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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 evaporation techniques and provides insight into the production rates of salt and fuel requirements. Methods of calculation are provided for determining 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.
2007 Elsevier Ltd. All rights reserved.
Keywords: Salt; Evaporation; Brine; Stone boiling; Numerical methods
1. Introduction
Saltmaking from brine has been a common worldwide industry 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 locally 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 saltenriched plants (Adshead, 1992), the final step in salt production 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
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0305-4403/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jas.2007.10.013
1454
concentration, fire temperature, and vessel heat transfer properties 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 untested evaporation conditions. The great utility of numerical
simulations is the speed at which experiments can be performed. 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 mw 1:52 104 S2 9:50 103 S
18
16
26.2 wt%
14
12
20 wt%
10
8
15 wt%
6
10 wt%
4
2
0
5 wt%
0
10
15
20
25
30
35
40
45
50
D
g
Rn
f u es e
Dg
Dg
Tmax Tmin
2
es 0:6108aw exp
17:27T
237:3 T
The activity coefficient of water aw is a function of the concentration of dissolved salts. The following correlation was derived from experimental vapor pressure data published for
sodium chloride (Lide, 1991).
aw 0:0011m2 0:0319m 1
emax emin
11
2
The vapor pressure e (kPa) can be determined from the relative humidity
e
1455
Hr es
100
12
where Hr is the relative humidity (%). Wind speed is incorporated using empirically determined coefficients for the atmospheric 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 u 6:431 0:536U2
13
2460
Gsc dr us sin4sind cos4cosdsinus
p
14
1456
Radians
18
21
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 diurnal 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 carbon dioxide. The net long-wave radiation can be determined
by
4
4
p
T Tmin
Rs
Rnl s max
0:340:14 e 1:35
0:35
2
as bs Ra
22
where s is the StefaneBoltzmann constant (4.903
109 MJ K4 m2 day1), T is the maximum and minimum
23
Latitude
Month
Temperature ( C)
Humidity (%RH)
Solar Radiation (MJ m2 day-1)
Wind Speed (m s1)
Michoacan, Mexico
Shanghai, China
16.83 N
May 2000
27.2
77
29.1
5
31.17 N
July
28.4
83
30.8
4
Weather data were obtained from the National Climatic Data Center of the
U.S. National Oceanic and Atmospheric Administration (www.noaa.gov). Solar radiation for a cloudless day was calculated from Section 2.1.3.
200
Evaporation Rate, mm/day
Salt Produced, kg
180
160
140
120
100
80
60
40
20
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
1457
1458
Table 2
Physical properties of various materials at 20 C
Material
Density (g cm3)
Source
1.33e1.50
1.60e1.82
7.87
7.15
8.96
8.77
11.36
0.4e0.7
0.41e0.63
74.48
46.9
393.7
70.6
34.7
0.92
0.4473
0.837
0.3846
0.3771
0.1287
C
A, B, F
D
D, G
D
E
D
Data from [A] Dondi et al. (2004); [B] Bhattacharjee and Krishnamoorthy (2004); [C] Abu-Hamdeh and Reeder (2000); [D] Davis (1998); [E] Copper Development Association (2007); [F] Lange (1952); [G] MatWeb (2007).
q
l
26
24
25
35
20
30
Brine Concentration 18
16
25
Crystallized Salt
14
12
20
10
15
8
6
10
4
5
0
2
0
10
15
20
25
0
30
1459
1 2n 1
2n 1
T n1 M 2t T n
T n1
29
tDt T n
M 2n t
2n t
Time (min)
Fig. 3. Brine evaporation from a lead pan placed over fire. Pan conditions are:
pan exterior 200 C, pan volume 126 L, pan thickness 0.8 cm, and pan
heated area 0.9 m2. Initial pan heat-up time is negligible.
27
28
where k is the thermal conductivity (W m1 K1), r the density (kg m3), and Cp the heat capacity of the object
(J g1 K1). For simplicity, here it is assumed that the object
is spherical and that only the one-dimensional direction
need be considered. For irregularly shaped objects, the
4
M4
T1
T0
Mt
M t
30
where M 4 for both Eqs. (29) and (30). At the surface, equations accounting for convection must be utilized assuming that
the heat capacity of the outer half-slab can be neglected
tDt T n
nN
2n 1=2
tDt T a 2n 1
tDt T n1
2n 1
nN
nN
2
2
31
where Tn represents surface temperature and Tn1 the temperature at 1 positional step below the surface.
4.2. Numerical simulation of stone boiling
Solving these equations allows for the determination of the
average stone temperature with time after immersion. Initially,
the heat transferred raises the temperature of the brine up to its
boiling point. Any additional heat released by the stone serves
to evaporate water and concentrate brine. Eventually the brine
is concentrated to a maximum value of about 29.0 wt% at its
boiling point with further evaporation resulting in the formation of salt crystals.
For the numerical model, the boiling stone is assumed to be
chert. Chert was well known to Native Americans and was
commonly used to make stone tools. Although the physical
properties of chert are not well studied, there are numerous
studies on the analogous material of amorphous or fused
quartz. The thermal conductivity of chert can be determined
from a polynomial fit of published data by Kanamori et al.
(1968) and Clauser and Huenges (1995)
k 4:67 109 T 3 8:53 106 T 2 6:29 103 T
9:85 102
32
33
where Cp is the heat capacity (J mol1 K1) and T is the temperature (K) for the range of 298e844 K. At higher temperatures the equation changes to
Cp 58:928 1:0031 102 T
34
3
20
0.50
18
0.45
16
0.40
14
0.35
12
0.30
10
0.25
0.20
0.15
0.10
Heat transferred, MJ
Salt Produced, kg
2
0
0.05
9
0.00
Time (minutes)
Fig. 4. Numerical simulation results for Native American stone boiling. Represented here are results for placing a 700 C stone with a volume of 10 L into
a ceramic pan containing 30 L of 10 wt% brine initially at 25 C. The stone is
assumed to be a spherical nodule of chert.
25
1460
20
Volume Ratio
Brine/Stone
1.0
2.0
3.0
4.0
15
10
0
200
300
400
500
600
700
800
900
1000
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 Engineering 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 excavations at Chidham, West Sussex. Britannia 23, 27e44.
Brown, I.W., 1980. Salt and the Eastern North American Indian: an archaeological study. In: Lower Mississippi Survey Bulletin, No. 6. Peabody Museum, Harvard University.
Brown, I.W., 1981. The Role of Salt in Eastern North American Prehistory.
Louisiana Archaeological Survey and Antiquities Commission Anthropological Study No. 3. Department of Culture, Recreation and Tourism, Baton 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 Geophysical 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 saline waters in Aux Vases and Cypress Formations, Illinois Basin. Aquatic
Geochemistry 5, 281e311.
Dondi, M., Mazzanti, F., Principi, P., Raimondo, M., Zanarini, G., 2004. Thermal 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 Processes 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. Pacific 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
MatWeb, 2007. Material Property Database. Available from: http://www.matweb.com (accessed 03.07.07.).
McCracken, J.P., Smith, K.R., 1998. Emissions and efficiency of improved
woodburning cookstoves in highland Guatemala. Environment International 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 Shavington, 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.