
also in summer.
As far as the proportional occiu>nce of components is concerned
it is not in full agreement with the content of components and we
can state, it is rather in agreement with the season. For instance
minimum nival % representation of bicarbonates occurs in spring,
when the amount of sulphates and chlorides reach its maximum.
Similarly the calcium content use to be at minimum in spring and
other cations at maximum.
The dependencies of variations of river water composition: Analysis
of factors, influencing the river water composition showed, several
factors make • elt themselves, acting usually simultaneously. As the most important factors, which form the basic water qualities, are
considered the hydrogeological conditions of the drainage area,
that means the subsoil (mother rock with its surface layer - soil).
The water composition is effected by soil conditions in substan-
tially lower extent. The effect is so slight, that the correlation
between river water composition and soil types was not found.
The amount of the total mineralization as well as the proportional
substitution of the more important water components and their
mutual relations are effected by hydrogeological conditions. In
the connection with hydrogeological conditions the types of waters
are changed and namely the values of coefficients of prevailing
ions, pertaining to the respective type of water.
•
•
-159-
The river water composition depends to a great extent, but not
fully - as some authors claim - on the precipitation conditions
and on discharge conditions connected with them. The effect of
precipitation on the variation of river water composition is dou-
ble-dealing:
1. physical - as result of the dilution with more mineralized
river water,
2. chemical - the contribution and the direct enrichment'of water
with chemical components.
For the rough appreciation of the first - physical - effect it is
sufficient to perform more detailed observations of discharges
and eventually also the precipitation sums for the characteristic
period. For a more thorough appreciation it is necessary to perform
more detailed meteorological observations.
For the appreciation of the chemical effect it is to be informed
about data on the composition of précipitations for actual cases,
because the precipitation waters are different according to the
region (mountaineous, low-land, industrial) as well as according
to the seasons. These variations are not very important in our
conditions but they must be taken into consideration in a more
detailad study. The over-all mineralization of precipitation waters
in our country is about 40 - 60 me/ and the residue about 30 -
- 40 me. Prevailing anions are bicarbonates and 'in some cases al-
so sulphates. From cations prevail calcium and sometimes sodium
and potassium.
The chemical effect of precipitations in these regions where waters
are slightly mineralized, is substantially higher than in regions
with higher mineralization, especially as far as variations of
mutual ratios of water is concerned.
Detailed analysis of more important components of the total mine-
ralization showed the dependencies of variations and the relations
of these variations to the variations of mineralization, thus being
able to use the results for the forecasting.
•
•
-1 60
• The dependencies of components, which under ideal conditions would
be the function of mineralization, are correlation relations as
result of differently applied influence of natural factors. The
I degree of dependence is relatively high for bicarbonates, calcium,
. specific conductance and dried residue, lower for magnesium, chlo-
rides and namely for sulphates and alcalies, but for the most
part they are above the limit of importance also for the 1-percent
probability (p = 0.01). The lower degree of dependence is evident
at those components, which are under more prenounced influence
of climatic conditions.
For particular components the relationships were computed, which
are stated in respective tables. In all cases it concerns the
linear regression. Similarly the relationships of some more in-
portani. -omponents to the specific conductance were evaluated
and in tables particular equations expressing the relationship
between the components and the specific conductance are presented.
During the elaboration of nomograms and statistical evaluation
of results obtained on rivers, observed during long periods I have
stated, that between the composition of water and discharges in
the river there are dependencies of curves (hyperbolic), for which
a general relationship y = axk is valid. Correlation coefficients
at more important components are relatively high (about 0.7) and
at components.(AC, À/9+, J'e- and Cr) are substantially lower
and in many cases below the limit of importance at 5-per cent,
reliability (p = 0.05). Relatively high dispersion of points is
partly due to discharge tendencies, partly to the source of wnCer,
taking part on the feeding of river as well as to the perlde.
and degrees of the leaching of the subsoil after a more iwportaro
outflow - run-off in rivers.
This assumption was verified by means of selection of random quan-
tities belonging to respective factors. We have obtained higher
degrees of dependence thus verifying the correctness of the as-
sumption.
As far as the influence of discharge tendencies upon the water
composition is concerned they make felt themselves as fôllows:
•
At increasing tendency the content of the total mineralization
I is higher as at decreasing tendency, at equal discharge conditions.
iBut the relationship is ()loser at decreasing tendency than at
lincreasing tendency of discharges. The slightest relationships
are at stabilized water stages.
The balance of water component run-off. The special part of this
work deals with the balance of the run-off of chief water compo-
nents. Besides the total yearly balance the distribution of . com-
ponents run-off over the year (aocordîni to months and seasons)
was made and the specific run-off and its distribution over the
, year (for the first time for our rivers) were evaluated. The va-
riability of components run-off during the year is rather high in
' the flysh region and low for instance in the region'of young tar- t tiary eruptive rocks, eventually in other formations. The varia-
bility of the run-off is greatly influenced by the subsoil and by
fluctuations of water run-off in the river. The highest run-off (in
per cent) occurs in spring and in winter. The water from precipi-
' tations was also taken into account, i.e. the balance of mate-
rials - components fallen on the surface of area drained by re-
spective river. The contribution falling on the leaching of ma- , terials from the subsoil was also evaluated, what was necessary
to be done in the estimation of chemoerosion. This approach to
the evaluation of cl,ieiLIoeron is different from the approach of
Braïnikova and Alekin, which include into chemoerosion the whole
amount of components. The run-off of ions from the watershed (cat-
' chment area) appears to be influenced by the quality and the kind
of the subsoil, eventualiy also by other factors and it is not
dependent solely on the specific water discharge and concentration
of materials as cited by Alekin and BraInikova. For the chemo-
erosion characteristic it is possible to use the 80 called coef-
ficients of usabily of the subsoil, event. the coefficients of
chemoerosion (1) used in the work.
For instance the run-off of ions from flysh region are of about
6 - 5.5 times higher than from the region of young tertiary erupti-
ve rocks and they differ from other hydrogeological regions.
Between the run-off of materials and river discharges there is
•
•
-16 2-
a very close relationship with correlation coefficients of about
rx4e . 0.8 - 0.99. The dependencies of the variations of run-off
components upon the discharge are linear.
On the basis of data and relationships derived for.particular
components in the relation to the total mineralization, to the
discharges and then for the run-off of ions in the relation to
the discharges the forecast of water composition was made. The
forecast was based on the assumptions, the data about water dis-
. charges, specific conductance and alcality are available.
For the forecast we have used the total and partial correlations.
Better results can be obtained according to relationships from
partial nonlinear regressions.
As to b. able to use easily these results, without difficult com-
putations two nomograms were elaborated:
a) for the linear regression of the components dependence upon
the total mineralization,
b) for nonlinear regression of the components dependance upon
the discharge.
•
•
• Page
-16 3-
CONTENTS
in the in the trans- original lation: text:
Introduction 5 2
I. GENERAL CHEMICAL CHARACTERISTICS OF • STREAMING SURFACE WATERS 9 • • • • • • 6
A. ON THE EVALUATION OF WATERS IN GENERAL 10 8
B. CHARACTERIZATION OF WATERS OF SLOVAK RIVERS 13 12
•
II. EFFECTS OF IMPORTANT FACTORS ON THE COMPOSITION OF RIVER WATER 34 28
A. EFFECTS OF ANNUAL SEASONS ON THE COMPOSITION OF WATER 35 31
B. PRECIPITATION CONDITIONS AND THEIR EFFECT ON THE COMPOSITION OF RIVER WATERS 47 . . . . . 41
C. SUBSOIL AND.ITS EFFECTS ON THE COMPOSITION OF SURFACE WATERS . 52 47
1. The composition of river water as related to soil conditions 53 48
2. Dependence of the composition of river water on geological bedrock 54 50
III. DEPENDENCE OF RIVER WATER COMPOSITION CHANGES 62 60
A. RELATIONS OF COMPONENTS TO TOTAL MINERALIZATION 63 62
B. RELATIONSHIP BETWEEN SPECIFIC CONDUCTIVITY AND OTHER MAIN COMPONENTS OF WATER 71 70
C. DEPENDENCE OF CHANGES OF THE COMPOSITION OF WATER ON THE FLOW 76 73
•
-1614-
1. General correlations among the changes of the composition of water (entire complexes of observations) 76 76
2. Partial correlation of the changes of the composition of water . 82 81
IV. THE BALANCE OF THE DISCHARGE OF COMPOUNDS DISSOLVED IN WATER 91 89
TOTAL DISCHARGE OF COMPOUNDS IN OUR RIVERS 96 . 98
1. Distribution of the discharge of compounds 107 109
2. Specific discharge of ions and of total mineralization 112 115
V. FORECAST OF THE COMPOSITION OF RIVER WATER 119 116
Bibliography 135 134
Russian summary 145
English summary 152 148
-165-
Michel Antoni‘e, M.Sc., Ph.D.
•
• HYDROCHEMICAL CHARACTERISTICS AND THE DEPENDENCE OF THE
CHANGES OF SURFACE WATER COMPOSITION •
Decimal classification 627
Published by the Hydrological Research Institute in Bratislava
in the series entitled WORKS AND STUDIES as the issue No. 27 in
the Slovak Publishing House of Technical Literature (SPHTL) in
December 1964. This is the publication No. 2792 of the SPHTL.
Editorial board: J. Furdik, M.Sc., Editor-in-Chief, M.AntonA l
M.Sc., M. Bako, M.Sc., Ph.D., J. Baller, M.Sc., O. Bogatyrev,
M.Sc., Ph.D.p...Brachtl, M.Sc., Ph.D., K. Brys, B.Sc., I. Grund,
M.Sc., Ph.D., M. Hdn, M.Sc., J. Mihâl, B.Sc., Ph.D., J. Prochdzka,
M.Sc., Ph.D., Doc. K. Rohan, Ph.D., J. Szolgay, M.Sc., Ph.D.,
F. 'àltein, M.Sc., O. nich, M.Sc., Ph.D.
Managing editor: Ofga Dobiâgovâ
Tedhnical editor: Andrej Uram
Photoprint: Hydrological Research Institute, Bratislava
162 pages, 27 diagrams, 63 tables
12.81 author's sheets, 13.07 editor's sheets,
Permission No. 214/1-64-K-05+41468
600 copies 63 - 008 - 65 First edition
63/i
•
