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angewandte Limnologie: Verhandlungen

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Modeling chemical water quality in reservoirs

Marc J. Zimmerman

To cite this article: Marc J. Zimmerman (1984) Modeling chemical water quality in reservoirs,
Internationale Vereinigung für theoretische und angewandte Limnologie: Verhandlungen, 22:1,
254-260, DOI: 10.1080/03680770.1983.11897298

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 Verh. lnternat. Verein. Limnol. 254-260 Stuttgart, Juli 1984

Modeling chemical water quality in reservoirs

~ARCj.ZD{MERMAN

With 2 figures in the text

Introduction
Interest in modeling water quality of reservoirs and lakes received its greatest impetus in the
1960 s with the explosion of public interest in the perceived deterioration of water quality result-
ing from s<realled cultural eutrophication. Papers presented here and at the colloquium following
this congress on the problems of eutrophication of Lake Geneva testify to the continuing im-
portance of research in this area.
Since "eutrophication" became a popular word, many of us as limnologists have earned good
livings capitalizing on justifiable fears about water quality problems associated with nutrient en-
richment and/o r pollution. In addition to innumerable field studies related to environmental
water quality, many different approaches to chemical water quality modeling have been de-
veloped to deal with eutrophication-related problems. Three major approaches to water quality
modeling can be identified: empirical regressions (i. e., loading models), chemical equilibrium cal-
culations, and ecosystem compartment models, as well as combinations among these. Along with
the variety of models available, data requirements vary widely and include field data, detailed labo-
ratory analyses, theoretical chemical thermodynamics coefficients, and biological rate coefficents.
Where data resources are insufficient, a good deal of educated guesswork may also be included.
This paper briefly examines the three broad classes of water quality models listed above. lt at-
tempts to consider some of the more persistent paradoxes and difficulties in model use, particu-
larly with respect to biogeochemical applications and interpretations. While many of the ex-
amples cited derive from lake studies, my main concerns are the implications for reservoir water
quality modeling and management.

Water quality models

The general acceptance of phosphorus as the nutrient most often limiting algal
growth, most often the culprit of cultural eutrophication, and most amenable to control
has led to its being a central target of water quality modeling efforts. Thus, while P itself
is not a problem, its causal relationships are of great concern. In this regard, P loading
and total P chlorophyll a relationships have been subjects of many empirical regression
or correlation studies since VOLLENWEIDER's (1968) seminal report.
Data requirements for these models include estimates of lake area and volume, nutri-
ent loadings, flushing and sedimentation rates, and measurements of total P and chlo-
rophyll a concentrations in surface waters. It is not unusual to have errors in excess of
100% associated with these values. The uncertainty generated by these potential sources
of error has rarely been examined (REcKHow 1979).
The assumptions upon which VOLLENWEIDER's equation (and other related models) is
based are worth mentioning when assessing its applicability to reservoirs:
l. Nutrient flushing, loading and sedimentation are constant through time.
2. Sedimentation is proportional to concentration.

0368-0770/84/0022-0254 $ 1.75
© 1984 E. Schweizerbart'sche Verlagsbuchhandlung, D·7000 Stuttgart l
 M. J. Zimmerman, Modeling chemical water quality 255

3. Stratification effects are not considered.

4. Outflowing nutrient concentrations are assumed equal to mean lake concentrations.
Needless to say, these assumptions are generally violated when applied to lakes as
well as reservoirs (DILLON 1974). In spite of making some fairly crude estimates of P
loading in lakes, JoNES & BACHMANN (1976) found a strong relationship (r = 0.89) be-
tween calculated total P and chlorophyll a and dose agreement with regression coeffi-
cients from other studies. However, they also found that data from impoundments did
not fit the chlorophyll a - total P relationship nearly as well as lake data, overestimat-
ing total P concentrations because of insufficient sedimentation rates. WESTERDAHL et al.
(1981) found that use of "VoLLENWEIDER-type analyses" could lead to classifying a par-
ticular reservoir in a range from oligotrophic to eutrophic.
For modeling chemical water quality relevant to multi-purpose reservoir management
requirements, empirical or semi-empirical methods fali short for several reasons (KRENKEL
& FRENCH 1982). Basically, their scale of resolution is too coarse. They are not intended
for use in examining fine details of water quality dynamics. By assuming a state of equilib-
rium with respect to a reservoir's hydrodynamics, biology, and chemistry, accurate short-
term predictions cannot be achieved. Furthermore, interactions between chemical and
biological constituents are not considered. Interna! nutrient loading is also ignored.
Nevertheless, in spite of their intensitivity, these methods do provide low-cost and fairly
accurate long-term predictions. Caution is advised w h en applying them to reservoirs.
Chemical equilibrium calculations have rarely been used exclusively in modeling
biogeochemical processes in lakes and reservoirs. The data requirements for a relatively
complete equilibrium description of an aquatic ecosystem are quite extensive and some-
what esoteric. Data needs for a description of even a relatively small system at equili-
brium include a large number of equilibrium constants and solubility products, as well
as analytical data. Many of these numbers are derived from experiments conducted
under highly specific, controlled conditions, whereas applications may be performed
for poorly defined natural environments. Effects of temperature and ionic strength may
have to be extrapolated in order to approach the range of expected environmental con-
ditions. There are also many different data sources from which to choose and values re-
ported may vary considerably, requiring discrimination among several alternatives.
Rather than develop a complete chemical equilibrium description, a more common
practice is to incorporate a limited number of chemical equilibrium calculations into an
existing ecosystem model. For example, the WQRRS (HEC 1975) model uses equi-
librium calculations only for pH-C02 equlilibria, the main purpose of which is to de-
termine the amount of co2 available for photosynthesis. LUM et al. (1981) add six in-
organic chemical variables to the WQRRS model in a chemical equilibrium reaction
subroutine. The resulting simulations model reasonably well most of the new variables,
the only major difficulty arising from inadequate field data for iron. HoFFMANN & EI-
SENREICH (1981) use the REDEQL2 model of MoREL & MoRGAN (1972) to simulate
variations in iron and manganese in the hypolimnion of Lake Mendota. By considering
effects of pH, pE, adsorption, and complexation, their modeling approach produces a
fairly detailed description of the dynamics of Fe and Mn in the system studied. How-
ever, a major drawback of this method is that the details of chemical speciation predic-
tions are largely unverifiable; there is no way of knowing with any degree of certainty
which dissolved complexes exist at any given time.
256 11. Chemical Limnology

For a number of reasons, limnologists have been loath to do more with equilibrium
calculations. A major reason for this timidity, I believe, is the necessity of reorienting
one's thinking away from the traditional biological view of limnological systems and al-
lowing physicochemical calculations to subsume some of the biological functions; i. e.,
giving organisms roles as "black boxes". In addition, it is often pointed out that (1) be-
cause solar energy inputs drive photosynthesis, a state of equilibrium is never achieved
in nature, and (2) thermodynamically favored reactions may be kinetically slow.
Perhaps that is why it has taken engineers (LUM et al. 1981) and chemists (STUMM &
MoB.GAN 1981; HoFFMANN & EISENREICH 1981) to make some of the frrst applications of
chemical equilibrium calculations to studies of water quality in aquatic environments.
However, unless coupled with a model which specifically treats hydrodynamic pro-
cesses, such as the LAKECOI (LUM et al. 1981) model, equilibrium calculations will
suffer from many of the same defects as regression or loading models. That is, they will
still fail to yield good short-term predictions which reservoir planners and operators can
use to prepare for potential water quality problems. For most water quality problems,
other than grossly polluted waters, short-term dynamics of relatively finely scaled pro-
cesses, such as winds, insolation, and high and low flows are critical for making deci-
sions. T o address such problems, models must be employed which explicitly treat the
fme resolution space-time processes responsible for the appearance of the water quality
problems under study.
The final category of model which I would like to consider is the ecosystem com-
partment model. U se of ecosystem models, in general, has been widely criticized (Purr
& DENMAN 1975). Due to their complexity, they tend to be less accurate in some of
their detailed predictions than are regression models, in general. In spite of their draw-
backs, they still are the accepted choice for use in reservoir water quality management
(KALcEVA et al. 1982). A prime utility of ecosystem models lies in allowing one to con-
sider hydrodynamic influences and spatial and temporal dynamics at a finer scale of re-
solution than the other models described.
As an example of ecosystem compartment models, I have chosen CE-QUAL-R1
(Environmental Laboratory 1982). Like LAKECOI, it is a derivate of the WQRRS
model. WQRRS and CE-QUAL-R1 are well-known and widely used for modelling
river and reservoir water quality in the United States. The major attribute of
CE- QUAL-R1 which makes it a popular model for reservoir water quality is the inclu-
sion of state-of-the-art hydrodynamics (.KB.EmEL & FB.ENCH 1982), enabling users to gen-
erate accurate temporal and spatial simulations of reservoir thermal structure as well as
dynamics of several water quality variables.
Data and labor requirements for use of a modellike CE-QUAL-R1 are extensive. At
present, the model simulates 34 physical, chemical, and biological water quality
variables. Data-base needs include initial conditions, morphometric coefficients, reac-
tion rates, and hydrometeorological and inflowing water quality time sequences. Miss-
ing data may have be estimated by various means including regression analysis, inter-
polation, literature examination, or scientific judgment. As is the case for the other
models described, the potential for error in generating data is great. Finally, the whole
model must be calibrated by varying coefficients in order to achieve a best fit to known
field conditions. Calibration is not unlike the practice of discarding oudier values when,
for some adequately rationalized reason, this can help improve agreement in a correla-
tion model. A few examples of output from CE-QUAL-R1 should serve to foeus on
Fig. 1. Development of simulated (P) and observed (O) anoxic conditions in DeGray Lake, Ar-
kansas, in 1979.

some of the strengths and weaknesses of ecosystem compartment models as they are
currently applied to chemical aspects of reservoir modeling.
Probably the single most widely accepted and important chemical indicator of water
quality is dissolved oxygen concentration. Oxygen is also an important variable to
model since it integrates biogeochemical and physical processes. Furthermore, effects of
individual processes on oxygen concentration can be studied separately. By incorporat-
ing hydrodynamic processes into a one-dimensional representation of a reservoir, it is
possible to examine, temporally and spatially, the development of anoxia and resultant
chemical phenomena. Reservoirs frequently experience anoxic conditions that develop
metalimnetically, not hypolimnetically, Fig. l depicts and compares the initiation of
simulated and observed anoxic conditions in the metalimnion of DeGray Lake, Ar-
kansas. Except for relatively minor details, the simulations match reservoir conditions
quite well. The ability to generate simulations of this sort is especially important to re-
servoir planners who may have to make decisions about outlet port locations for con-
trolling releases to maintain downstream water quality.
Fig. 2 presents simulations and observations of temporal changes in oxygen, man-
ganese, and sulfide profiles later in the same year. By and large, these simulations do a
reasonable job of tracking the dynamics of the variables considered. They also serve to
point out some of the difficulties and paradoxes with which one must deal when mod-
eling limnological systems with this approach. Both simulations and observations of
oxygen profiles exhibit similar trends. Dissolved oxygen concentrations increase with
time in the surface waters, while continuing to decrease in the hypolimnion. Such be-
havior is to be expected as cooling mixes and deepens the epilimnion, and the deeper
waters remain stratified.
Dissolved manganese and sulfide profiles, however, do not adhere to such reasonable
trends, nor do they follow accepted aquatic chemical theory. Unlike the simulations in
which manganese and sulfide concentrations decrease when oxygen is present, the data
values derived from field sampling decrease (to zero in the case of sulfide) then increase.
Moreover, both elements appear in the "dissolved" or reduced state, according to field
data, when oxygen concentrations in the epilimnion and hypolimnion are sufficient to

17 Verh.lnternat. Verein. Limnol. Bd.22

258 li. Chemical Limnology

10/30/79 11/27/79 12/11/79

60

,---
jJ
J
(p ' l
50

(
------- -----~
íp J (p
r

40h-
30
' ,_
l
t-O
' '\
'r-o
--' ---
l
l
l l
\ l ~o
20 l l \
l l
J
, ,l
l
l l
\0 l

o
o 10 o 10 12 o 10 12
OXYGEN, MG/L

50 -t ------~~, ..
rp t-p
40,.- .------------ ----L~---
---
.--,, ......------
1
30 J ;,
......-o
20
l
..................
... __ _ l

----------- -..,
l
' '---- -- -------
10

0~--~--L---~--~~

o 0.1 0.2 0.3 0.4 0.5 o 0.1 0.2 0.3 0.4 0.5 o 0.2 0.4 0.6 0.8
MANGANESE, MG/L

so r---.---,---.---,---,

íp
----,...;.---o
____
íp p

40

30

-o

o L---L---L---J---J-~
o 0.1 0.2 0.3 0.4 0.5 o 0.1 0.2 0.3 0.3 0.4
SULFIDE, MG/L

Fig.2. Comparison of simulated (P) and observed (O) proflles of oxygen, dissolved manganese,
an d sulfide on three days in late 1979.

cause their oxidation. Of course, "dissolved" is just an operational definition to describe

passage through a filter of known pore size.
Such inconsistencies obviously lead to questions about the validity of the field data as
well as of the model formulation. lt is quite likely that model simulations will never be
able to handle situations where data fluctuations defy rational analysis; data verification
 M. J. Zimmerman, Modeling chemical water quality 259

can only go so far. It is more probable, in this case, that the data should be questioned;
the analyses may have been spoiled by careless handling or some other unexpected
cause. Other possible factors rendering interpretation difficult are the low sulfide con-
centrations observed which are at the lower end of the detection limits reported by the
analysts; many of the values hover around 0.0-0.1 mg/1 sulfide.
In order to decompose into one dimension a three-dimensional system which
changes in time and space, one must, of necessity, lose some of the fine detail inherent
in observations of the real world. Variability is smoothed out as the model averages sys-
tem behavior into stable, comprehensive trends. Thus, the one-dimensional ecosystem
model, too, suffers from the scale of resolution problem; the degree of resolution of the
ecosystem approach falls somewhere between that of loading models and equilibrium
calculations, complicating the match-up between model predictions and sample ob-
servations made at a specific point in time and space.

Conclusions
In the brief space available, I have attempted to discuss various water quality modeling ap-
proaches as they pertain to reservoirs. One point that I have tried to emphasize has been the insen-
sitivity of these models to data variability as well as to violations of their own assumptions.
Within the context of their intended purposes and constraints, all the techniques seem capable
of producing reasonably good characterizations or simulations of the systems considered. Loading
and empirical regression models yield good predictions of chlorophylla concentrations which
may indicate the necessity of controlling nutrient inputs. Equilibrium calculations provide de-
tailed descriptions of biogeochemical events associated with eutrophication and, thus, can aid in
assessing some of the more diverse ramifications of water quality management. Finally, ecosystem
level models are particularly valuable for their ability to simulate operational conditions of reser-
voirs; they account for time-dependent behavior and the effects of hydrodynamics on physical,
chemical, and biological aspects of wat er quality.
We may actually view these approaches as a continuum, or hierarchy, potentially comple-
menting each other to yield a more temporally and spatially complete biogeochemical conceptua-
lization of an aquatic system. At the coarsest level of resolution lie the loading and regression
models. Next, fali the one-dimensional ecosystem compartment models which incorporate up-to-
date hydrodynamic simulation capability. At the finest level are chemical equilibrium calculations
which can provide highly detailed descriptions of system chemistry. No one modeling approach is
best for all possible applications. Having a spectrum of tools available will allow the analyst to
choose the best approach for a specific situation.
I have not intended to endorse any particular modeling approach, but rather have tried to in-
dicate that al! the models discussed can be used valuably as dictated by requirements for the ap-
propriate scale of resolution. I would also suggest that we may see no major denouements in the
future and that the best we may do in the field of water quality modeling, and perhaps, in limno-
logy in general, is to refine some of our already already adequate techniques, with respect to their
underlying assumptions and limitations.

Acknowledgment
The author thanks JAcK B. WAIDE for helpful discussions, advice, comment, and encourage-
ment during the preparation of this paper.

References
Dn.r.oN, P. J., 1974: A critical review of VOLLENWEIDEil's nutrient budget model and other related
models.- Water Res. BulL 10: 969-989.
260 li. ehemical Limnology

Environmental Laboratory, 1982: eE-QUAL-R1: a numerical one-dimensional model of reser-

voir water quality. - lnstruction Rep. E-82-1. USAE Waterways Experiment Station,
Vicksburg, Mississippi.
HEe (Hydrologic Engineering Center), 1975: Water quality for river reservoir systems. -No.
401-F2-L2100, U. S. Army Corps of Engineers, Davis, ealifornia.
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model for the variation of iron and manganese in the hypolimnion of Lake Mendota. - En-
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model.- EcoL Modelling 14: 95-123.
MoREL, F. M. & MoRGAN, J. J., 1972: A numerical method for computing equilibria in aqueous
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Author's address:
U.S. Army Engineers Waterways Experiment Station, Environmental Laboratory, P. O.
Box 631, Vicksburg, Mississippi 39180, U.S.A.