ELSEVIER

The Science of the Total Environment 180 (1996) 187-200

Modelling the long-term changes in stream, soil and

ground water chemistry for an acid moorland in the Welsh
uplands: the influence of variations in chemical weathering
M. Cristina Forti>*, Colin Nealb, Alice J. Robsonb
Insiituto

National da Pesquisas Espaciais - INPE, CP 515, Sao Jose dos Campos, CEP 12201-970. Sao Paula, Brazil
bInstitute of Hydrology,
Maclean Building,
Crowmarsh
Gifford,
Wallingford,
Oxon, OX10 888, UK

Received 30 June 1995; accepted 16 August 1995

Abstract
A long-term model of stream acidification, MAGIC, has been applied to an acidic moorland catchment, the Gwy,
in mid-Wales.This application has been used to examine the effects of variability of weathering on soil, groundwater
and stream water chemistry from 1844 to the present day and onwards to 2080 with a predicted acidic oxide reduction
of 60% in the future. The results show that weathering initially affects soil, groundwater and stream water chemistry
profoundly. Despite this, the results indicate that a simple two-layer (one soil and one groundwater
end-member)
model can still provide a good prediction of long-term stream water quality even when each soil and groundwater area
is heterogeneous in composition. The work provides support for the use of the lumped MAGIC model.However,for
the predictions to be applicable it is shown that it is critical that the relative contribution of waters and soil exchange
materials from the hydrochemically distinct regions within the catchment are adequately represented within the model.
This probably means that further field work is required to examine source area contributions.
Keywords: Heterogeneity;

Weathering;

Modelling;

Soil water; Groundwater

1. Introduction
Rain is involved in a complex but poorly defined
mixture of physical, chemical and biological processeswithin the soil and groundwater areas on
transport through catchments to generate a stream
flow response.These processescontrol the surface
drainage water chemistry and this critically im-

pacts on the vitality of stream ecology (Neal et al.,

1994).Major studiesover two decadeshave shown
that acidic deposition and land use change over
large tracts of acidic and acid sensitive soils have
affected stream water quality to the detriment of
stream ecology (Harriman et al., 1994). Consequently, major efforts are now being made on examining potential remedial solutions and in
assessing the potential

* Corresponding author.
0048-9697/96/$15.00
SSDI

control strategies.

0 1996 Elsevier Science B.V. All rights reserved

0048-9697(95)04935-G

of emission

and land

use

E8E

M.C.

Forti

et al. /The

Science of the Total

Central to planning new environmental management strategies is the development of reliable longterm bydrochemical
models which describe the
chemical transfers occurring in catchments. These
models are needed to predict the effects of changes
in atmospheric pollution and land use on the
various chemical stores within catchments and
hence on stream water chemistry. While the nature
of catchments is such that they are complex and
highly heterogeneous, in relation to soil and
groundwater chemistry, the models are relatively
simple in structure in that they lump together
such variability
(Christophersen
et al., 1993).
ile such lumping is necessary, given the
complex environment being described and the ease
sf overparameterising
model structures,
both
theoretical
and
practical
difficulties
arise
(Christophersen
et al., 1993; Neal, 1995). The theoretical difficulties occur because, in lumping, the
underlying equations that apply at any instance at
the local (e.g. micropore) scale are not necessarily
applicable at the time averaged or the large (e.g.
catchment) scale. Practical problems occur due to
the difficulties of adequately measuring chemical
variability and our inability in knowing how to integrate the variability into catchment average
values, on the basis of flux transfers, for use in the
lumped models. There may be missing processes
that account for acidity regulation in the soil and
groundwaters,
and field prograrnmes
are still
required to identify them (Neal, 1995).
Recent desk studies, following field measurement of chemical variability, have highlighted the
problems of spatial heterogeneity within catchment in terms of chemical variations within the
soil (Neal, 1992; Neal et al., 1994). These studies
describe the impact of variations
in the exchangeable cation fraction of the soil matrix which
is a critical control in determining the regulation of
soil water acidity by base cation supplies from the
soil surface and hence, on transfer to the stream,
stream water acidity. However, no adequate companion studies have been undertaken to examine
the effects of heterogeneous weathering reactions
in the soil and groundwater zones. This shortfall is
potentially an important omission as (1) variations
in chemical weathering probably provide the main
driving force for ensuring the high variations in
the exchangeable cation fractions of the soil ma-

Environmenr

180 (1996)

187-200

trix, as well as the soil water compositions;

(2)
chemical weathering is the major process by which
acidity, generated from atmospheric pollution and
from within
the soils, is neutralized.
Thus,
weathering
is the critical step in determining
stream ecology vitality.
In this paper, the question of the effects of
weathering heterogeneity on stream water quality
is addressed. This is done by the application of one
of the most widely used long-term acidification
models, MAGIC (Cosby et al., 1985a,b), to predict
the evolution of stream water quality, under different weathering regimes. The approach taken
parallels that of the earlier desk studies which describe the soil exchange variations. However, this
new study advances the earlier studies by directly
(1) relating the cation exchange variations to the
weathering process, (2) producing an application
for long-term simulation (the earlier studies took
no account of long-term changes in the chemical
stores within the soils) and (3) modelling a term for
groundwater
variability. The application is applied to the Gwy, the main headwater catchment
of the river Wye, a typical example of a British
upland
acid-moorland
system.
The results
presented here update earlier work described in
Robson et al. (1991) and Neal et al. (1992), in the
light of further data.
2. Study area
The Afon Gwy is the principle headwater tributary of the River Wye in the Plynlimon area of
mid-Wales. The area, 24 miles inland of the west
coast of mid-Wales,
forms part of a deeply
dissected plateau, much of it over 450 m, rising to
750 m on the summit, Pumlumon Fawr. The River
Wye drains to the south-east of this area. Stream
channels are irregular in profile, and the steps
often coincide with bands of resistant rock. The
river valleys tend to be deeply incised and are
separated by broad boggy interfluves. Thus, the
landscape of the Plynlimon is dominated by rolling
hills dissected by steep valleys. The Plynlimon
massif, on which Plynlimon lies, is composed of
lower Palaeozoic rocks (Ordovician
slates and
Silurian mudstones; Breward, 1990). Soil cover
consists of a mosaic of acid upland types including
peats, brown earths, stagnogleys and stagnopod-

M. C. Forti

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Science of the Total

201s. The summits of the Plynlimon Massif have

extensive areas of peat (depth around OS-l.5 m),
with grassy areas over the rock pavements from
which peat has been eroded. These peats probably
exert an important effect in the control and storage
of water (Knapp, 1970; Institute of Hydrology,
1972). Brown earths are present on the betterdrained, steeper slopes. Podzols and stagnopod201s have developed on the mid-slopes, and gleys
are present in the wetter, poorly drained areas of
boulder clay. In the valley bottoms, peat bogs are
common, with depths ranging between 0.8 and
1.2 m.
Drift deposits within the catchments are locally
derived and consist of a stony boulder clay found
mainly at the base of slopes, with shale or grit colluvium on the slopes themselves.
Plynlimon has a cool and wet maritime climate,
a result of its proximity to the Irish Sea and Atlantic Ocean. The Institute of Hydrology monitors
climate and rainfall inputs using a network of
automatic weather stations and ground level and
canopy-level rain gauges (Institute of Hydrology,
1976). Mean monthly temperatures are lowest for
February (l.SC) and peak in August (13.1C).
Rainfall averages around 2500 mm/year but varies
with altitude; the increase in average annual
precipitation, per 100 m of ascent, is estimated to
be 171 mm (Newson, 1976). Thus, the tops of the
catchments may receive around 25% more rain
than near the outflows. Sixty percent of rain falls
between October and March, with rain occurring,
on average, on 2 out of every 3 days over the
winter. Seventy-five percent of rainfall is of the
westerly synoptic type (Lamb, 1972) and 10% from
cyclonic circulation. Five percent of precipitation
falls as snow. Estimated annual evaporation for
the forested areas is between 29% and 32%, of
which around 25% occurs through interception
loss and 4-7%
through
transpiration.
Over
grassland areas, evaporational losses are estimated
to be around 15-17% (Hudson, 1988).
The Gwy catchment is 390 ha in area, with an
altitude range of 380-730 m. Average rainfall is
2424 mm/year and average runoff is 2083 mm/year.
The dominant vegetation on the Gwy catchment
is an acid Nardus-Festuca
grassland and it occupies some 56% of the catchment. This vegetation
characterises the long well-drained slopes of acidic

Environment

180 (1996)

187-200

!89

podzol soils. Hill top peats, which CQW~ 37% of

the catchment, support Eriophorum, C&ww
and
Vaccinium species and are highly acidic. The remaining podzol of the catchment (7%) comprises
improved grassland.
The episodic stream response of the Gwy catchment to rainfall is very flashy, influenced by the
thin soils and steep slopes. The hydrological response is promoted by a range of mechanisms. The
soils have high near-surface hydraulic conductivities which transmit throughflow
water quickly,
and macropore flow and overland flow have been
observed. Rainfall chemistry
is variable but
dominated by sea salts given the predominance of
westerly winds supplying rain from the Irish Sea
and North Atlantic Stream chemistry is also influenced by marine salts, but is highly damped relative to rainfall inputs (Robson,
1993). The
stream chemistry is generally dilute but is acidic
(pH - 4.8) poorly buffered and aluminium rich at
high flows (Reynolds et al., 1986). At baseflow, the
streams are well buffered (alkalinity
- 65 pequiv./l) and of fairly high pH (pH - 6.5). This response may be broadly explained in terms of the
varying contributions
from waters which have
been neutralized by bedrock, and from the acid
soil waters.
3. The modelling approach
3.1. The MAGIC model
MAGIC
(Model of Acidification
of Ground
waters In Catchments) is a model designed to examine the long-term changes in stream and soil
waters occurring in response to acidic inputs to the
system (Cosby et al., 1985 a,b). MAGIC assumes
that atmospheric deposition, mineral weathering
and cation exchange processes in the soil and
groundwater
zones are responsible
for the
observed stream water chemistry in a catchment.
A summary of the main processes represented in
the model are as follows:
(1) Strong acid anion concentrations
are
calculated for the soils and stream waters. Sulphate is assumed to follow a Langmuir isotherm
(Singh, 1984)
Es = E,
where E,

(S042-)/[C

+ (S0,2-)1

is the maximum adsorption

capacity of

190

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et al. /The

Science of the Total

the soils and C is half the saturation concentration. This allows for the lags which can occur between atmospheric deposition and the resultant
changes in stream water sulphate concentrations.
Chloride, nitrate and fluoride are assumed not to
have an adsorbed phase. Loss of ammonia and nitrate to the vegetation is included within the model
by estimating a percentage uptake.
(2) Cation exchange processes involving aluminium, sodium, calcium, magnesium and potassium
are assumed to be operative. The general form for
the exchange reactions between the ions IV+ and
N+ and their adsorbed states MX,,, and NX,, is
n Mm+ + m NX, = m N+ + n MX,,,
The total cation exchange capacity is then defined as
CEC=C
Exchangeable cations.
Equilibrium expressions for the cation reactions
are approximated by
SMUIN= ( N+ ) m En&( Mm+ ) n EmN
where Sr,,rVIN
is the selectivity coefficient

between M

and N; ( ) refers to the chemical activity of an ion

in solution, and E is the exchangeable fraction for
the appropriate ion on the soil complex, e.g.
EN = XKEC
with Xequalling the amount of adsorbed cation N.
(3) Aluminium concentrations
are assumed to
be in equilibrium with the solid phase Al(OH)s.
3 H+ + Al(OH)s(s)

= A13+ + 3 HZ0

(4) Allowance is made for dissolution of carbonic acids caused by the elevated Pco2 levels in
the soils, and for the effects of degassing as water
moves from the soils to the stream.
(5) It is assumed that there are constant longterm net inputs of base cations from mineral
weathering. These are difticult to measure and
must therefore be estimated.

Environment

180 (1996)

187-200

(6) Organics are modelled within MAGIC

a triprotic representation.

using

3.2. A two-layer MAGIC application

A two-layer version of MAGIC
(Jenkins and
Cosby, 1989) is used in the application, enabling
the simulation of two chemically distinct waters.
The top layer (here termed soil layer) represents
the lumped 0, E, B and C podzol horizons and the
peats of the area, whilst the bottom layer (termed
groundwater
layer) represents the deeper till
layers and other water stores such as groundwater
which produce baseflow. The flow proportions included in the model are those suggested by a twocomponent mixing approach outlined previously
(Neal et al., 1990): all the rain passes through the
soil layer and a portion of this percolate contributes directly into the stream, whilst the remainder is routed via the groundwater layer to the
stream.
Rainfall chemical inputs to the catchment were
taken as the rainfall flux adjusted for occult and
dry deposition of sea-salts and anthropogenic
sulphur compounds. Chloride is assumed to be
conserved within the catchment. Sulphate is currently assumed to be in near-equilibrium,
so that
the total sulphate input is equal to the stream output. Differences between the rainfall concentrations and the stream outflow
concentrations
(allowing for evaporation effects) are assumed to
result from dry and occult deposition, and these
components are incorporated within the adjusted
rainfall. For the sulphate input, this adjusted
value (56 pequiv./l) lies near modelled estimates of
total sulphate for the area (56 and 49 pequiv./l for
1987 and 1988, respectively; Robson, 1993). The
rainfall inputs for the period 1844-1984 were
varied according to the deposition
sequence
outlined by the Warren Spring Laboratory (1983).
The two layers in the model are conceptualised
such that different reaction mechanisms dominate
in each layer. The water from the soils is known to
be organic and aluminium rich and acidic, indicating that ionic exchange mechanisms and organic acid deprotonation reactions are the most
important
influence on soil water chemistry.
Water from the groundwater sources is rich in base
cations, but low in exchangeable cations, as it

M.C.

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Environment

180 (1996)

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191

comes from a high weathering zone. In this application, it is therefore assumed that ion-exchange
occurs in only the soil layer and that the ion exchange capacity of the groundwater
zone is small
enough to be neglected. On the other hand,
weathering
takes place predominantly
in the
groundwater zone.
The soil characteristics
used in the model are
given in Table 1. The depth of the soil (0.9 m) corresponds to the average combined depth of the 0,
E, B and C horizons and of the peats. The bulk
density and cation exchange of the soil is
calculated from field data for the Gwy soils (Robson, 1993). An average depth of 1 m is assumed for
the groundwater
zone. The groundwater
layer is
represented as being denser and of lower porosity
than the soil layer. The partial pressure of carbon
dioxide is assumed to be 30 times atmospheric
pressure for both the soil and the groundwater
zones (Neal and Whitehead, 1988). For the stream,
the PCO, is set to 2.5 times atmospheric pressure,
in line with average observed values for the
Plynlimon streams (Neal and Hill, 1994).
The concentration of organic acids in the two
MAGIC
layers is calculated from the average
observed dissolved
organic carbon, using a

calibrated conversion
formula from the programme of Schecher
and Driscoll
(1988),
ALCHEMI
(Robson, 1993): this conversion is
equivalent to assuming 18 carbon atoms per molecule of organics. The organic dissociation constants used in MAGIC are specified to be the same
in both the soil and groundwater
zones; they
match the default diprotic system values for the
ALCHEMI
programme.
Very little is known
about the sulphate
characteristics of the Gwy soils. The selected constants which describe the isotherms were chosen to
be typical of values used in earlier MAGIC applications to the uplands (Jenkins et al., 1988;
Whitehead et al., 1988; Jenkins and Cosby, 1989).
The same sulphate absorption isothe;m was used
in the two layers.
The model was calibrated to the present day
chemistry of the stream water, the soil water and
the groundwater
by adjusting weathering rates,
uptake rates and the initial soil base saturation
(Table 2). Given the limitations of the assumptions
required within the mixing approach, and the analytical error in the chemical measurements, a
perfect match between the modelled and the
observed chemical species in the stream is not

Table 1
Soil characteristics

Table 2
Calibrated
parameters
cation to the Gwy

used in the two-layer

Depth Cm)
Porosity
Bulk density (kg/m3)
E, (mequiv./kg)
C (mequiv./m3)
Cation Exchange Capacity
(mequiv.!kg)
Temperature
(C)
Pco, (atm)
%lo(KAl(oH)3)
Exchangeable
Na
K
Mg
Ca
BS

Cation

MAGIC

model

Soil layer

Groundwater
zone

0.9
0.55
800
3
70
45

1
0.35
1460
3
70
0. I

7.6
0.009
7.5

Top

Weathering
(mequiv.
m2/year) (negative
values = uptake)
Percentage uptake (of
the input to the layer)
Selectivity coefficients

7.6
0.009
9.5
Initial

(%) 1984:
0.10
0.00
1.90
4.8
6.7

values for the two-layer

base saturation

Ca
Mg
Na
K
NH.,
NO,
Ca
m
Na
K

layer

5
0
-11
0
98
15
-1.4
0.14
-1.35
-5.09
16.15

(1844)
Na
K
Mg
Ca

0.10
0.05
7.0
9.0

MAGIC

appli-

Bottom
layer
47
35
32
-15
0
80

192

M. C. Forti

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achievable. The alkalinity gives a good indication

of the overall composition of a water sample and,
whereas some deviations in individual determinants are acceptable, it is important that the
modelled alkalinity is accurate. The selectivity
coefficients
and initial base saturation
were
calibrated by running the model for the period
1844- 1984 so as to match present day base saturation characteristics
of the upper soils and peats
(Robson,
1993). Weathering/uptake
rates were
then adjusted for the two layers in order to match
stream and end-member chemistries as closely as
possible. Nitrate and ammonia were modelled by
calibrating catchment uptake to match the difference between the inputs and the outputs.
Weathering-inputs/biological-uptake-rates
were
used to match observed base cation concentrations.
Optimisation was performed manually, by adjusting parameters so as to match present day
stream chemistry as closely as possible.
The model has also been used to estimate future
changes in stream, soil and groundwater
components. This was done by continuing the already
calibrated run for 1844- 1984, using a linear future
sulphate deposition reduction scenario of 60% of
present day levels, starting in 1984 and being completed by the year 2084, and held at a constant
level thereafter.
The mean annual proportion
of soil and
groundwater
contributions
to stream water was
calculated to fix the flow pathways required for
the MAGIC
application. As MAGIC
bases its
predictions on knowledge
of all of the major
chemical determinants, not just alkalinity, it is also
necessary to have a full estimate of present day
end-member chemistries which can be used as a
guideline within
the model calibration.
The
approximate end-member chemistry of the soil
waters is expected to lie between the weighted
average of the grassland soil chemistry (incorporating the 0, E, B and C horizons) and the peat
water chemistry (Table 3). It is necessary to lump
together the soil and peat waters so as to restrict
the complexity of the MAGIC
application. Although there are chemical differences between
these waters, they are both very distinct from
baseflow. Table 3 shows the likely range that each

Environment

180 (1996)

187-200

of the determinants will fall within. The mean

flow-weighted
proportion
of soil water for the
Gwy is calculated to be 0.48 from the hydrograph
split.
3.3. Two- by two-layer application
To evaluate the soil heterogeneity within the
catchment as a function of variations in withincatchment weathering rates, the MAGIC model
was applied in a separate way from the two-layer
application described above. For this case, here
termed the two by two application, the MAGIC
model was applied using all the parameters set for
the two-layer application with the exception that
(1) the weathering rate was allowed to vary by
fixed amounts to cover a range spanning what
might be observe in the field. The weathering rates
set correspond to times three (M3) times two (M2),
divided by two (D2) and divided by three (D3), the
value obtained for the two-layer application.
(2) the exchangeable cations and base saturation
levels for the soil under pristine (1844) conditions
were varied to allow a model fit for the condition
where the cation exchange selectivity coefficient
was fixed to the values determined by the primary
two-layer application (Table 4). In other words, it
was taken that the thermodynamic
constants for
cation exchange were fixed and that any variations
in weathering rate would be reflected solely in
terms of changes in the soil water chemistry and
base cation levels.
From these results, a time series of water quality
determinands was constructed for the soil and
groundwater
areas. This was undertaken to illustrate the effects of variations in weathering
rates on their chemistry. The stream water chemistry for the mixed waters was then determined using
these end-member compositions. To represent the
largest potential variations that might be estimated
for the stream (relative to the two-layer application) the M3 and D3 compositions were mixed. In
order to do so, the mixing volumes for each layer
had to be estimated and this was done by
calculating a mixing volume for the two soil and
two groundwaters such that the alkalinity matched
the soil water, groundwater
and stream water
values for the two-layer model. This was required
as equal contributions
of each water type would

M.C.
Table 3
Rainfall, stream

water

Ca

et al. /The

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Environment

I80 (1996)

187-200

193

and soil chemistry

Rainfall

Na

Forri

Grassland

Peat

Stream

Oh

Eag

Bs

113
(0- 1026)
9
(O-89)

108
(43-222)

126
(48-209)

126
(74-209)

169
(83-470)

146
(109-217)

;:-29)

;:-29)

122
(61-174)
13
(2-30)

;:-26)

;;-91)

:;9-78)

:07_248)

:fO-23)

p:*-78)

:367-57)

p:3-70)

(5263-293)

:2:-80)

;O-46)
143
(8-1239)

70-28)
147
(42-338)

:o-11)
157
(48-310)

:o-9)
141
(54-254)

;l-16)
140
(51-237)

:o-18)
165
(101-282)

%208)

;;O-219)

1:2-W)

f;a-94)

(659-119)

40-26)
201
(68-451)
112
(O-625)

;;-1210)

&07)

$84-7.7)

;;-86)
4.2
(3.9-4.7)

&IO)
4.5
(4.2-4.8)

:09_164)
4.8
(4.4-5.0)

fo6_436)

(6250-117)

pzso-105)

f97_45)

lb-7)
34
(o-208)

:o-22)

;;-33)
403
(150-1500)

:p6-66)
15
(O-30)
261
(75-625)

:0-n)
3.9
(3.5-4.1)
145
(72-302)
0

;o-19)
5.2
(4.8-6.7)
6
(O-15)
4
(O-10)
176
(54-350)

Mg
K
Cl
so4

;:8-125)

NO3

PH

;30-4.7)

H
Al
DOC

;?6-2250)

Average values shown with ranges

sionless); from Robson (1993).

in parentheses;

units

are in pequiv./l

lead to major differences in chemistry compared to

the two-layer application: a situation which is not
allowable as the simulation must match the field
observation for the stream.
For the calculation, pH was estimated directly
Table 4
Base saturation
levels (BS%) and exchangeable
cation percentages for the soil under pristine conditions
(1844) for the two
by two-layer
model corresponding
to weathering
rates times
three (M3) and divided by three (D3)
BS
Soil water
M3
69.6
D3
9.09
Groundwater
M3
0.50
D3
0.01

Ca

Mg

Na

46.2
4.33

23.2
4.63

0.16
0.09

0.08
0.04

0.28
0.0

0.21
0.0

0.04
0.0

0.03
0.0

&4)
133
(32-292)
except

for aluminium

1144
(392-2750)
and DOC

(PmolIl)

and pH (dimen-

from the alkalinity because, on mixing of waters

from the different areas, pH (and H+) does not
behave conservatively whereas alkalinity, strong
acid anions and strong base cations do. The pH for
the mixed stream, soil water and groundwater was
calculated assuming the same PCO~ levels as in the
two-layer case.
4. Results
4.1. The two-layer case
The modelled chemistry of the stream, soil water
and groundwater together with the exchangeable
cation data for the soils compares well with the
observed values (Table 5) and previously published data (Robson et al., 1991; Robson, 1993).
Stream, soil and baseflow alkalinity are all well
simulated by the calibrated model. Individual
stream chemical determinands are well matched

M.C.

194
Table 5
Modelled
two-layer

Na
Ca
Mg
K
Cl
so4
NO3

PH
Alk
DOC

stream, soil water

model

Forti

et al. /The

and groundwater

Science of the Total

chemistry

Stream

Soil water

Groundwater

142.6
38.9
52.4
2.4
165.1
71.3
8.6
5.2
-8.3
30.0

138.1
24.5
38.8
3.5
165.1
76.8
14.8
4.2
-51.8
120.0

146.6
51.7
64.4
1.4
165.1
66.2
3.0
5.3
30.2
21.0

Environment

180 (1996)

and lie within 1 pequiv.il of the observed stream

chemistry, whilst for the soil layer, modelled soil
water concentrations
lie inside the observed
ranges. For the groundwater,
the modelled concentrations are also satisfactory.
The time trends of reconstructed soil, ground
and stream water chemistry from 140 years ago,
that is pre-acidification, up to 2084, are shown in
Fig. 1. The alkalinity shows a decline from 1844 to
the 1980s and recovery thereafter. Initial recovery
is fast and is followed by a very gradual long-term
improvement in alkalinity.
The soil, groundwater and stream alkalinity approximately parallel one another throughout the

for the

ALKALINTR

30

'\

PH

'.\

"\.._. c" '.

-SO
1844

1884

1924

1964

2004

2044

2084

SULFATE

CALCIUM

CI,.

1844

-----k

\._

1924

1884

1964

I1

1.

2004

2044

2084

MAGNESIUM

BSh
15-

187-200

..
.\
-..\

lo-

.\

..,_. *.l

-.------

57

1844

STREAM

Fig. 1. Time trends of reconstructed

Base Saturation
(%) and pH) from

-..-..-

soil, ground and stream

1844 up to 2084.

.-

SOIL WATER

water

chemistry

I
1884

1924

1964

__- - - - - _

(Alkalinity,

2004

GROUhTI

Ca, SO,

2044

2084

WATER

and Mg

in mequiv.il,

M.C.

Forti

et al. /The

Science

of the Total

modelled record. Stream pH falls rapidly as deposition increases in the 1950s levels out in the
1980s and then rises in the future in response to
increase followed by decrease in atmospheric deposition. The stream chemistry follows a similar
pattern to the soil and groundwater,
but the pH
variations are greater owing to the lower partial
pressure of carbon dioxide in the stream. As a consequence, CO2 degassing occurs as water moves
from catchment to stream, and the pH of the
stream is not bounded by the two end-member pH
values, especially at higher pH levels. Sulphate
concentrations in the stream, soil and groundwater
change in line with the assumed changes in sulphate deposition. The groundwater takes longer to
adjust to changes in sulphate concentration
because it is replenished from the soil and is therefore
only indirectly linked to the rainwater. The stream

Environment

180 (1996)

187-200

195

concentration represents a direct mix of the soil

and groundwater.
Predicted future sulphate concentrations decrease in both the soil and groundwater,
with
a reversal
in the sulphate
concentration
gradient between the soil and
groundwater.
Modelled groundwater
sulphate
concentrations are lower than in the upper soils
for the period prior to 1970. In future years, sulphate concentration in groundwater
takes longer
to decline than in the upper soil water.
4.2. The heterogeneous

two- by two-layer

case

The effect on soil and groundwater chemistry of

varying weathering rates is very large. However,
the shape of the time series patterns broadly
follows that described for the two-layer case(Fig.
2a-c). In detail, there are some deviations in pattern. For example, in the case of alkalinity, the

ALKALINITY

(al
40

.._

SOIL

---_._

\V;\TER

-.
180-

-. ., ,,... ...... .. ... ..,.....

, .______--

,, GROUND

----WATER

. . . . ..,,,,,.,.,,......... ......

120-

M3

M2

Fig. 2. Time trends for the two-layer

MAGIC
model for different
by three (D3) and divided by two (D2). (a) Alkalinity
(mequiv./l)
(mequiv./l)
and Base Saturation
(%).

D2

-..

D3

TWO

weathering
rate values:
and pH; (b) Magnesium

LAYER

times three (M3), times two (M2), divided

and Calcium (mequiv./l)
and (c) Sodium

196

44. C. Forti

et al. /The

of the Total Environment

Science

(b)

180 (1996)

187-200

MAGNESIUM
80 -

,, -\
,,

60 -

,I
__,

.:

,-.

,*

.-

,/..

. . ,,...... -.._,,,.,,...

\ SOIL
*\
..
:
.
..., \ 1

WATER

1~~~,,~,~-~,~

.,,,,,,_._,................
.

.,_.._
--------.._..
_.-..-.._.__,
207.
1844

,
,884

,
1924

,
1984

,
2004

2044

2084

CALCIUM
14Oj
80

,*-.

..

L
\

SOIL

,--a_

(lo

___-----,._. ...
,.

----____

--

M3

-\

WATER

M2

.,, .,.,.._...

80 i

r-

D2

-..

. ...,
..,

...

. ..-----I

GROUND

D3

WATER

TWO LAYER

SODIUM
,42 ___^--------___,----..--.---~

----.-__SOIL

,40

.._......

. . . . . . .._....

____

104 GROUND

WATER
158 _

._,_ ,,~~,~,,,,,,,,,,,_,,_,_,,,,.,,

952 -

--

M3

....

M2

D2

Fig. 2. Continued.

WATER

. ..--- . . . . . .._........_........................

-..

D3

lW0

LAYER

M. C. Forti

et al. /The

Science

of the Total

time of minimum alkalinity varies according to the

weathering rate, the position occurring earlier for
the lower weathering rates. For both the soil and
groundwaters, the higher the weathering rate, the
higher the alkalinity and base cation concentrations, released by weathering, and the lower the
pH. For the soil, where there is a significant cation
exchange fraction on the soil matrix, the exchangeable base cation levels increase as weathering increases (Fig. 2~).
STREAM

142.0

___.__---__.___l--.-..--

.___,________

Environment

180 (1996)

197

187-200

With regards to the stream water composition,

the effects of mixing the M3 and D3 soil waters
and groundwaters under the condition that the
mixed waters matches the 1984 alkalinity and pH,
is such as to systematically lower the pH and the
alkalinity, calcium and magnesium concentrations
under the pristine and future times relative to the
1984 value (Fig. 3). The deviations increase both
backwards and forwards in time around the 1984
point. Despite this, there is a very close corWATER

_----

SODIUM
141.0 -

TWO LAYER

Fig. 3. Time trends for stream water chemistry

mequivA
except for pH.

MODEL

for the two-layer

----and two-

TWOBYTWOLAYERMODEL
by two-layer

model

from

1844 to 2084. Units

are

198

M.C.

Forti

et al. /The

Science

of the

respondence to the two-layer and the two- by twolayer models; the results are the same, for practical
purposes.

Total Environment

180 (1996)

187-200

Table 6
Calibrated
parameters
values for the MAGIC
the recalibrated
two-layer
model

5. Discussion
The results presented here show that variations
in weathering rate will have a very strong influence
on soil and groundwater
chemistry. Changes in
weathering rate change cation supplies to the soil
solution.
Thus increasing
or decreasing
the
weathering rate provides corresponding
increases
or decreases in base cations and alkalinity.
In nature, there is a large variation in soil and
groundwater compositions and, in part, variations
in weathering clearly can have a substantial influence. Despite the heterogeneity, the integrated
value, characterized by the stream chemistry, indicates that, volumetrically, the extremes observed
in the soil and groundwater
areas may well have
little influence on the modelled values as they
counterbalance each other out. For this reason, it
may well be argued that there is no need for undue
effort in trying to match models to include these
extremes. Furthermore,
if one tries to recalibrate
the two-layer model using weathering rates higher
or lower than the optimised value, it becomes
more and more difficult to fit the averaged base cation levels. Thus it seems that the model has provided a means of estimating the gross weathering
rate reasonably well.

STREAM

Weathering
(mequiv.
m*/year)
(negative
values = uptake)
Percentage uptake (of
the input to the layer)
Selectivity

coefficients

Ca
Mg
Na
K
NH,
NO,
K
Ca
Mg
Na
K

Initial

Top layer

Bottom
layer

18.7
18.0
3.1

11.5
5.5
5.5

98
15

0
80
6

of

-1.9
-0.19
3.01
-1.76

base saturation

W44)

42.21
0.11
0.10
18.0
25

Na
K
Mg
Ca

However, complacency must not set in. The

application of the model made here has been
undertaken on the basis of accurately sampled soil
exchangeable cations and representative
soil
waters together with a firm hydrograph split of soil
and groundwater
types. However, there is considerable uncertainty over what the contributions
from the soils are, both in terms of their average
chemistries and the volumetric fluxes as shown by

WATER

5o1

application

TWOLAYER

--___

Fig. 4. Modelled
predictions
for Alkalinity
(mequiv./l)
two-layer
construct where the catchment is represented
by three (D3) two-layer
calibration.

TWO

BY TWO LAYER

_..-.._

TWO

LAYER

RECALIBRATED

and pH for the case where the stream water is modelled on the basis of the
as a straight average of the weathering
rate values times three (M3) and divided

M.C.

Forti

et al. / The Science

Table I
Modelled
stream, soil water and groundwater
quiv./l) for the year 1984 and exchangeable
saturation
(%) for the years 1984 and 1844
Stream
Na
Ca
Mg
K
Cl
so4
NO3

PH
Alk
1984
BS%
Ca
Mg
Na
K
1844
BS%
Ca

water

140.1
39.4
53.7
2.8
165.1
69.0
10.9
5.2
-8.6

of the Total Environment

chemistry
(pecations and base

Soil water

Groundwater

137.5
33.8
51.0
3.5
165.1
77.0
14.8
4.3
-30.8

145.6
50.9
59.4
1.4
165.1
52.3
3.0
5.3
37.3

27.4
19.6
7.7
0.07
0.07
43.2
25
18
0.11
0.1

Mg
Na
K

Robson (1993). For example, Fig. 4 shows the

modelled predictions of alkalinity and pH for the
case where the stream water is modelled on the
basis of the two-layer construct where the catchment is represented as a straight average of the D3
and M3 values. The basic information on the parameters set and data tit for this application are
given in Tables 6 and 7. The results show a very

Table 8
Adsorbed

cations

Adsorbed

ratio

ratio

values calculated

for the different

weathering

I80 (1996)

199

187-200

different pattern from the two-layer application.

This is the case even though the results would
match baseflow, stormflow
and average stream
water chemistry. On this basis, and from previous
findings (Hooper and Christophersen,
1992), it is
important that sound measurements are obtained
to characterise the contribution
of the different
types of water. Furthermore, while one type of heterogeneity has been examined here, that associated
with variations in weathering rate, the full heterogeneity of the system may well be much more complex. For example, from the previous work of Neal
et al. (1994), the variations in the adsorbed cation
ratios of soil were shown to be very large indeed.
While the range of values estimated in this study
is large (Table 8) it is an order of magnitude or
more smaller than that observed in the field by
Neal et al. (1994).
The actual heterogeneity of the system may well
be much greater than that mimicked in this paper.
Other influences such as variation in the soil selectivity coefficients and variations in weathering
rates for individual cations may well come into
play. Also, the weathering rate variations that
occur within the catchment may be larger than
that modelled, and this too could contribute to the
differences observed.
6. Conclusions
This study indicates that
ing rate can critically affect
and groundwater chemistry.
gration of the variability

variations in weatherthe variations in soil

Despite this, the intewithin a simplified

rates

D3

D2

Two-layer

M2

M3

MAX

NaiCa
Na/Mg
Ca/Mg
Al/Na3
A12/Ca3
A12/Mg3

0.00088
0.00163
1.85
312 057
66.8
423

0.00079
0.00159
2.00
277 325
38.8
309

0.00057
0.00142
2.50
187 585
6.48
101

0.00033
0.00112
3.41
37 624
0.0499
1.97

0.00026
0.00088
3.41
2791
0.00014
0.00537

3.4
1.8
1.8
112
4.8 x 10
7.9 x lo4

The MAX Ratio

for the adsorbed

listed in the table provides a measure of the scale of variability.

cation ratios across the range of weathering.

It is the ratio of the maximum

ratio

and minimum

values

200

M.C.

Forti

et al. / The Science of the Total Environment

modelling structure may well be valid provided

that the relative inputs of the various distinct
chemical regions are taken into account. However,
it remains critical that the relative contributions of
inputs are established by field observation and in
this sense the present work adds to the value of the
chemical mixing approach.
Acknowledgements
One author, M.C. Forti was in receipt of a grant
from Conselho National de Pesquisas - CNPq
(National
Research Council Brazil; Proc.
460073/95-8) which gave the opportunity to do this
work.
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