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ARE THE CURATIVE PROPERTIES OF BLACK MUD

FROM THE DEAD SEA DUE TO THE PRESENCE OF BITUMEN


(ASPHALT) OR OTHER TYPES OF ORGANIC MATTER?
ARIE NISSENBAUM1, , JRGEN RULLKTTER2 and YOSEPH YECHIELI3
1 Department of Environmental Sciences and Energy Research, Weizmann Institute of Science,
Rehovot 76100, Israel; 2 Institute of Chemistry and Biology of the Marine Environment (ICBM),
Carl von Ossietzky University of Oldenburg, D-26111 Oldenburg, Germany; 3 Geological Survey
of Israel, Jerusalem 95501, Israel ( author for correspondence: tel./fax: +972-8-934-4232;
e-mail: arie.nissenbaum@weizmann.ac.il)

Received 1 June 2001; accepted in revised form 8 April 2002

Abstract. Deep black clayey sediments of the Dead Sea, previously covered with water at times
of higher sea level, are being mined for therapeutic purposes and for the preparation of cosmetic
products under the name Black Mud. It was claimed that the beneficial properties are due to the
presence of bitumen (asphalt) as attested by the colour. Less commonly, the curative properties have
been ascribed to humic acids or to organic matter derived from algae in the lake. Asphalt from the
Dead Sea has been of major economic importance to the region and was used as a medication for 2000
years until the mid-20th century. Geochemical analysis of the Black Mud showed that it contains
relatively little organic matter (ca. 0.60.8% organic carbon) and that the organic matter is mostly
derived from the land masses surrounding the lake. Asphalt was totally absent and the concentration
of humic acids very low. The black colour of the mud is rather due to the poorly crystallised iron
sulphides. Based on this, the therapeutic properties of the mud are ascribed to its content of reduced
sulphur species, its physical and chemical properties and possibly its brine content, but not to the
presence of organic matter.
Key words: asphalt, bitumen, Black Mud, Dead Sea, medicine, organic matter, sediments,
sulphides

1. Introduction
In recent years, the unique chemical and physical properties of the Dead Sea (with
a total salt content of about 320 g L1 , high magnesium and bromine content in
the brine and a density of 1.23 g cm3 ) made it an important centre for the production of natural medications and cosmetics. In addition to the healing properties
of the lake water itself, mud from the lake is considered to be of high therapeutic
value. The mud that is used for this purpose is the so-called Black Mud, a deeply
black, shiny mud, rich in salts, which is applied to part of or the whole body. The
Black Mud, when applied as heated mud packs or simply by smearing all over
the body, is used as treatment in case of arthritic diseases. Although it does not
provide a cure, it helps in alleviating the pain suffered by inflammatory and noninflammatory joint diseases such as psoriatic arthritis or osteoarthritis. In addition,
Environmental Geochemistry and Health 24: 327335, 2002.
2002 Kluwer Academic Publishers. Printed in the Netherlands.

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the Black Mud has been extensively used as a base for the preparation of soaps,
creams and unguents for skin care. The manufacturers of those products claim that
the mud has major effects on revitalising and toning the skin. Those products are
exported today and are sold all over the world.
The mud, when fresh, is shiny black in colour and sheen and very closely
resembles the asphalt (bitumen) blocks, which can be occasionally found along
the shores of the Dead Sea (Nissenbaum et al., 1980). The reputation of Dead
Sea asphalt, which has been in use for 10,000 years or so (Nissenbaum, 1994),
frequently resulted in assuming that all black materials associated with the Dead
Sea are asphaltic in nature. Yet, other types of black materials are quite common in
the Dead Sea area. For example, black manganese crusts cover calcium carbonate
layers along the shores (Ehrlich and Zapkin, 1985; Nishri and Nissenbaum, 1993);
black flint pebbles abraded from the walls of the Rift Valley, in which the Dead
Sea is sited, are abundant in the area; deposits of the black so-called oil shales of
Senonian (Upper Cretaceous) age are found in some locations along the coast of the
lake and the deeply black, thermally metamorphosed equivalent of this formation,
in Arabic called Hajar Musa (the stone of Moses), can easily be confused with
asphalt by sight. However, none of those materials contains asphalt, and only the
Senonian oil shales contain related organic matter.
While the therapeutic and cosmetic properties of Black Mud from the Dead
Sea remain unchallenged, the following paper examines the possible presence of
asphalt, and other types of organic matter, as an important constituent of the mud.
Organic matter that is occasionally referred to in the advertisements for commercial
products of Dead Sea mud as tar or simply as organic matter is sometime listed as
an active ingredient that may be responsible for some of the claimed cosmetic and
dermatological properties of the Black Mud.
1.1. THE BLACK MUD
Black Mud is the common name given to detrital black, fine muds of the Holocene Zeelim formation, which is found in the erosional fans of wadis (seasonal
dry river beds) along the southern basin of the Dead Sea (Yechieli, 1993). The
best exposures are in the Zeelim fan where the receding lake level caused the
exposure of sediments that were under water for the last several thousand years.
The sediment section is at least 7 m thick and ranges in age from the recent until
at least 2500 years BP. The mud is being mined from the top 12 metres of the
sediment section.
According to Raz (1993) the Black Mud is mostly formed from detrital matter
which is brought in by the Jordan River in the north of the Dead Sea and swept
by currents along the western coast of the lake to be deposited in protected bays.
The black colour is a result of reductive processes that occur after deposition.
Analytical data by Raz (1993) showed that the major components of the waterinsoluble fraction of the mud are carbonates such as calcite and dolomite (66%) and

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TABLE I
Chemical composition of interstitial brines in recent Dead Sea muds (including Black Mud)
Borehole

Na+
(g L1 )

K+
(g L1 )

Ca2+
(g L1 )

Mg2+
(g L1 )

Cl
(g L1 )

SO2
4
(g L1 )

Br
(g L1 )

YM4 (0.1 m)
YM4 (0.3 m)
YM4 (0.8 m)
YDS
Dead Sea water

3.0
31.6
19.4
20.0
39.7

7.8
6.9
4.5
5.5
7.6

28.2
17.6
6.9
8.0
17.2

92.1
45.8
20.5
20.0
42.4

326
217
103
110
219

0.1
0.8
2.2
0.9
0.4

10.4
5.7
2.7
2.6
5.3

clays, quartz and feldspars (34%). The water-soluble component is mostly halite.
The black mud contains a saline interstitial water with a chemical composition,
which is generally similar to that of the Dead Sea brine, but is usually enriched in
the cations Mg2+ , Na+ and Ca2+ and the anion Br . The sulphate concentration
is usually higher than that of the Dead Sea water (Yechieli, 1993; Yechieli and
Ronen, 1997). Table I gives the typical chemical compositions of the interstitial
brines in Dead Sea recent sediments (regular sediments as well as Black Mud)
from several locations in the Dead Sea coastal area.
The Black Mud is extensively used in the Dead Sea area for therapeutic purposes and is also widely used as a basis for the manufacturing of cosmetic preparations and products that are locally used in spas and exported all over the world.
The beneficial effectiveness of Black Mud treatment, especially when combined
with sulphur baths, against skin diseases and rheumatoid arthritic diseases has been
extensively documented in the medical literature (Sukenik et al., 1990; Sukenik,
1996; Elkayam et al., 2000).
1.2. DEAD SEA BITUMEN AS A MEDICATION
Asphalt from the Dead Sea has been extensively used as a remedy since ancient
times as described by Nissenbaum (1999). (The terms bitumen and asphalt are
frequently used interchangeably, although in the geochemical literature the term
bitumen is usually employed to describe organic matter that can be extracted from
sediments by solvents; the term asphalt is retained for native solid organic matter
which occurs in rocks and sediments). Pliny the Elder (Pliny, 1948), in the first
century AD, describes the list of ailments against which bitumen can be employed
because it is astringent, dispersive, contractive and agglutinating. Although Pliny
(1948) does not specifically refer to Dead Sea material, he was well aware of the
asphalt production from the lake and indeed mentions about it, as well as bitumen
from other sources, just before he describes the medical applications of bitumen. In
another place, he provided a detailed description of the appearance of asphalt in the

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Dead Sea and its collection by the local people. Josephus Flavius, the 1st century
AD Jewish historian, provided a description of asphalt collection from the Dead
Sea (Flavius, 1959) and wrote that this asphalt is used for the cure of mens bodies;
accordingly it is mixed in great many medicines. The continuing importance of
Dead Sea asphalt in medicine is attested to by the visit of Galen to Palestine in 166
AD. Galen, a physician to Emperors and also the most influential medical practitioner of the ancient world, went to the Dead Sea to examine two of its products:
asphalt and balsam. Galen (according to Matthiolus, 1530, as quoted by Forbes,
1959) says that the Dead Sea produces the best bitumen that gives good results in
sealing fresh cuts and in all things that need to be dried and moderately warmed.
The Venerable Bede (Bede, 1896), writing in the beginning of the 8th century AD,
in the portrayal of the Dead Sea says that its bitumen is used for the healing of
the human body. A Moslem physician, El Tamimi, working in Jerusalem at the
end of the 10th century, wrote that Jewish Bitumen, collected from the Dead Sea,
is used in the preparation of theriac, a medicine in which snake venom was an
ingredient (Z. Amar, Bar Ilan University, personal communication).
In the 20th century, Dead Sea asphalt also roused interest as medication, probably due to its similarity in colour and smell to the widely used tar products and
Ichthyol, a dermatological drug extracted by distillation of bituminous shales,
particularly near Seefeld, Austria. Blocks of floating asphalt were collected in
the mid-1930s, transported to the Teva Pharmaceutical Industry in Jerusalem and
dry-distilled. An odorous blackish liquid with high boiling point, containing 4.6%
sulphur (by weight), was separated and was labelled bitupal (Bitumen Palestine).
It was used for the treatment of dermatological conditions as pioneered by Prof.
A. Dostrovsky, Hadassa Hospital, Jerusalem. A 30% concentration of bitupal
in zinc paste was used between 1942 and 1957 to treat 298 inpatients suffering
from a variety of skin diseases, such as eczemateous eruptions of several types,
neurodermatitis, psoriasis, pruritus and other conditions (Dostrovsky et al., 1959).
More than 10,000 outpatients were also treated, but were not included in this report.
The conclusions from this study were that bitupal is particularly effective against
resistant dermatoses such as mummular eczema and seborrahic dermatitis, and
beneficial in the treatment of other eczemas. Infantile atopic dermatitis, localised
neurodermatitis and denuded areas of Pemphigus vulgaris also responded very
well to this treatment. The nature of the active ingredient in the bitupal was not
investigated. It was noted that no side effects were observed in the treated patients.
Shannon and Kamnitzer (1959) have made a preliminary clinical evaluation of
bitupal and straight asphalt distillate on pruritus and dermatoses associated with
it, as well as comparing it with tar and steroid treatments. The trial group consisted of 85 patients, and the results indicated that bitupal had a very strong antipruritic effect, equivalent or better than 2.5% cortisone ointment. It also had strong
anti-eczemateous and anti-inflammatory properties with very little side effects.
Sulman (1960) investigated for many years the effect of bitupal on canine
dermatoses. Bitupal, occasionally in combination with other medications, was used

331

BLACK MUD FROM THE DEAD SEA

to treat 100 dogs suffering from various skin diseases. According to Sulman (1960),
all the dogs reacted favourably to the treatment. The advantages of the use of
bitupal are its quick drying action, soothing effect on the skin, its application
to bare skin, requiring no bandaging, and the speedy healing effect. His conclusions were that bitupal is an effective anti-pruritic, anti-eczemteous and antiinflammatory agent with a wide margin of safety.
Thus, the medical applications of Dead Sea asphalt extended over 2000 years,
and it is no wonder that its repute for healing, and in particular for dermatological diseases, continues as of today and that this reputation is being utilised for
commercial endeavours.

2. Geochemical analysis of Black Mud


The total organic carbon content of bulk Black Mud is low at 0.60.8% organic
carbon (Corg ) and is not markedly different from the range of values observed in
other sediments from the Dead Sea (Table II). Therefore, if asphalt is present in the
Black Mud, it must be in very low concentration since the asphalt contains about
80% Corg (Nissenbaum et al., 1980).
TABLE II
Concentration of total organic carbon in Dead Sea sediments
Source of data

Year of
collection

Water depth (m)

Corg (%)

Comments

Neev and Emery (1967)


Nissenbaum et al. (1972)
Nissenbaum et al. (1972)
Anderson et al. (1977)
Levy (1987)

1960 (?)
1965
1965
1975 (?)
ca. 1980 (?)

Up to 2
0.230.25
0.340.40
0.380.87
0.641.00
(average = 0.8)

Oldenburg et al. (2000a)

1998

0.450.81

Oldenburg et al. (2000a)

1998

Not given
810
165330
160330
Various locations.
Mostly in relatively
shallow water
Surface sediment
from shallow water
Black Mud

0.620.78

b
b

a Location unspecified. The value of 2% is quoted as maximum value. The analytical procedure is

not given.
b Organic carbon determined after HCl treatment and drying. Samples run in triplicate.
c Organic carbon determined by combustion and titration. No details of the analytical methods are
given. Some errors may have been introduced by oxidation of sulphides.
d Determined by coulometry. Sediments collected on land, but they represent sub-aquatic sediments
which were exposed due to the lowering of the lake level with consequent receding of the shore line.

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It is appropriate to comment on the scatter of values for organic carbon values


that are reported in Table II. There are three major reasons for this scatter. The first
is that as expected from a narrow, land locked, body of water with very limited productivity, the distribution of organic carbon in the sediments will be quite variable
spatially due to differences in the input of organic matter from the neighbouring
land area due to geographical and physiographical variations. Second, the presence
of large amounts of soluble salts in the interstitial water of the sediments, and
the occurrence of halite and gypsum often requires the thorough washing of the
sediment with water prior to analysis. The sediment is then dried and analysed.
This procedure, however, results in introducing large uncertainty as to the original
weight of the sediment relative to which the organic carbon concentration should
be reported. Third, the presence of poorly crystallised iron sulphides in the sediments that reacts with the oxidising solution often used to estimate organic carbon
content (e.g. Levy, 1980) will produce too high organic carbon values. Taking all
this into consideration, the conclusion is that Dead Sea sediments are impoverished
in organic carbon.
A detailed molecular and isotopic geochemical analysis of Black Mud and
of underlying sediments from the Zeelim formation by Oldenburg et al. (2000a)
indicated the absence of asphalt. For example, the distribution of n-alkanes in asphalt (Figure 1) is typical for petroleum-related products, while the Black Mud
shows an n-alkane distribution which is typical of epicuticular waxes of higher land
plants (Eglinton and Hamilton, 1967). The distribution of n-alkanes in sediment
collected in the central part of the shallow Southern Basin of the lake matches
almost exactly the pattern of the Black Mud, indicating a common source for

Figure 1. Distribution of n-alkanes in Black Mud, surface sediment from the Southern Basin of the
Dead Sea and in floating block of Dead Sea asphalt (data from Nissenbaum, 1969; Rullktter et al.,
1985; Oldenburg et al., 2000a).

BLACK MUD FROM THE DEAD SEA

333

the n-alkanes. Other geochemical parameters such as the distribution patterns of


n-alcohols, fatty acids, sterols and pentacyclic triterpenoids and the carbon isotopic
composition of these compounds conclusively point to the organic matter being
mostly derived from terrestrial higher plants, which were swept into the Dead Sea.
Evidence for a minor contribution by autochthonous organisms was seen by the
carbon isotopic values of phytol and some sterols (Oldenburg et al., 2000a). No
molecular geochemical indicators were found which could be ascribed to asphalt.
The concentration of total sulphur in the Black Mud is around 0.3% (Oldenburg
et al., 2000a). Most of the reduced sulphur was in the form of pyrite, but a considerable percentage was found as metastable iron sulphides and elemental sulphur.
This is different from the findings of Nissenbaum and Kaplan (1976) who did
not detect pyrite or elemental sulphur in surface sediments collected when the
sediments were covered by lake water. Nissenbaum and Kaplan (1976) found that
the reduced sulphur was in the form of AVSs (acid volatile sulphides), presumably
iron sulphides. It is possible that the elemental sulphur and the pyrite are diagenetic
products formed after the sediments were exposed. Sulphur isotopic analysis shows
that the reduced sulphur species were very probably formed by microbiological
activity in the sediments (Oldenburg et al., 2000b) as was also found earlier by
Nissenbaum and Kaplan (1976) for sediments in the shallow and deep parts of
the lake.
The deeply black colour of the sediments is due to the presence of poorly
crystallised iron monosulphide. This is indicated by the simple test of reacting the
sediments with diluted hydrochloric acid. The colour disappears immediately, and
a smell of hydrogen sulphide develops at the same time.
Occasionally, it is claimed in commercial advertisements for Dead Sea Black
Mud that its main therapeutic properties are due to the presence of large amounts
of humic acids that accumulated since the last Ice Age. Analysis by Nissenbaum
et al. (1972) showed that humic and fulvic acids in the sediment from the Southern
Basin constitute less than 0.1% of the dry sediment weight. Even in the deep sediments, the concentration of humic substances is only about 0.2% of the sediment
weight. Those concentrations are well below values that are found in oceanic and
lacustrine sediments.
It has also been claimed that the organic compounds that are medically active in
the sediments are due to contribution from the indigenous algal population of the
lake. This is contrary to the findings of Oldenburg et al. (2000a) who showed that
by far the dominant contribution to the total organic matter is from the watershed
and that indigenous algal contribution is of minor importance.

3. Conclusions
The Black Mud, which occurs in coastal areas of the Dead Sea that were previously covered by lake water, but are now exposed due to the lowering of lake level

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ARIE NISSENBAUM ET AL.

during the last 30 years or so, and which is widely used in therapy and cosmetics,
is basically not different from other recent sediments of the Dead Sea. There is no
geochemical evidence whatsoever for the presence of Dead Sea asphalt in the Black
Mud. The black colour of the mud is due to the presence of poorly crystallised
inorganic iron monosulphide. Neither does it contain significant amounts of humic
substances, which also have been claimed as a reason for the therapeutic properties
of the Black Mud. The curative properties of the Black Mud are probably due to
its high salt content in the hypersaline interstitial brines, the absorption of sunlight
and skin heating by the deep black material and by the interaction of the sulphides
and elemental sulfur with the skin, and not to the presence of asphalt (bitumen) or
any other type of organic matter.

Acknowledgements
The authors are very grateful to Mrs. L. Chernobrov, reference librarian, Wix
Library, Weizmann Institute, for the invaluable assistance in collecting some of
the cited articles.

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