See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/222780084

Methods for calculating brine evaporation rates during salt production

Article  in  Journal of Archaeological Science · June 2008

DOI: 10.1016/j.jas.2007.10.013

CITATIONS READS

45 16,116

1 author:

D. Glen Akridge
NorthWest Arkansas Community College
35 PUBLICATIONS   329 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Cathodoluminescence of Meteorites and Lunar Samples View project

All content following this page was uploaded by D. Glen Akridge on 17 October 2017.

The user has requested enhancement of the downloaded file.

 Journal of Archaeological Science 35 (2008) 1453e1462
http://www.elsevier.com/locate/jas

Methods for calculating brine evaporation rates during salt production

D. Glen Akridge*
Arkansas Archeological Society, 5411 W. Wheeler Road, Fayetteville, AR 72704, USA
Received 11 July 2007; received in revised form 17 October 2007; accepted 22 October 2007

Abstract

Salt is recognized by archaeologists as an important commodity due to the biological need for sodium and other cultural uses. Numerous
studies have described the various techniques used in converting brine to crystallized salt, but few, if any, have attempted to quantify the physical
processes of evaporation in pre-industrial societies. Apart from the few areas where salt mining is possible, nearly all forms of salt production
require evaporation of water to concentrate brine and ultimately produce salt crystals. This study quantifies three of the most common evapo-
ration techniques and provides insight into the production rates of salt and fuel requirements. Methods of calculation are provided for determin-
ing evaporation through (1) direct solar heating of brine, (2) applied external heat to a vessel, and (3) an immersed heated object (e.g., stone).
These results provide physical constraints on the evaporation process and provide investigators with techniques for estimating efficiency and
total production of prehistoric and historic saltworks.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Salt; Evaporation; Brine; Stone boiling; Numerical methods

1. Introduction
Saltmaking from brine has been a common worldwide in-
dustry for thousands of years, beginning by at least the fourth
millennium B.C. in Europe (Olivier and Kovacik, 2006) and
by the first millennium B.C. in China (Flad et al., 2005) and
Central America (Andrews, 1983). Solar evaporation of brine
to form salt continues to be a viable commercial process to this
day along coastal areas (Kostick, 2002). The procedures used
in making salt varied by geographic region and resources lo-
cally available. The quantity desired by the local population
may have also influenced the choice of salt production
methods. Although the process often involved techniques
such as leaching, extraction, filtering, and burning of salt-
enriched plants (Adshead, 1992), the final step in salt produc-
tion invariably required evaporation of water from brine to
precipitate salt crystals. Numerous studies have focused on
the techniques and archaeological remnants of saltworks.
These studies have tended to leave open the question of
* Tel.: þ1 479 790 0261; fax: þ1 479 575 5453.
E-mail address: dgakridge@hotmail.com
efficiency and total salt production, except in the few cases
where historic descriptions of saltworks exist (e.g., Chiang,
1976). Few have attempted to quantify the process of evapora-
tion. Quantifying the process of salt production does more
than provide estimates for the total salt produced. It provides
insights into the required human labor expenditure and the de-
gree to which the local economy depended on salt. The salt
trade would have largely been determined by the amount of
excess salt that could be produced. In the case of brine boiling
to obtain salt, the need for substantial quantities of fuel (e.g.,
wood) often resulted in serious environmental changes to the
surrounding landscape (Early, 1993).
Quantifying the production of salt can be accomplished
through experimentation or by numerical simulation. Experi-
mentation is often advantageous because it can provide
insights into the subtleties of the process that might not be
realized otherwise, but suffers greatly from the need to control
variables. Salt production is a labor intensive and time
consuming task, and in the case of solar evaporation may
take weeks to obtain salt. This makes experimentation diffi-
cult, especially in light of the multitude of potential variables
such as ambient temperature and humidity, brine volume and

0305-4403/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jas.2007.10.013
1454 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462
concentration, fire temperature, and vessel heat transfer prop-
erties that need to be monitored and maintained. In addition,
experimentation results are generally only relevant for the
tested scenario and provide only limited insight into other un-
tested evaporation conditions. The great utility of numerical
simulations is the speed at which ‘‘experiments’’ can be per-
formed. Simulations of processes taking hours or weeks can
be performed in seconds allowing for greater exploration of
variable effects and deeper understanding of the physical
mechanisms underlying evaporation.
This paper lays out in detail all the necessary steps in
simulating evaporation in three different scenarios: (1) solar
evaporation, (2) evaporation from an externally heated pan,
and (3) evaporation from a hot immersed object. Each scenario
involves evaporation of a fixed volume of brine to dryness
resulting in the precipitation of salt crystals. For any batch
evaporation the amount of salt produced can be determined by
 
ms ¼ mw 1:52  104 S2 þ 9:50  103 S
where ms is the mass (kg) of salt crystallized, mw is the mass
(kg) of the water evaporated, and S is the initial salt concentra-
tion of the brine in wt% NaCl (Fig. 1). For ease of calculation,
the dissolved salt is assumed to be pure sodium chloride. So-
dium and chlorine make up 85% of the inorganic constituents
found in seawater (Lide, 1991) and natural inland brines are
often of even higher purity (Bowman, 1956). Consequently,
the presence of other minor components has little impact on
the numerically simulated results. Exceptions may be inland
lakes containing high concentrations of sulfates. In these
cases, adjustments may need to be made to account for the
mass, density, and vapor pressure differences of a sulfate-
rich brine.
2. Solar evaporation
In solar evaporation a vessel or ponded area containing
brine is allowed to evaporate under the prevailing
20
18
16
NaCl Crystallized (kg)
14
12
10
8 for daily calculation steps and uses 24 h averages for temper-
6 ature, humidity, and wind speed. For modeling past saltmaking
4 10 wt%
2
0
0 5 10 15 20 25 30
Water Evaporated (kg)
Fig. 1. Graphical representation of Eq. (1). The maximum sodium chloride
brine concentration is 26.2 wt% (at 25  C). For comparison, seawater has
a salt content of about 3.5 wt%.
environmental conditions. This technique works best at low
latitudes where sunlight duration and intensity are highest
and areas with low relative humidity and rainfall. Solar evap-
oration also becomes the default method when fuel resources
are scarce and boiling of brine is unfeasible. Historically
this technique was common in coastal areas (e.g., LeConte,
1862) and continues to be a viable commercial process world-
wide (Kostick, 2002). Solar evaporation could have been prac-
ticed at many inland salines where brine concentrations tend to
be high (e.g., Demir and Seyler, 1999) thus reducing total
evaporation time.
2.1. Calculation method for solar evaporation
Calculating evaporation rates for brine solutions requires
a slight modification to the standard Penman (1948) equation
used by hydrologists to determine evaporation from open
water sources. The Penman approach combines the effects
ð1Þ of radiation and aerodynamic forces controlling evaporation
and has been shown to adequately predict evaporation in
a wide variety of environments (e.g., Finch, 2001). The Pen-
man equation is generally expressed as:
D g
lE ¼ Rn þ f ðuÞ ðes  eÞ ð2Þ
Dþg Dþg
where E is the evaporation rate expressed as mm/day, l is the
latent heat of vaporization, D is the gradient of the vapor pres-
sureetemperature curve, g is the psychometric constant, Rn is
the net solar radiation, f(u) is a function of wind speed, and es
and e are the saturation vapor pressure of water and ambient
water vapor pressure, respectively. In this paper the Penman
equation has been modified to reflect the reduced vapor pres-
sure of a salt solution. A similar approach has been used pre-
viously in determining evaporation from saline lakes (Calder
and Neal, 1984). Additional details of the equation and its var-
iables are discussed by Allen et al. (1998) and Shuttleworth
(1993).
2.1.1. Calculating aerodynamic terms
The aerodynamic forces acting on evaporation are primarily
the result of environmental variables governing diffusion of
26.2 wt% water molecules away from the liquid surface of water or
brine. The modified Penman equation for predicting potential
evaporation rates from a free water surface requires knowledge
20 wt%
of several local climate variables. The method shown here is
15 wt%
endeavors, historical weather data including average climate
conditions for each month can be obtained for a variety of lo-
5 wt%
cales from several sources, including the National Climatic
35 40 45 50 Data Center in the United States.
The latent heat of evaporation l (MJ kg1) varies with tem-
perature according to
l ¼ 2:501  0:002361T ð3Þ
 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462
where T is in degrees celsius. The temperature T for daily time
steps is simply defined as the mean of the daily maximum and
minimum temperatures.
Tmax þ Tmin
T¼
2 Hr es
The saturation vapor pressure es (kPa) is determined from the
average daily temperature and is an indication of the rate at
which water molecules can escape from the liquid surface.
When dissolved salts are present the saturation vapor pressure
is lowered due to the decreased chemical potential of the liq-
uid water. To adjust for this lowering effect the water activity
coefficient aw is inserted into the basic equation.
17:27T
es ¼ 0:6108aw exp
237:3 þ T
The activity coefficient of water aw is a function of the con-
centration of dissolved salts. The following correlation was de-
rived from experimental vapor pressure data published for
sodium chloride (Lide, 1991).
aw ¼ 0:0011m2  0:0319m þ 1
where m is the concentration of sodium chloride in moles per
liter of water. Density of NaCl solutions has been measured by
Romanklw and Chou (1983). Based on their published data,
the following equation was developed to calculate NaCl solu-
tion density over the temperature range of 25e45  C and con-
centration range of 0e26.2 wt%.
 0:012
25  
D¼ 2:754  105 S2 þ 6:872  103 S þ 0:99704
Tsol
where D is the solution density (g cm3), S is the NaCl con-
centration in wt%, and Tsol is the solution temperature ( C).
The saturation vapor pressure is a function of temperature
and the gradient of this function (kPa  C1) is also required
and can be calculated by
4098es
D¼ 2 ð8Þ
ð237:3 þ TÞ
The psychrometric constant (kPa  C1) is given by
g ¼ 0:000655P
where P is the atmospheric pressure (kPa). If the atmospheric
pressure is unknown, an approximate value can be calculated
based upon a site’s elevation
 5:26
293  0:0065z
P ¼ 101:3 ð10Þ
293
where z is height above sea level (m).
In a similar fashion to the mean temperature, the daily
mean vapor pressure is the average of the maximum and min-
imum values.
1455
emax þ emin
e¼ ð11Þ
2
The vapor pressure e (kPa) can be determined from the rel-
ative humidity
ð4Þ
e¼ ð12Þ
100
where Hr is the relative humidity (%). Wind speed is incorpo-
rated using empirically determined coefficients for the atmo-
spheric resistance encountered in diffusion of the water
vapor away from a liquid surface. For an open water surface
the wind function is given by
f ðuÞ ¼ 6:43ð1 þ 0:536U2 Þ ð13Þ
ð5Þ
where the wind speed U2 (m s1) is measured at 2 m above the
surface.
2.1.2. Determining net radiation
Solar radiation aids in promoting evaporation by impart-
ing energy into the absorbing material. The radiational
ð6Þ energy available at the ground surface is a combination of
both short and long-wavelength radiation and is the differ-
ence between the upward and downward radiation fluxes.
The amount of solar energy reaching the ground surface
can be reduced by cloudiness and atmospheric interferences
or increased with increasing altitude. This net radiation, Rn,
can be determined in three ways: (1) direct measurement
using a radiometer, (2) published tables based on latitude,
or (3) calculations incorporating Earth’s orbital characteris-
tics. Radiometers measure the net radiation by monitoring
the temperature difference across two parallel plates. They
ð7Þ require periodic calibration and each measurement locale
must be generally free of any obstructions blocking incom-
ing or outgoing radiation. Approximate values for the net
radiation reaching the ground surface can also be found in
published tables (e.g., Lide, 1991). These tables are gener-
ally organized by latitude and indicate the average net
radiation for a cloudless sky during each month of the
year. These tables do not usually account for altitude
differences but are generally accurate to within 10% during
summer months and 15% during winter months (Lide, 1991).
ð9Þ 2.1.3. Calculating net radiation
The following series of equations are required when deter-
mining the net radiation by accounting for Earth’s orbital char-
acteristics. The extraterrestrial radiation Ra (MJ m2 day1)
can be calculated for any latitude and day of year by adjusting
the solar constant Gsc for the solar declination
24ð60Þ
Ra ¼ Gsc dr ½us sinð4ÞsinðdÞ þ cosð4ÞcosðdÞsinðus Þ
p
ð14Þ
where Gsc ¼ 0.0820 MJ m2 min1, dr is the inverse relative
EartheSun distance, us is the sunset hour angle (rad), 4 is
1456 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462

the latitude (rad), and d is the solar declination (rad). Angles in temperature during a 24 h period (K), e is the water vapor
radians can be obtained by converting decimal degrees. pressure (kPa), as and bs are regression terms mentioned ear-
lier, Rs is the solar radiation (MJ m2 day1), and Ra is the ex-
p
Radians ¼ ½Decimal degrees ð15Þ traterrestrial radiation (MJ m2 day1). The net radiation Rn
180
(MJ m2 day1) is simply the difference between the incoming
The inverse relative EartheSun distance dr is given by effective solar radiation and outgoing long-wave radiation.
 
2p Rn ¼ Rns  Rnl ð23Þ
dr ¼ 1 þ 0:033 cos J ð16Þ
365

where J is the number day of the year (e.g., 1 for January 1 or
365 for December 31). The solar declination d is
 
2p
d ¼ 0:409 sin J  1:39 ð17Þ
365
The sunset hour angle us is given by
us ¼ arccos½ tanð4ÞtanðdÞ
The number of daylight hours N can be determined by
24
N¼ us ð19Þ
p ous weather data and site specific information. Historical
The solar radiation is calculated by adjusting the extrater-
restrial radiation for the relative sunshine duration
 n
Rs ¼ as þ bs Ra ð20Þ
N
where Rs is the solar radiation (MJ m2 day1), n is the actual
duration of sunshine (hours), N is the maximum possible
amount of sunshine (hours), and as and bs are regression pa-
rameters with recommended values of 0.25 and 0.50, respec-
tively. The effective solar radiation reaching the ground
surface is reduced by solar reflection caused by albedo
Rns ¼ ð1  aÞRs
where Rns is the net solar radiation (MJ m2 day1), and a is
the albedo of the surface. For open water Shuttleworth
(1993) recommends an albedo value of 0.08. However, for
shallow evaporation pans the underlying reflectivity of the
pan must be considered. For example, dark earthenware or
wooden pans filled with water may have an albedo closer to
0.05. When evaporating brine, salt crystals will begin to
form, thus increasing the reflectivity. Rife et al. (2002) found
that albedo values of 0.3 were appropriate for modeling diur-
nal weather cycles over a salt-encrusted playa.
The flux of long-wave radiation reflected by the ground
back into space is given by the StefaneBoltzmann law minus
that which is absorbed by clouds, water vapor, dust, and car-
bon dioxide. The net long-wave radiation can be determined
by
 4  
T þTmin4  pffiffiffi Rs
Rnl ¼s max 0:340:14 e 1:35 0:35
2 ðas þbs ÞRa
where s is the StefaneBoltzmann constant (4.903 
109 MJ K4 m2 day1), T is the maximum and minimum
2.2. Results from numerical simulations
To illustrate the utility of predicting solar evaporation rates,
two examples from the literature will be briefly discussed here.
These examples were selected because sufficient evaporation
variables are specified to allow for numerical modeling of
the described saltmaking process. The first example is an eth-
ð18Þ nographic description of saltmaking from the western coast of
Mexico. The second simulation uses historic descriptions of
19th century Chinese coastal tradition using portable wooden
pans to evaporate brine. Each case requires the input of numer-
weather data including long-term averages can be obtained
from a variety of sources. The data used here were derived
from the online databases of the National Climatic Data Cen-
ter of the National Oceanic and Atmospheric Administration
(www.noaa.gov); and Weather Underground (www.wunder-
ground.com). Model inputs are summarized in Table 1.
Williams (2002) describes a traditional Mesoamerican salt-
works operating on the western coast of Mexico in the state of
Michoacan. The La Placita saltworks operates during the dry
season, roughly from April to mid-June. Specialists, called sal-
ineros, scrape the upper surface of soil from a nearby dry es-
tuary. The salt-encrusted sand called salitre is first filtered
ð21Þ through a tapeixtle using seawater and the resulting enriched
brine is transferred to specially prepared evaporation pans
called eras. According to Williams, La Placita has 18 eras
with most measuring approximately 3 m  3 m in dimension.
Each era is lined with beach sand and lime and can hold about
400 L of brine. Every day 2e3 buckets of brine must be added
to maintain a consistent level. It takes 5 days of evaporation to
concentrate the brine sufficiently to begin collecting salt, about
25e30 kg are then collected every other day from each era.
An average of 7 tons of salt can be produced at each saltmak-
ing site during the dry season.
Table 1
Monthly weather averages for selected saltmaking locales
Michoacan, Mexico Shanghai, China
Latitude 16.83 N 31.17 N
 Month May 2000 July
Temperature ( C) 27.2 28.4
Humidity (%RH) 77 83
Solar Radiation (MJ m2 day-1) 29.1 30.8
ð22Þ Wind Speed (m s1) 5 4
Weather data were obtained from the National Climatic Data Center of the
U.S. National Oceanic and Atmospheric Administration (www.noaa.gov). So-
lar radiation for a cloudless day was calculated from Section 2.1.3.
 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462 1457

Based on the information that Williams (2002) supplies, an
estimate for the average evaporation rate can be derived. Dur-
ing the first 5 days of evaporation, the brine concentrates up to
a maximum value of about 26.2 wt%. Once the maximum
value is reached, further evaporation results in the formation
of salt crystals. Eq. (1) indicates that producing 12.5e15 kg
of salt per day requires the evaporation of 35e43 kg of water.
Converting the mass of the water evaporated to volume and di-
viding by the surface area of an era (w9 m2) results in an
evaporation rate of 3.9e4.8 mm day1.
Using the steps outlined in Section 2.1 we can numerically
simulate the evaporation process during Williams’ field season
at La Placita in 2000. Input values used for the model are listed
in Table 1. The albedo of the pan is expected to be relatively
high (w0.3) owing to the lime-lined pan and the constant pre-
cipitation of salt crystals at the bottom of the pan. Results for
the numerical simulation suggest that the evaporation rate
should be in the range of 4.1e4.7 mm day1 following the
initial 5-day concentration period, essentially identical to that
obtained in practice. The range in evaporation rate given by
the numerically calculated results reflects the potential varia-
tion in cloud cover from 0 to 20%. Assuming an initial brine
concentration of about 15 wt% and an average cloud cover of
10%, Fig. 2 represents model results from the numerically sim-
ulated evaporation occurring from a single era at La Placita dur-
ing the first 20 days of May 2000. Interestingly, extrapolating
the production rate of the era in Fig. 2 to the entire field season
(w75 days) yields approximately 790 kg of salt. This correlates
to an average of about 9 eras in use at La Placita based on the
estimate of 7 tons of salt produced each season. This agrees
well with Williams’ (2002: p. 243) assertion that not all of
the 18 eras are in use at one time.
Similarly, solar evaporation along the coastal margin of
China utilized enriched brine obtained by leaching salty earth
or in some cases from ashes that were spread onto the ground
(Chiang, 1976). The practice of using portable wooden pans
for evaporation began in the 18th century in the Hangchou
Bay area. Although variations in size were common, the typ-
ical wooden pan was about 2.5 m long, 1 m wide, and 3e
6 cm deep. Chiang (1976: p. 526) states that ‘‘crystallization
8 200
Evaporation Rate, mm/day
Evaporation Rate (mm/day)
of salt in these portable pans took only 1 day under fine
weather in summers.’’ Although we are not told of the brine
strength or volume in these pans, some reasonable assump-
tions can be made. If the brine is near saturation (26.2 wt%)
and averages 3 cm in depth, then numerical calculations
indicate that the evaporation rate would be 4.8 mm day1
(see Table 1 for model inputs). Upon complete evaporation
the depth of the salt crystals would be about 5 mm indicating
the total evaporation time to be about 5 days. This is somewhat
longer than the estimate given by Chiang (1976) unless he was
referring to incipient crystallization which could begin on the
first day.
The two examples provided here illustrate the value of
numerical modeling in addition to historic descriptions. Com-
puter simulation of the well documented La Placita saltworks
in Mexico provides remarkable agreement between the
author’s observations and numerical results. However, historic
descriptions of 18th century Chinese saltmaking appear to
differ from the numerically calculated evaporation rate.
Numerical modeling provides an independent means for vali-
dating historical claims regarding salt production.
3. Evaporation from an externally heated pan
This technique typically involves the suspension of a vessel
over a fire or the emplacement of a vessel directly onto a bed
of hot coals. Heat is transferred through the base and walls of
the vessel and warms the interior fluid. The amount of heat
transferred to the brine is governed by the energy output of
the fire and efficiency of heat transfer in a particular brine-
boiling setup. The efficiency is defined as the amount of
heat transferred into the brine relative to the total heat pro-
duced by the fire. For an open fire efficiency is low owing
to the loss of heat by combustion gases escaping around the
vessel. Glanville (2005) calculated an efficiency of about
20% for the 19th century methods of brine boiling in iron ves-
sels described by LeConte (1862) along the east coast of the
United States. This value is somewhat better than the approx-
imately 15% efficiency for boiling water in cooking vessels
over an open fire (McCracken and Smith, 1998) but less
than the more optimal 28e40% efficiency of well vented
wood stoves (Joshi et al., 1991). For earthenware vessels
180

with substantially lower thermal conductivity than iron

7 Salt Produced, kg 160
(Table 2), efficiency is reduced even further and may be as
Salt Produced (kg)

140 low as 2e5% (Glanville, 2005).

6 120
100
5 80
60
4 40
20
3 0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Day of Month (May 2000)
Fig. 2. Numerical simulation results for a 9 m2 era at La Placita saltworks in
Michoacan, Mexico.
Although efficiency is a poorly known variable and is
unique to each setup for brine boiling with externally applied
heat, the amount of salt produced can be determined by simply
estimating the temperature on the exterior surface of the ves-
sel. This method eliminates (or sidesteps) the issue of effi-
ciency and focuses directly on the heat being transferred
through the vessel and into the brine. Thus, the amount of
heat calculated would be the absolute minimum required to ac-
complish evaporation and would represent a system of 100%
heat transfer efficiency. Heat loss by escaping combustion
gases, evaporating water molecules, and conduction through
1458 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462
Table 2
Physical properties of various materials at 20  C
Material Density (g cm3)
Clay (9.3e18.3 wt% H2O) 1.33e1.50
Brick, clay 1.60e1.82
Iron (100%Fe) 7.87
Cast iron (3.16%C) 7.15
Copper 8.96
Bronze (89%Cu þ 11%Sn) 8.77
Lead 11.36
Data from [A] Dondi et al. (2004); [B] Bhattacharjee and Krishnamoorthy (2004); [C] Abu-Hamdeh and Reeder (2000); [D] Davis (1998); [E] Copper Develop-
ment Association (2007); [F] Lange (1952); [G] MatWeb (2007).
vessel walls to surrounding air all contribute to lowering the
overall efficiency.
3.1. Calculation method for evaporation by externally
applied heat
By concentrating solely on the heat transferred through
a vessel’s wall, a one-dimensional steady-state heat transfer
equation can be applied
k The discovery of several late Roman age lead pans in Britain
q ¼ A ðTe  Ti Þ
Dx
where q is the heat transfer rate in joules per second (J/s), A is
the heated surface area, Dx is vessel thickness, k is the thermal
conductivity in watts per meter-kelvin (W m1 K1), and Te
and Ti are the temperature (K) of the vessel exterior and inte-
rior surfaces, respectively (Geankoplis, 2003). This equation
assumes that a constant flow of heat is applied to the vessel ex-
terior. Materials of high thermal conductivity (Table 2) allow
for substantially more heat to be transferred through the vessel
whereas increasing the vessel’s wall or basal thickness reduces
heat flow. For most practitioners of brine boiling, the primary
means of evaporation control comes from varying the amount
of external heat applied to the vessel which in turn determines
the temperature of the vessel’s exterior. The temperature of the
internal surface Ti is typically the same as the boiling point of
the brine and will change as evaporation proceeds and the
brine concentrates to a maximum value of about 29.0 wt%
at the boiling point. Although at very high external tempera-
tures, the interior surface may exceed that of the boiling brine.
The boiling point of sodium chloride brine can be estimated by
the boiling point elevation equation
Tb ¼ Kb mi þ 100  C
where Tb is the boiling temperature ( C) of the brine, Kb is the
proportionality constant for water (0.512  C/m), m is the brine
concentration (mol NaCl per L of water), and i is the number
of dissociated ions per formula unit (NaCl ¼ 2). At high alti-
tudes where pure water boils at temperatures below 100  C,
the appropriate boiling point should instead be inserted into
the equation. Finally, the evaporation rate (g/s) can be deter-
mined by
Thermal conductivity (W m1 K1) Specific Heat (J g1 K1) Source
0.4e0.7 C
0.41e0.63 0.92 A, B, F
74.48 0.4473 D
46.9 0.837 D, G
393.7 0.3846 D
70.6 0.3771 E
34.7 0.1287 D
q
E¼ ð26Þ
l
using Eq. (3) to determine the latent heat of vaporization.
3.2. Numerical simulation of applied external heat
Simulating the effects of brine boiling requires knowledge
of both the physical characteristics of the pan and the amount
of applied heat (i.e. temperature on pan exterior). Often one or
the other of these criteria is unknown for a specific saltwork.
ð24Þ
provides constraints on these variables which can be used to
demonstrate the numerical model. Lead melts at 327  C and
salt practitioners would likely have kept the external tempera-
ture well below this value to avoid accidental melting of the
pan. At Shavington, Cheshire, a lead pan measuring 100 cm
by 90 cm by 14 cm deep was found cut into eight pieces, pre-
sumably as a first step to recycling the material (Penney and
Shotter, 1996). At 0.8 cm thickness, the original weight of
the pan would have been approximately 118 kg. Although
none of the surviving Roman era lead pans have been found
in situ, they likely would have been placed across earthen
flue trenches much like many ceramic salt pans elsewhere in
Britain (e.g., Bradley, 1992). Fires were presumably kept rel-
atively low, 200e250  C, to prevent damage to the pan.
Numerically simulating the evaporation from the Shaving-
ton salt pan requires only an estimation of the initial brine con-
centration. Here an arbitrary 10 wt% is used, but this value has
only a minor impact on the duration of the evaporation pro-
cess. Even if the temperature on the pan’s exterior is kept rel-
atively low (w200  C), Fig. 3 demonstrates a fairly quick
evaporation for the Shavington pan. Neglecting substantial
heat loss, the brine is brought to a boil in only 3 min and con-
tinues until 14 min, whereby evaporation has resulted in the
ð25Þ maximum allowable brine concentration. Further evaporation
after 14 min results in salt crystals forming inside the pan. Ul-
timately, about 14 kg of salt can be recovered in less than
20 min of boiling, assuming 10 wt% brine in a 126 L pan.
4. Evaporation using hot immersed objects
A third evaporation scenario considered here is that of a hot
object (e.g., stone) placed inside a pan of brine. This method is
believed to have been utilized for salt production in eastern
 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462 1459

35 20 analytical solution to the conduction equation becomes con-

Brine Concentration (wt% NaCl)

Brine Concentration 18 siderably more complex.

30
16 Finite difference methods can be used to obtain a numerical

Crystallized Salt (kg)

25 14 solution to Eq. (27), which involves computing temperature
Crystallized Salt
12 changes after small positional (n) and time (t) steps are incre-
20
10 mented (Geankoplis, 2003: pp. 386e387; Carslaw and Jaeger,
15
8
1959). The positional steps effectively divide the object into
6
concentric rings that are Dx (m) thick. For a sphere, the tem-
10
perature can be determined by
4
5
2

1 2n þ 1 2n  1
0 0 tþDt T n ¼ T nþ1 þ ðM  2Þt T n þ T n1 ð29Þ
0 5 10 15 20 25 30 M 2n t 2n t
Time (min)

Fig. 3. Brine evaporation from a lead pan placed over fire. Pan conditions are:
where M ¼ Dx2/(aDt). At the center (n ¼ 0) the equation
pan exterior ¼ 200  C, pan volume ¼ 126 L, pan thickness ¼ 0.8 cm, and pan changes to
heated area ¼ 0.9 m2. Initial pan heat-up time is negligible.
4 M4
tþDt T 0 ¼ T1 þ T0 ð30Þ
Mt M t
North America from about A.D. 1000e1400 (Brown, 1980,
1981). Stone boiling as a cooking technique probably began where M  4 for both Eqs. (29) and (30). At the surface, equa-
with the introduction of pottery (ca. 2500 B.C.), if not earlier, tions accounting for convection must be utilized assuming that
and continued into the historic period (Sassaman and Rudol- the heat capacity of the outer half-slab can be neglected
phi, 2001). Thick-walled ceramic ‘‘pans,’’ most in association
with salines, have been found with capacities ranging from 40 nN ð2n  1Þ=2
to 400 L. The enormous size and weight of these vessels when tþDt T n ¼ tþDt T a þ 2n  1 tþDt T n1 ð31Þ
2n  1
filled with brine would have made them practically immovable þ nN þ nN
2 2
and suspension over a fire seems equally unlikely. Brown
(1980, 1981) concluded that these salt pans were placed in ba- where Tn represents surface temperature and Tn1 the temper-
sin-shaped ground depressions and heated stones from nearby ature at 1 positional step below the surface.
fires were dropped into the pan to facilitate evaporation. The
lack of exterior discoloration from fires on many pans and 4.2. Numerical simulation of stone boiling
the occasional find of stones inside pans (e.g., Bushnell,
1907) lend support to the conclusion that stone boiling was Solving these equations allows for the determination of the
at least one method utilized by Native Americans to evaporate average stone temperature with time after immersion. Initially,
brine. the heat transferred raises the temperature of the brine up to its
boiling point. Any additional heat released by the stone serves
4.1. Calculation method for stone boiling to evaporate water and concentrate brine. Eventually the brine
is concentrated to a maximum value of about 29.0 wt% at its
A hot object transfers its internal heat energy to the sur- boiling point with further evaporation resulting in the forma-
rounding fluid through convective heat transfer at the object’s tion of salt crystals.
surface. This transfer of heat is governed by the unsteady-state For the numerical model, the boiling stone is assumed to be
conduction equation chert. Chert was well known to Native Americans and was
commonly used to make stone tools. Although the physical
vT v2 T properties of chert are not well studied, there are numerous
¼a 2 ð27Þ
vt vx studies on the analogous material of amorphous or fused
quartz. The thermal conductivity of chert can be determined
where a is the thermal diffusivity (m2/s), t is time (s), and T is
from a polynomial fit of published data by Kanamori et al.
the temperature (K) of the object. Thermal diffusivity is
(1968) and Clauser and Huenges (1995)
simply

k k ¼ 4:67  109 T 3  8:53  106 T 2 þ 6:29  103 T

a¼ ð28Þ
rCp  9:85  102 ð32Þ

where k is the thermal conductivity (W m1 K1), r the den- where k is thermal conductivity (W m1 K1), and T is the
sity (kg m3), and Cp the heat capacity of the object stone temperature (K). Similarly, Robie et al. (1978) have de-
(J g1 K1). For simplicity, here it is assumed that the object veloped expressions for the heat capacity of quartz
is spherical and that only the one-dimensional  direction
need be considered. For irregularly shaped objects, the Cp ¼ 44:603 þ 3:7754  102 T  1:0018  106 T 2 ð33Þ
1460 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462

where Cp is the heat capacity (J mol1 K1) and T is the tem- 25

Volume Ratio
perature (K) for the range of 298e844 K. At higher tempera- Brine/Stone
tures the equation changes to 20 1.0

Water Evaporated (kg)

2.0
3.0
Cp ¼ 58:928 þ 1:0031  102 T ð34Þ 4.0
15
3
for the range 844e1800 K. The density of chert is 2.6 g cm .
This information together can be used to determine the ther- 10

mal diffusivity (a) properties of chert for the numerical model.

Fig. 4 graphically represents a simulated evaporation of 5
placing 700  C chert stone(s), representing 25% of the total
40 L volume, into a salt pan containing 10 wt% brine at 0
25  C. Boiling begins immediately for brine surrounding the 200 300 400 500 600 700 800 900 1000

stone and continues for about 4 min, by which time the stone
temperature now equals that of the brine and no further heat is
transferred. During the first 2 min the evaporating brine con-
centrates from 10 wt% up to 29.0 wt%. At 1.6 min salt crystals
begin forming and continue until the stone and brine reach
thermal equilibrium. For this scenario, 373 g of crystallized
salt would be produced. Emplacement of additional hot stones
into the pan would continue the evaporation process.
From the short timescales involved to obtain salt, it seems
this method would clearly be effective in evaporating brine.
Unlike suspension of a pan over a fire, stone boiling releases
all of its internal heat directly into the brine. However, there
may be practical limitations for manipulating large volumes
of very hot stones. Stones heated to high temperatures often
shatter and large stones would be difficult to transport from
a fire to the brine pan. Smaller stones would make handling
easier, but would require more repeated firings to achieve
the same evaporation as large stones. The smallest salt pan
found at the Kimmswick site near St. Louis (Bushnell, 1907)
had a volume of approximately 40 L. Assuming a scenario
similar to that outlined above, emplacement of 25 vol% stone
into the salt pan would translate to 26 kg of extremely hot
stone(s) that would have been manipulated. This seems to sug-
gest that stone boiling may actually require a tremendous
amount of human labor to achieve significant quantities of
salt. Fig. 5 indicates the potential evaporation that could be
Initial Stone Temperature (°C)
Fig. 5. Evaporation curves for stone boiling with various brine:stone volume
ratios. Curves represent an initial brine temperature of 25  C and 10 wt%
concentration.
obtained with various brine/stone volume ratios. The 10 wt%
brine is assumed to initially be at 25  C before emplacement
of a hot spherical stone of chert. Even for a Vb/Vs ¼ 1 and
an initial stone temperature of 1000  C, the mass of the stone
would still exceed the mass of the evaporated water by a factor
of 2.5. Lower stone temperatures or smaller volumes of stone
would result in greater discrepancies between stone mass and
evaporated water mass.
4.3. Hot objects with negligible internal resistance
An alternative mathematical treatment can be applied when
the hot object has negligible internal resistance to the flow of
heat. These objects (e.g., copper and iron) have high thermal
conductivities and will have an approximately uniform inter-
nal temperature profile at any given time following immersion
into brine. To maintain an energy balance, heat loss through
the vessel wall or to the atmosphere is assumed to be minimal
relative to the rapid rise in brine temperature. The total amount
of heat transferred at any given time can be determined by
 
Q ¼ Cp rVðT0  TN Þ 1  eðhA=Cp rVÞt ð35Þ
20 0.50
18 0.45
where Q (J) is the total heat transferred, V (m3) is the volume
of the object, h is a heat transfer coefficient for natural convec-
Heat Transferred (MJ)

16 0.40
tion (w5000 W m2 K), A is the heated area (m2), and t is the
Salt Produced (kg)

14 0.35
elapsed time (s) after immersion (Geankoplis, 2003: pp. 277e
12 0.30
286, 357e359).
10 0.25
8 0.20
5. Conclusions
6 0.15
4 0.10
Heat transferred, MJ The goal of this paper is to develop a mathematical basis
2 Salt Produced, kg 0.05
for brine evaporation that can be used by investigators to quan-
0 0.00
0 1 2 3 4 5 6 7 8 9 titatively describe salt production activities. The methods de-
Time (minutes) scribed herein cover three distinct techniques for evaporating
brine: (1) solar evaporation, (2) boiling due to an externally
Fig. 4. Numerical simulation results for Native American stone boiling. Rep-
resented here are results for placing a 700  C stone with a volume of 10 L into applied heat source, and (3) boiling caused by a hot immersed
a ceramic pan containing 30 L of 10 wt% brine initially at 25  C. The stone is object. Historically these techniques were sometimes used in
assumed to be a spherical nodule of chert. combination to achieve the desired evaporation results. Input
 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462
parameters for the three models range from common weather
variables for solar evaporation to pan and stone physical
dimensions for brine boiling. No one evaporation method
can be considered superior since other factors such as fuel
availability, sunshine intensity, brine concentration, and even
the cultural value placed on human labor make the choice of
evaporation technique unique to each culture. However, the
calculation methods given here do allow for direct compari-
sons to be made regarding evaporation efficiency. Brine boil-
ing offers the quickest means of evaporation, typically on
the order of minutes for the examples given here, but this
does not account for the time spent acquiring fuel. Solar evap-
oration does not require fuel but may take days or weeks to
accomplish and is limited to geographic areas with high evap-
oration and little precipitation.
Although beyond the scope of the current paper, quantify-
ing salt production opens up new areas of research that can
be addressed. Changes in production methods through time
can be the result of either cultural or technological factors,
or both. In a simple least-cost model, humans would be ex-
pected to seek strategies to minimize labor and fuel require-
ments in the salt production process. Salt production has
often been described as a labor intensive endeavor requiring,
in the case of brine boiling, extraction of substantial quantities
of fuel from the local environment. The calculations presented
herein offer a direct means to evaluate technological changes
for improved evaporation efficiency. For example, Eq. (24)
describes the direct relationship between vessel thickness
and the rate of heat transfer. Thinner vessel walls require
proportionately less fuel to achieve evaporation. In addition,
determinations of minimum energy (fuel) requirements can
be made which provide insight into local deforestation or other
resource depletion. Early (1993) noted that the removal of fruit
bearing plants and nut bearing trees from the vicinity of a salt-
works may have altered diet and even changed the local pop-
ulation of wild animals that depend on these resources. These
and other concerns can now be better addressed by quantifying
the brine evaporation process.
Acknowledgments
The author thanks Ann M. Early and Dan F. Morse for
helpful discussions on this subject. Ashley Dumas and Robert
C. Mainfort provided insightful comments on an early draft of
this paper. Valuable comments were also received from two
anonymous reviewers that greatly improved this manuscript.
References
Abu-Hamdeh, N.H., Reeder, R.C., 2000. Soil thermal conductivity: effects of
density, moisture, salt concentration, and organic matter. Soil Science So-
ciety of America Journal 64, 1285e1290.
Adshead, S.A.M., 1992. Salt and Civilization. St. Martin’s Press, New York.
Allen, R.G., Pereira, L.S., Raes, D., Smith, M., 1998. Crop evapotranspiration:
guidelines for computing crop water requirements. In: Irrigation and
Drainage Paper, 56. Food and Agriculture Organization of the United
Nations, Rome.
1461
Andrews, A., 1983. Maya Salt Production and Trade. University of Arizona
Press, Tucson.
Bhattacharjee, B., Krishnamoorthy, S., 2004. Permeable porosity and thermal
conductivity of construction materials. Journal of Materials in Civil Engi-
neering 16, 322e330.
Bowman, H.H.M., 1956. Salinity data on marine and inland waters and plant
distribution. The Ohio Journal of Science 56 (2), 101e106.
Bradley, R., 1992. Roman salt production in Chichester Harbour: rescue exca-
vations at Chidham, West Sussex. Britannia 23, 27e44.
Brown, I.W., 1980. Salt and the Eastern North American Indian: an archaeo-
logical study. In: Lower Mississippi Survey Bulletin, No. 6. Peabody Mu-
seum, Harvard University.
Brown, I.W., 1981. The Role of Salt in Eastern North American Prehistory.
Louisiana Archaeological Survey and Antiquities Commission Anthropo-
logical Study No. 3. Department of Culture, Recreation and Tourism, Ba-
ton Rouge.
Bushnell, D.I., 1907. Primitive salt-making in the Mississippi Valley, I. Man
No. 13. London.
Calder, I.R., Neal, C., 1984. Evaporation from saline lakes: a combination
equation approach. Hydrological Sciences Journal 29, 89e97.
Carslaw, H.S., Jaeger, J.C., 1959. Conduction of Heat in Solids, second ed.
Clarendon Press, Oxford.
Chiang, T.C., 1976. The production of salt in China, 1644e1911. Annals of
the Association of American Geographers 66, 516e530.
Clauser, C., Huenges, E., 1995. Thermal conductivity of rocks and minerals.
In: Ahrens, T.J. (Ed.), Rock Physics and Phase Relations e a Handbook
of Physical Constants. AGU Reference Shelf, vol. 3. American Geophys-
ical Union, Washington, pp. 105e126.
Copper Development Association. <http://www.copper.org> (accessed
03.07.07.).
Davis, J.R. (Ed.), 1998. Metals Handbook. ASM International, Materials Park,
Ohio.
Demir, I., Seyler, B., 1999. Chemical composition and geologic history of sa-
line waters in Aux Vases and Cypress Formations, Illinois Basin. Aquatic
Geochemistry 5, 281e311.
Dondi, M., Mazzanti, F., Principi, P., Raimondo, M., Zanarini, G., 2004. Ther-
mal conductivity of clay bricks. Journal of Materials in Civil Engineering
16, 8e14.
Early, A.M., 1993. Caddoan saltmakers in the Ouachita Valley: the Hardman
Site. In: Research Series, No. 43. Arkansas Archeological Survey,
Fayetteville.
Finch, J.W., 2001. A comparison between measured and modeled open water
evaporation from a reservoir in south-east England. Hydrological Pro-
cesses 15, 2771e2778.
Flad, R., Zhu, J., Wang, C., Chen, P., von Falkenhausen, L., Sun, Z., Li, S.,
2005. Archaeological and chemical evidence for early salt production in
China. Proceedings of the National Academy of Sciences of the United
States of America 102, 12618e12622.
Geankoplis, C.J., 2003. Transport Processes and Separation Process Principles,
fourth ed,. Prentice Hall, New Jersey.
Glanville, J., 2005. Brine transport and woodland salt making in southwestern
Virginia: an hypothesis. Paper presented at the Eastern States Archeological
Federation Meeting, Williamsburg, Virginia, USA, November 12, 2005.
Joshi, V., Venkataraman, C., Ahuja, D.R., 1991. Thermal performance and
emission characteristics of biomass-burning heavy stoves with flues. Pa-
cific and Asian Journal of Energy 1, 1e19.
Kanamori, H., Fujii, N., Mizutani, H., 1968. Thermal diffusivity measurement
of rock-forming minerals from 300 to 1100 K. Journal of Geophysical
Research 73 (2), 595e605.
Kostick, D.S., 2002. Salt. In: Metals and Minerals. U.S. Geological Survey
Minerals Yearbook, vol. 1. U.S. Government Printing Office, pp. 1e17
(Chapter 64).
Lange, N.A., 1952. Handbook of Chemistry, eighth ed. Handbook Publishers,
Sandusky, Ohio.
LeConte, J., 1862. How to Make Salt from Sea-Water? Governor and Council
of South Carolina, Columbia.
Lide, D.R. (Ed.), 1991. CRC Handbook of Chemistry and Physics, 72nd ed.
CRC Press, Boca Raton.
1462 D.G. Akridge / Journal of Archaeological Science 35 (2008) 1453e1462
MatWeb, 2007. Material Property Database. Available from: http://www.mat-
web.com (accessed 03.07.07.).
McCracken, J.P., Smith, K.R., 1998. Emissions and efficiency of improved
woodburning cookstoves in highland Guatemala. Environment Interna-
tional 24 (7), 739e747.
Olivier, L., Kovacik, J., 2006. The ‘Briquetage de la Seille’ (Lorraine, France):
proto-industrial salt production in the European Iron Age. Antiquity 80,
558e566.
Penman, H.L., 1948. Natural evaporation from open water, bare soil, and
grass. Proceedings of the Royal Society, Series A 193, 120e145.
Penney, S., Shotter, D.C.A., 1996. An inscribed Roman salt-pan from Shaving-
ton, Cheshire. Britannia 27, 360e365.
Rife, D.L., Warner, T.T., Chen, F., Astling, E.G., 2002. Mechanisms for diurnal
boundary layer circulations in the Great Basin Desert. Monthly Weather
Review 130, 921e938.
View publication stats
Robie, R.A., Hemingway, B.S., Fisher, J.R., 1978. Thermodynamic properties
of minerals and related substances at 298.15 K and 1 bar (105 pascals)
pressure and at higher temperatures. In: USGS Survey Bulletin, 1452.
U.S. Government Printing Office, Washington.
Romanklw, L.A., Chou, I.-M., 1983. Densities of aqueous NaCl, KCl, MgCl2,
and CaCl2 binary solutions in the concentration range 0.5e6.1 m at 25, 30,
35, 40, and 45  C. Journal of Chemical and Engineering Data 28, 300e
305.
Sassaman, K.E., Rudolphi, W., 2001. Communities of practice in the early pot-
tery traditions of the American Southeast. Journal of Anthropological Re-
search 57, 407e425.
Shuttleworth, W.J., 1993. Evaporation. In: Maidment, D.R. (Ed.), Handbook of
Hydrology. McGraw-Hill, New York.
Williams, E., 2002. Salt production in the coastal area of Michoacan, Mexico.
Ancient Mesoamerica 13, 237e253.