Water Research 36 (2002) 1286–1296

Methods for preparing synthetic freshwaters

E.J. Smitha, W. Davisonb,*, J. Hamilton-Taylorb
a
Windermere Laboratory, Centre for Ecology and Hydrology, Far Sawrey, Ambleside, Cumbria LA22 0LP, UK
b
Environmental Sciences Division, Institute of Environmental and Biological Sciences, Lancaster University, Lancaster LA1 4YQ, UK
Received 30 November 2000; received in revised form 7 June 2001; accepted 16 July 2001

Abstract

Synthetic solutions that emulate the major ion compositions of natural waters are useful in experiments aimed at
understanding biogeochemical processes. Standard recipes exist for preparing synthetic analogues of seawater, with its
relatively constant composition, but, due to the diversity of freshwaters, a range of compositions and recipes is required.
Generic protocols are developed for preparing synthetic freshwaters of any desired composition. The major problems
encountered in preparing hard and soft waters include dissolving sparingly soluble calcium carbonate, ensuring that the
ionic components of each concentrated stock solution cannot form an insoluble salt and dealing with the
supersaturation of calcium carbonate in many hard waters. For acidic waters the poor solubility of aluminium salts
requires attention. These problems are overcome by preparing concentrated stock solutions according to carefully
designed reaction paths that were tested using a combination of experiment and equilibrium modeling. These stock
solutions must then be added in a prescribed order to prepare a final solution that is brought into equilibrium with the
atmosphere. The example calculations for preparing hard, soft and acidic freshwater surrogates with major ion
compositions the same as published analyses, are presented in a generalized fashion that should allow preparation of
any synthetic freshwater according to its known analysis. r 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Synthetic; Freshwaters; Soft; Hard; Acid

1. Introduction Freshwaters have such diverse compositions that there

When performing experiments relevant to natural
waters, it can be advantageous to use a medium with the
same major ionic composition as the natural water being
studied, but without the other natural components, such
as trace components, colloids and organic substances.
Such an approach has been used for many years in
understanding the chemistry of seawater [1] and for
preparing pH buffer solutions in seawater media. As
seawater has a reasonably constant composition a single
recipe can be used, allowing a standard protocol for the
preparation of its synthetic analogue to become
established [2].
*Corresponding author. Fax: +44-1524-843854.
E-mail addresses: esmith@ceh.ac.uk (E.J. Smith),
w.davison@lancaster.ac.uk (W. Davison).
can be no simple single protocol for their preparation
and consequently simple salt solutions such as NaNO3
are often used instead [3]. Other solutions which may be
used as surrogates for freshwaters are the commercially
available certified reference materials (CRMs) for
natural waters. Examples may be obtained from the
European Commission’s BCR programme in Europe
and NIST in the USA. Methods for preparing these
CRMs have been published in the open literature (for
example, major elements in synthetic freshwater (CRMs
398 and 399) and nitrate in synthetic freshwater (CRMs
479 and 480) [4]. However, these methods do not
describe how to produce synthetic freshwaters of any
desired chemical composition. This paper presents
methods for producing synthetic surrogates with the
same major cation and anion compositions and ionic
strengths as their natural counterparts. Although the
complicated interaction of rain water with the terrestrial

0043-1354/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 3 - 1 3 5 4 ( 0 1 ) 0 0 3 4 1 - 4
 E.J. Smith et al. / Water Research 36 (2002) 1286–1296
environment produces a wide variety of fresh water
compositions, they may be broadly characterized as
hard, soft or acidic waters. In this paper we system-
atically consider the common problems that are
presented in preparing a solution of synthetic fresh-
water, irrespective of its composition. Recognising that
there can be no ‘‘standard’’ chemical composition of
lake water, protocols are developed and presented for
designing recipes to produce freshwaters of any required
chemical composition.
Three lakes were selected to represent freshwaters
with different chemical compositions. Esthwaite Water,
Cumbria [5] and Rostherne Mere, Cheshire [6] are used
as examples of circumneutral soft and hard waters,
respectively and Seathwaite Tarn, Cumbria [7] is used as
an example of an acidic water. Esthwaite Water is a
small, eutrophic lake in the English Lake District with a
high biological productivity and a seasonally anoxic
hypolimnion [8]. The high productivity of Esthwaite
Water is partly attributed to its location in a shallow
valley with relatively rich alluvial soil [5]. Numerous
studies of Esthwaite Water have resulted in comprehen-
sive descriptions of its chemical and biological char-
acteristics [5].
Rostherne Mere is situated in the Shropshire–
Cheshire basin in England [9]. It is a seasonally
anoxic, hard water lake, dominated by calcium carbo-
nate with a well known major ion chemistry [6]. The
high alkalinity of Rostherne Mere may be attributed to
the groundwater and slow surface drainage from a
catchment of glacial drift which contains evaporites and
limestone sources. Seathwaite Tarn is a small, oligo-
trophic, acid, upland reservoir in the English Lake
District. The reservoir is surrounded by sphagnum and
peat bog, and its inflow comes from streams draining a
mountainous area of 465 ha consisting mainly of grass-
land.
The production of a synthetic inorganic surrogate of a
freshwater is not a straightforward matter on two
counts. Firstly, dissolving several salts in one solution
tends to produce common ion effects. These effects occur
when the dissolution of an inorganic salt causes the
solution to become supersaturated with respect to
another salt resulting in the precipitation of a new solid.
For example, the dissolution of calcium and sulphate
salts in the same solution tends to lead to super-
saturation with respect to calcium sulphate and its
possible precipitation. The other main difficulty is that
the synthesis of both soft and hard waters requires the
dissolution of calcium carbonate which is a relatively
insoluble salt. The dissolution problems are exacerbated
by the fact that some hard waters commonly approach
saturation or oversaturation with respect to calcite (and
other calcium mineral phases). Specific procedures have
been developed to create conditions which are conducive
to rapid dissolution of calcium carbonate.
1287
The basis of devising a synthetic freshwater recipe is
to (a) examine systematically its analytically determined
chemical composition to determine the salts required
and (b) arrange the salts into groups to prevent
incongruent solubility and produce three or four
concentrated ‘‘stock’’ solutions depending on the final
water composition (soft and acidic waters require three
solutions, hard waters require four). For the sake of
clarity, the stock solutions will be numbered and
prefixed by S, H or A to denote which water they refer
to (soft, hard or acid water, respectively). The stock
solutions are made up (using special procedures where
required to ensure complete salt dissolution) and mixed
together to produce the final solution. Since the
production of some stock solutions results in solutions
with excess CO2, equilibration with the atmosphere has
to be re-established by bubbling the final freshwater
solution with air prior to use.
1.1. Designing a synthetic soft or hard freshwater recipe
The first requirement for producing a recipe is to list
the major ion composition (molar units) of the required
freshwater (e.g. Tables 1 and 2). Most compositions
include Mg2+, Ca2+, Na+ and K+ and Cl , SO24 and
HCO3 . Additional components may be NH+ 4 -N and
NO3 -N, depending on their importance to the user
requirements. As CO23 is present at low concentrations
for most natural waters in the pH range 7–8, the
frequently measured alkalinity for soft and hard waters
is assumed to be equal to the concentration of the
HCO3 ion. Since solutions are electrically neutral, the
sum of all the cationic charges should equal the sum of
the anionic charges. The charge balance should therefore
be checked to see whether this condition is satisfied or
not. This is most conveniently done if concentrations are
expressed in equivalents (mol L 1  charge). For the
component salt solutions the charges must balance
perfectly. However, as the published composition of a
water is usually determined analytically, the concentra-
tions of cations and anions often do not balance exactly,
as is evident from Table 1, columns 3 and 7, and Table 2,
column 3 for the examples shown. Small adjustments
must be made to the concentrations of some of the
cations and/or anions to achieve perfect balance. First
select some value of total microequivalents (approxi-
mately midway) between the two cation and anion sums.
Small adjustments should then be made to the anion and
cation concentrations until their sums are both equal to
this midway point. The biggest adjustments should be
made to the ions present at the highest concentrations
with small adjustments to minor components. The
individual cation and anion equivalents shown in the
Esthwaite Water example were adjusted until
SCZ+=SAZ =925 meq L 1. These adjustments are
shown by Table 1, columns 4 and 5.
1288 E.J. Smith et al. / Water Research 36 (2002) 1286–1296

Table 1
The major ion composition of a typical soft water and acid water

Esthwaite Water Seathwaite Tarn

Published concn. Adjustment Balanced concn. Published concn. Adjustment Balanced concn.
(meq L 1) (meq L 1) (meq L 1) (meq L 1)
1 1 1 1
mmol L meq L mmol L meq L

Na+ 249 249 +1 250 193 193 193

Ca2+ 263 526 +4 530 28 56 56
Mg2+ 60 120 120 33 66 66
K+ 25 25 25 9 9 +1 10
Al3+ 6.5 19.5 1.5 18
H+ +7 7
SCZ+ 920 +5 925 343.5 350

Cl 280 280 280 228 228 +2 230

NO3 31 31 1 30 36 36 36
SO24 115.5 231 1 230 42 84 84
HCO3 386 386 1 385
SAZ 928 3 925 348 350

Table 2
The major ion composition of a typical hard water

Rostherne Mere

Published concn. Adjustment Balanced concn.

(meq L 1) (meq L 1)
1 1
mmol L meq L

Na+ 670 670 5 665

Ca2+ 1230 2460 10 2450
Mg2+ 410 820 5 815
K+ 110 110 5 105
SCZ+ 4060 25 4035

Cl 680 680 +5 685

NO3 100 100 100
SO24 600 1200 +10 1210
H2PO4 30 30 30
HCO3 2000 +10 2010
SAZ 4010 +25 4035

1.2. Procedure for selecting the salts for the soft water
recipe
Once the chemical constituents have been balanced,
the salts required may be calculated. It is important to
avoid using low solubility salts (for example calcium
sulphate and magnesium carbonate) as these are difficult
to dissolve and may precipitate out of solution. The
solubility information provided in Table 3 may be used
to assist in the choice of suitable salts. More exhaustive
solubility data are available [11].
The following section outlines the steps required to
select the appropriate salts at the correct concentration
for the synthetic freshwater recipe for Esthwaite Water
(Table 4). No completely general protocol can be
provided because of the diversity of possible composi-
tions, but the principles are illustrated. CT denotes the
sum of the carbonate components (HCO3 +CO23 ).
(i) Use the measured concentration of Mg2+ to
calculate the amount of MgCl2 required
(120 meq L 1).
 E.J. Smith et al. / Water Research 36 (2002) 1286–1296 1289

Table 3
The solubilities of inorganic salts [10]a

Anion O2 OH Cl CO23 HCO3 NO3 SO24

Na+ dec. 109 36 21 9.6 87 19.4

K+ dec. 112 34.7 112 22.4 31.6 11.1
Mg2+ ss 0.0009 54.2 ss F 70 33
Ca2+ dec. 0.156 74.5 ss F 129 0.21
Al3+ ss ss 70 dec. F F 63 38
NH+4 37 12 192 75
a
ss denotes sparingly soluble, dec. denotes decomposes. The solubilities in the table are given as 100 times the mass (g) of anhydrous
solute per unit mass of water (g), at 201C, unless otherwise stated i.e. 100  g g 1.

Table 4
Matrix of salts used and summation of major cations and anions for Esthwaite Water and Seathwaite Tarn

Esthwaite Water Seathwaite Tarn

1
meq L Cl NO3 SO24 CT SC Z+
Cl NO3 SO24 SC Z+

Na+ 230 20 250 73 36 84 193

Ca2+ 160 30 a
340 530 56 a
56
Mg2+ 120 a
120 66 66
K+ 25 25 10 10
Al3+ 18 18
H+ 7 7
SAZ 280 30 230 385 925 230 36 84 350
a
Insoluble salt.

(ii) The balance of Cl required in the solution is
supplied by adding CaCl2 (160 meq L 1).
(iii) Use the measured concentration of NO3 to
calculate the amount of Ca(NO3)2 required
(30 meq L 1).
(iv) The balance of Ca2+ required in the solution is
supplied by adding CaCO3 (340 meq L 1).
(v) Use the measured concentration of K+ to calculate
the amount of KHCO3 required (25 meq L 1).
(vi) Use the measured concentration of SO24 to
calculate the amount of Na2SO4 required
(230 meq L 1).
(vii) The balance of Na+ required in solution is supplied
by adding NaHCO3 (20 meq L 1).
The table should be checked upon completion to
ensure that the charge balance has not been violated.
It is convenient to make synthetic lake water by
preparing separate concentrated stock solutions which
are then mixed in appropriate volumes to produce one
solution of the required composition. Therefore, once
the required salts are known they should be grouped
together in compatible combinations into the minimum
number of stock solutions. Table 3 may be used to avoid
placing incompatible salts in the same stock solution,
which may result in the solution becoming oversaturated
with respect to relatively insoluble salts. Tables 5
and 6 summarize the stock solutions used for Esthwaite
Water and a typical hardwater, Rostherne Mere. The
potential of the 1000  concentrated stock solutions to
exceed saturation limits was checked using the geo-
chemical equilibrium speciation code MINTEQA2
version 3.11 [12]. The model output indicated that it is
necessary to use 3 stock solutions for the soft water
recipe and 4 for the hard water, as at these higher
concentrations a separate solution of MgSO4 is required
to avoid precipitation. If placed in solution 1 or 2, an
insoluble precipitate of CaSO4 may form and if placed in
stock solution 3, MgCO3(s) may form. Calcium carbo-
nate is only sparingly soluble and consequently difficult
to dissolve. The calcium carbonate is therefore placed in
its own separate stock solution for both soft and hard
freshwater recipes (Tables 5 and 6). A separate
procedure was developed to ensure its reliable dissolu-
tion (Experimental section). Tables 5 and 6 show the
required concentrations of each ion for each salt for the
soft and hard water recipes in mg L 1 and the mass of
salt required to make up an appropriate volume of each
stock solution.
Stock solutions S1, S3, H1, H3 and H4 are prepared
at much higher concentrations than are required for the
completed lake water for several reasons. Firstly, it is
1290 E.J. Smith et al. / Water Research 36 (2002) 1286–1296

Table 5
Recipe for Esthwaite Water (Cumbria)
1
Stock solution meq L Final required concentration (mg L 1) Mass (g) of salt per volume Concn. factor
of MilliRo water
CZ+ AZ

S1 1L
MgCl2
6H2O 120 1.458 4.254 12.168
CaCl2
6H2O 160 3.206 5.672 17.500  1000
Ca(NO3)2
4H2O 30 0.601 1.860 3.542

S2 5L
CaCO3 340 6.814 10.201 0.0936  1.1

S3 1L
Na2SO4 230 5.288 11.046 16.334
KHCO3 25 0.977 1.525 2.502  1000
NaHCO3 20 0.458 1.220 1.678

Table 6
Recipe for Rostherne Mere (Lancashire)
1
Stock solution meq L Final required concentration (mg L 1) Mass (g) of salt per volume Concn. factor
of MilliRo water
CZ+ AZ

H1 1L
CaCl2
6H2O 685 13.727 24.285 7.491  100
Ca(NO3)2
4H2O 100 2.004 6.200 1.181

H2 5L
CaCO3 1665 33.367 F 0.458  1.1

H3 1L
KHCO3 75 2.932 F 0.751
KH2PO4 30 1.173 2.910 0.408  100
NaHCO3 270 6.207 F 2.268
Na2SO4 395 9.081 18.971 2.805

H4 1L
MgSO4
7H2O 815 9.904 39.143 10.044  100

much easier and more accurate to weigh out several
grams of each salt rather than only a few milligrams.
Secondly, the high concentrations of ions in the stock
solutions ensure that they are relatively stable and free
from contamination. This enables stock solutions S1, S3,
H1, H3 and H4 to be made up in advance. Suitable
storage in a cool place out of direct sunlight will ensure
that they keep indefinitely. Finally, only a few millilitres
of each solution is required to make up the complete
synthetic lake water and therefore stock solutions S1,
S3, H1, H3 and H4 may be used for many preparations.
In the two examples given, stock solutions S1 and S3
were prepared at 1000 times the final required concen-
tration for soft water (Table 5) and stock solutions H1,
H3 and H4 were prepared at 100 times the final required
concentration for hard water (Table 6). At 100 times the
final required concentration, sufficiently high masses of
salts are used to ensure easy weighing and good
accuracy, but still avoid exceeding the solubility of the
salts. Table 8 outlines the volumes of stock solutions
required to make the soft and hard waters.
Owing to the problems of dissolving calcium salts,
stock solutions S2 and H2 form the bulk of the synthetic
soft and hard waters (i.e. 4545 mL of stock solution S2
or H2 for 5 L of synthetic freshwater). It is made up at
1.1 times the final required concentration (as opposed to
 E.J. Smith et al. / Water Research 36 (2002) 1286–1296 1291

1000  or 100  for the other stock solutions) to ensure
that only a small mass of CaCO3 needs to be dissolved
and to allow for dilution resulting from the addition of
the other stock solutions.
1.3. Designing a recipe for an acidic freshwater
The general procedure for calculating the recipe for an
acidic water is similar to that used for soft and hard
waters. The essential differences will be highlighted.
Aluminium and hydrogen ions are more important in
acidic solutions and must be included in the list of major
ions. As very acid solutions (pHo5) contain effectively
no HCO3 , carbonate components can be omitted from
the basic recipe. Table 1 shows the published composi-
tion of Seathwaite Tarn water [7] and the final balanced
concentration after adjustments have been made. The
H+ ion may be used to balance the sum of the charges
for waters with pHp5, especially as H+ concentrations
are difficult to measure accurately with a pH electrode
[13,14]. Alternatively, if pH has been measured accu-
rately for the water in question, this value can be used to
calculate an initial H+ concentration prior to any
adjustment for the ion balance. The measured pH for
the Seathwaite Tarn water was 5.16. This value was used
to calculate an initial H+ of 7 meq L 1. The concentra-
tions of cations and anions and hence the salts required
for Seathwaite Tarn (in meq L 1) are summarized in
Table 4.
As for the soft water example, the salts should be
grouped together in compatible combinations using the
information from Table 3. Table 7 summarizes the
stock solutions used for Seathwaite Tarn and Table 8
shows the required volumes of stock solutions to make
up the freshwater. The suitability of the stock solutions
was again checked using MINTEQA2. The model
output indicated that the sodium sulphate should be
placed in its own solution as it was found to be likely
to form an insoluble precipitate of calcium sulphate
if dissolved in solution A1 and an insoluble
aluminium sulphate precipitate such as AlOHSO4 in
solution A3. With no CaCO3 to dissolve, all the stock
solutions can be 1000 times the concentration of the final
solutions.

Table 7
Recipe for Seathwaite Tarn (Cumbria)
1
Stock solution meq L Final required concentration (mg L 1) Mass of salt added to 1 L of Concn. factor
MilliRo water
C Z+ AZ

A1
NaCl 73 1.678 2.588 4.266 g
MgCl2
6H2O 66 0.802 2.340 6.696 g
CaCl2
6H2O 56 1.122 1.985 6.123 g  1000
KCl 10 0.391 0.355 0.746 g
NaNO3 36 0.828 2.232 3.060 g

A2
Na2SO4 84 1.931 4.034 5.965 g  1000

A3
AlCl3
6H2O 18 0.162 0.638 1.449 g
HCl 7 7.056  10–3 0.248 7 mL of 1 M HCl in 1 L  1000

Table 8
Dilution factors for making 5 L of Esthwaite Water, Rostherne Mere and Seathwaite Tarn synthetic waters

Soft water Hard water Acid water

Stock soln. Vol. (mL) Diln. factor Stock soln. Vol. (mL) Diln. factor Stock soln. Vol. (mL) Diln. factor

S1 5 1/1000 H1 50 1/100 A1 5 1/1000

S2 4545 1/1.1 H2 4545 1/1.1 A2 5 1/1000
S3 5 1/1000 H3 50 1/100 A3 5 1/1000
H4 50 1/100
Water 445 305 4985
1292 E.J. Smith et al. / Water Research 36 (2002) 1286–1296
Stock solution A3 presents a special problem since
aluminium salts are amphoteric and will only dissolve
readily at either high or low pH. Aluminium hydrolyses
upon dissolution in water to form several aluminium
hydroxyl species which determine the pH-dependent
solubility. MINTEQA2 was used to predict the most
favourable chemical conditions for reliable aluminium
dissolution. Calculation of the saturation status of a
solution of 6.3  10 3 mol L 1 of AlCl3 over a pH range
of 1–14 showed that aluminium is likely to precipitate
out in the pH range of 4–12 as an aluminium oxide.
Since the minimum solubilty of Al occurs at about
pH 6, it is necessary to avoid dissolving aluminium
salts in solutions with a pH in the range 5.5–6.5. To
ensure reliable dissolution of the aluminium salt, the
aluminium chloride was placed with the HCl in stock
solution 3.
2. Materials and methods
The following sections describe simple, reliable
procedures for making 5 L of soft, hard or acidic
synthetic freshwaters.
2.1. Preparation of stock solution 2 for soft and hard
freshwaters
The main problem associated with making soft and
hard freshwaters is the preparation of stock solutions S2
and H2. This involves the dissolution of calcium
carbonate which is only sparingly soluble under normal
conditions of temperature and atmospheric pCO2. A
combination of theoretical modelling using MINTE-
QA2 and laboratory experiments indicated that the
easiest and most reliable method of preparing stock
solutions S2 and H2 is by increasing the pCO2 in the
solution during dissolution of the salt. Stock solutions
S2 and H2 should be made up at 1.1 times the final
required concentration as follows. The pCO2 in 5 L of
water is increased by vigorously bubbling CO2 gas
through it for 10 min prior to addition of the appro-
priate mass of CaCO3. It is essential that a fine
powdered form of CaCO3 is used to promote dissolu-
tion. Upon addition of the CaCO3 powder, CO2
bubbling is continued for 4 h. The concentration of Ca
in solution after filtration through a 0.2 mm membrane
filter should then be determined to check for complete
dissolution.
It is possible to prepare stock solution S2 for the soft
water by bubbling the solution with air to encourage
dissolution if no carbon dioxide gas is available,
although dissolution is then much slower and more
unreliable. The dissolution kinetics of CaCO3 in
common laboratory solvents was investigated by Pingi-
tore et al. [15]. Fine grained CaCO3 powder of 0.1 g was
added to 500 mL of stirred distilled water maintained at
251C. It took about 30 h for sufficient CaCO3 to dissolve
to produce 7.5 ppm of Ca in solution. This method is not
recommended as it is very slow and there is a risk of a
residual CaCO3 phase.
An alternative method for preparing stock solutions
S2 and H2 involves the dissolution of calcium oxide in a
carbonate-free system. This is achieved by the removal
of all dissolved CO2 in the water by bubbling with
nitrogen gas for approximately 1 h. The use of a widely
available disposable plastic glove-bag ensures a com-
plete nitrogen blanket is achieved for the duration of the
dissolution procedure. CaO may then be added to the
solution and the solution bubbled with N2 for 1 h at
1 atm until complete dissolution is achieved (30–40 min
was found to be sufficient time for complete CaO
dissolution for the two stock solutions S2 and H2
tested). Once the solution reaches equilibrium, it
should be bubbled vigorously with CO2 for 10 min
to titrate rapidly the solution to a pH below 7. This
step is essential. It prevents the Ca from precipitat-
ing out of solution (as CaCO3) by rapidly lowering
the pH. It also converts all the excess OH ions to
HCO3 .
2.2. Preparation of other stock solutions
Composite stock solutions S1, S3, H1, H3 and H4
are made up in glass volumetric flasks at up to 1000
times the final concentration (depending on the final
required composition of the water). Care should be
taken with Na2SO4, which is difficult to dissolve.
This salt should be poured into the volumetric
flask dry, most easily from a weighing boat, and the
required water added while stirring magnetically to aid
dissolution.
The preparation of stock solutions A1 and A2 for
acidic freshwaters is simply a matter of dissolving the
required masses of salts in high purity water in glass
volumetric flasks (Table 7). As for the soft and hard
water stock solutions, each solution should be stirred
vigorously with a magnetic stirrer to avoid localized
supersaturation of salts and possible precipitation. More
care should be taken over the preparation of stock
solution A3. The bulk of the MilliRo water used to
make stock solution A3 should be acidified with HCl,
HNO3 or H2SO4 (depending on the required composi-
tion of the synthetic freshwater) prior to the addition of
the aluminium salt(s). To prepare stock solution A3 for
the Seathwaite Tarn Water, the glass volumetric flask
was half filled with MilliRo water, the hydrochloric acid
was added, and the solution stirred vigorously prior to
addition of the aluminium salt. The low pH (o3) of the
acid ensures that the added aluminium salt dissolves and
remains in solution.
 E.J. Smith et al. / Water Research 36 (2002) 1286–1296
2.3. Preparation of synthetic waters
The lake waters may be made up in either glass or
plastic containers. For the sake of robustness and ease of
availability, the lake waters used as examples were made
up in 5 L High density polyethylene (HDPE) containers.
The appropriate volumes of stock solutions S1 and S3 or
H1, H3, and H4 should be added to the required volume
of stock solutions S2 or H2, respectively, while it is being
vigorously stirred to avoid local supersaturation and the
volume made up to 5 L with high purity water (Table 8).
It is important to use high purity water to avoid
introducing contamination and organic substances into
the water. ‘‘MilliRo’’ grade water was used to make all
the lake waters discussed. It is produced by a Milli-RO
Plus Reverse Osmosis System which removes >99% of
dissolved organics, particles and microorganisms and up
to 99% of inorganic ions.
Calcium carbonate is dissolved in stock solutions S2
and H2 for the soft and hard waters, respectively by
increasing the pCO2. The final synthetic lake waters
therefore contain excess dissolved CO2. The pH of
circumneutral waters is controlled predominantly by the
equilibria of carbonate species, so the correct equili-
brium pH for the completed soft and hard waters will
not be achieved until the excess CO2 is removed and the
water is in equilibrium with the atmosphere. Although
the water would eventually (days or weeks) equilibrate
naturally by loss of CO2 to the atmosphere, the process
can be speeded up by bubbling the solution vigorously
with air. The waters are assumed to have reached
equilibrium when the pH does not change by more than
0.04 units over an hour. The soft and hard waters used
as examples took about four hours to equilibrate with
the atmosphere even with vigorous bubbling (Fig. 1).
Either water can be prepared from their stock solutions
in less than a day.
The acidic lake water may be made up in a HDPE 5 L
container by adding appropriate volumes of stock
solutions A1, A2 and A3 using the dilution factors
shown in Table 8. The container is 3/4 filled with
MilliRo water, and the 5 mL aliquots of stock solutions
A3, A1 and A2 added in that order while the water is
vigorously stirred. The addition of stock solution A3
(containing the aluminium solution) lowers the pH from
about 5.7 (the pH of distilled water in equilibrium with
the atmosphere) to approximately 5.2. This slightly
lower pH reduces the risk of aluminium precipitation
during solution mixing, as aluminium has a minimum
solubility at about pH 6. Once all stock solutions are
added and well mixed the volume is made up to 5 L.
There is usually no requirement to aerate the acidic
water as it was not bubbled with CO2 and CO2 has only
a small effect on the pH if it is below 5. The acidic
freshwater may be prepared in under an hour from its
stock solutions.
1293
Fig. 1. Equilibration of soft and hard water by bubbling with
air at 1 atm.
2.4. Final analytical composition
Once the synthetic freshwaters were made up,
subsamples were removed and filtered through 0.45 mm
Millipore HAWP filter membranes. These samples were
analysed for major cations, anions, alkalinity and pH to
confirm that they were of the required composition. The
major ion analyses were carried out by ion chromato-
graphy. Alkalinities were measured by Gran titration
and pH was measured using a glass electrode. The
aluminium concentration of the acidic freshwater was
measured by electrothermal AAS (Perkin Elmer
412002L).
The measured compositions of the soft, hard and
acidic synthetic lake waters are shown in Table 9. The
reported errors are one standard deviation of the mean
which was calculated from three replicate analyses of
each type of lake water. In addition to the pH being
measured for each synthetic freshwater, it was calculated
with MINTEQA2 using the measured concentration of
each component, the temperature of the solutions when
each pH measurement was made and the pCO2 for the
laboratory (3.6  10 4 atm). There was good agreement
between the measured and calculated pH values with
differences of 0.01 for Esthwaite Water and 0.03 for
Seathwaite Tarn. There was no difference between the
measured and calculated pH values for Rostherne Mere.
Measured concentrations of cations and anions agreed
well with the values calculated from the salts and the
charge balance was good for each solution. The
difference between the sum of the anions and the sum
of the cations for the Esthwaite Water analysis was
0.21%, for the Rostherne Mere analysis 0.34% and for
1294 E.J. Smith et al. / Water Research 36 (2002) 1286–1296

Table 9
The composition of the soft, hard and acid waters

Esthwaite Water Rostherne Mere Seathwaite Tarn Analytical method

Recipe Measured Recipe Measured Recipe Measured

(meq L 1) (meq L 1) (meq L 1) (meq L 1) (meq L 1) (meq L 1)

Mg2+ 120 12170.2 815 93479 66 6575 ICa

Ca2+ 530 55972 2450 2420724 56 5672 IC
Na+ 250 24071 665 69675 193 19777 IC
K+ 25 2474 105 9471 10 970.2 IC
Al3+ 18 2171 AAS
H+ 8b 8c
SCZ+ 925 944 4035 4144 350 356

Cl 280 27271 685 696713 230 23171 IC

NO3 30 2771 100 10372 36 4173 IC
SO24 230 22870.4 1210 122973 84 8271 IC
H2PO4 30 3272 IC
HCO3 385 41573 2010 2070710 1 Gran titration
SAZ 925 942 4035 4130 350 355

Modelledd Measured Modelledd Measured Modellede Measured

pH 7.83 7.84 8.49 8.49 5.09 5.06 Glass electrode
a
IC ion chromatography.
b
H+ calculated from measured pH from initial chemical determination.
c +
H calculated using MINTEQA2.
d
pH calculated using MINTEQA2.
e
The initial pH for Seathwaite Tarn was the same (5.10) as the value calculated using MINTEQA2.

the Seathwaite Tarn analysis 0.28%. It should be noted
that ionic balances are only approximate. For example,
calculation of the chemical speciation of the acid water
at 201C using the Alchemi-speciation program [16,17]
indicated there was some hydrolysis of Al. This
hydrolysis reduces the equivalent of Al from 18 to
12.1 meq L 1, which means that the average charge of Al
changes from Al3+ to Al2.1+ (Lydersen, pers. comm.).
2.5. Stability and storage
The saturation index (SI) was used to assess the
saturation status of a solution (or lake water) with
respect to a given mineral phase where SI=log10[(IAP)/
Ksp]. IAP is the ion activity product and Ksp is the
temperature dependent solubility product. The satura-
tion status for a sample composition of Rostherne Mere
and Seathwaite Tarn with respect to several mineral
phases was calculated using MINTEQA2 version 3.11
(Table 10).
Although the freshwater compositions used as exam-
ples of hard and acidic fresh waters are analyses of
natural waters, the waters appear to be supersaturated
with respect to several mineral phases. The hard water
appears to be oversaturated with respect to calcium
minerals such as aragonite and calcite while the acidic
water appears to be oversaturated with respect to several
aluminium oxides (Table 10). MINTEQA2 may not
have predicted the true saturation status of the acidic
water wholly accurately since (in keeping with other
speciation codes) it relies on the assumption that
solution Al can be depicted as an equilibrium reaction
between an Al(OH)3(s) phase and the free (aquo) Al3+
which may not be entirely valid (Lydersen et al., 1991).
It was observed by Lydersen et al. (1991) that the
relatively high concentrations of aluminium which are
often present in the runoff waters that enter surface
water systems would not occur if a crystalline
Al(OH)3(s) phase controlled the Al activities. High
concentrations of inorganic dissolved Al could, how-
ever, be explained by the formation of amorphous
Al(OH)3(s) structures which are soluble as small colloids
(Lydersen et al., 1991). Substantial amounts of amor-
phous Al(OH)3(s) are able to exist as colloids in solution
for time periods of several weeks or months [18,19].
Since colloids are not incorporated in any models,
equilibrium thermodynamics are only of limited use in
predicting actual solubilities of Al (Lydersen et al.,
1991). Therefore, it is possible that although MINTE-
QA2 predicts that the acidic water is oversaturated with
respect to several aluminium phases, it may in fact be
relatively stable for a few weeks. Additionally, the first
 E.J. Smith et al. / Water Research 36 (2002) 1286–1296
Table 10
The saturation status of Rostherne Mere (a hard water) and Seathwaite Tarn (an acid water) at 201C with respect to mineral phases
Rostherne Mere
a
Mineral Molecular formula SI
Aragonite CaCO3 0.557
Calcite CaCO3 0.711
Dolomite CaMg(CO3)2 1.016
Hydroxyapatite Ca5(PO4)3OH 10.724
a
SI denotes saturation index.
solid formed during precipitation of Al in the acid
freshwater solution is always an amorphous Al(OH)3 (s)
phase (Lydersen, pers. comm.). With a pH of 5.10 and
160 mg Al L 1, the ion activity product pertinent to pKs*
(based on the Alchemi-speciation) is 9.67. Most pKs*
values for amorphous Al(OH)3 in the literature range
from 10.4 to 10.8, which means that the solution is still
undersaturated with respect to an amorphous phase.
The oversaturation of surface lake waters with respect to
one or more mineral phases is not an unusual
phenomenon [20]. For example, waters in contact with
CaCO3 rich rocks (such as limestone and dolomite) may
be oversaturated with respect to calcite [20]. This
supersaturation may be the result of several factors
other than polymorphic mineral forms. The oversatura-
tion of surface lake waters is often caused by photo-
synthesis which reduces the concentration of dissolved
CO2 in the water, resulting in a pH rise and possibly
calcite precipitation at high levels of over-saturation.
Another factor which may contribute to a surface lake
water appearing to be supersaturated with respect to
specific mineral phases is the presence of organic
constituents which may result in the formation of
colloidal organic complexes.
The hardwater prepared according to the given
protocol is at equilibrium with atmospheric CO2. The
partial pressure of this gas, along with the alkalinity,
dictates the pH. To prepare waters with the same
composition, but different equilibrium pH values, the
water must be bubbled with a N2/CO2 gas mixture of
appropriate pCO2. Although adding concentrated acid
or base and re-equilibrating with the atmosphere will
change the composition, this procedure is often adopted
if compositional changes can be tolerated.
If the chemical composition of a synthetic freshwater
is supersaturated with respect to one or more mineral
phases, as are the examples of hard and acid synthetic
freshwaters given in this paper, the water will be in a
metastable condition which may result in loss of
chemical constituents from the water over an extended
period of time. It is important that this factor is
1295
Seathwaite Tarn
Mineral Molecular formula SIa
Al4(OH)10SO4 0.880
Alunite KAl3(SO4)2(OH)6 0.844
Boehmite AlO(OH) 0.619
Diaspore HAlO2 2.368
Gibbsite Al(OH)3 0.494
considered in the intended use of the lake water. It is
therefore advised that the water is prepared as close to
the intended use as possible and stored in a cold room at
101C to prolong its shelf life. It is also recommended
that the dissolved concentrations of any component(s)
which are important to the experiment being carried out
are monitored, particularly if the experiment lasts for
several weeks.
Because of inappropriate constants or equilibria used
in speciation codes and kinetic limitations on precipita-
tion, waters may be more stable than predicted. Studies
into the stability of synthetic freshwater materials
indicate that the freshwaters may be stable for extended
periods of time. Stability tests were performed on two
freshwater CRMs of pH 6.8 by analyzing randomly
selected samples after 1, 3, 6 and 12 months of storage at
+41C, +201C and +401C [4]. These tests found no
evidence of any instability.
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