Society for American Archaeology

Chemical Weathering of Bone in Archaeological Soils

Author(s): E. M. White and L. A. Hannus
Source: American Antiquity, Vol. 48, No. 2 (Apr., 1983), pp. 316-322
Published by: Society for American Archaeology
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RepORtS
CHEMICAL WEATHERING OF BONE IN ARCHAEOLOGICAL SOILS
E. M. White and L. A. Hannus
Weathering of hydroxyapatite,
Ca5(P043
(OH),
in bone
probably
is initiated
by organic
and carbonic acids
formed by
the microbial
decomposition of collagen.
This
weathering, independent of
soil
properties,
is caused
by protons replacing
Ca
from hydroxyapatite.
As
collagen
is
depleted, proton production
decreases and
weathering may
either continue
if protons
are available
from
the soil or be arrested
if
Ca
from
the soil
displaces
the
protons previously
added to the
hydroxyapatite.
The theoretical Ca/P
weight
ratio
of
unweathered bones is 2.15. Weathered bones that have been stabilized
by
Ca
may
have this ratio or a
higher
one
if
extra Ca has been added. A
group of
weathered bones
from
one site with a
slightly
acid soil had an
average
ratio
of 1.67,
which
probably promotes further weathering,
while bone at the same site with an
average
ratio
of
4.09 was less weathered and
apparently
stabilized.
Physical properties
of bones
change
in
recognizable stages
as bones weather
(Behrensmeyer
1978).
These
changes
in the
physical properties
are
contemporaneous
with chemical
changes
which occur in the
organic
and
inorganic
bone constituents. In an aerobic
weathering
environ-
ment suitable for
microorganisms,
the
organic collagen
could be
expected
to weather more
rapid-
ly
than the
inorganic hydroxyapatite
[Ca5 (PO4)3
OH]
which has a low
solubility
in
aqueous
systems
that are alkaline to
slightly
acid. Individual
elongated hydroxyapatite crystals
are
enclosed in a network of
collagen
so that the loss of the
collagen
weakens the
rigidity
of the bone.
The
rigidity
is
greatest
in the dense outer
part
of the bone where the
hydroxyapatite crystals
are
tightly packed
and
weathering
is slowest.
Inorganic weathering
of bone is
mainly
the
weathering
of
hydroxyapatite.
Ca and
P04
ions in a soil solution are in
equilibrium
with those ions in the surface of
hydroxy-
apatite. Hydroxyapatite
loses or
gains
Ca and/or
P04
ions, respectively,
if the solution contains
fewer or more of these ions than can be in
equilibrium
with the mineral. If the solution Ca ion con-
centration is
large,
fewer PO4 ions can be in the
solution,
and the reverse is true if the
PO4
ion
concentration is
large. Thus,
the ratio of the two ions in the solution affects the
hydroxyapatite
solubility
as well as the actual amount of one of the ions.
Hydrogen
ions
(protons)
from acids can
replace
Ca from
hydroxyapatite
so that Ca can be leached from bone
by
soil solutions. This
leaching
would create a
hydrogen-rich, Ca-poor hydroxyapatite, particularly
in the surfaces of
the mineral. However,
if the solution becomes less acid,
Ca could
replace protons
in the
hydroxy-
apatite
and the
original
mineral would be reconstituted. In more acidic soils, hydroxyapatite
weathering may
be increased because
PO4
ions are
precipitated
as Fe and Al
phosphates-
strengite
and variscite, respectively (Lindsay 1979:180).
This removes
P04
ions from the solution
and increases the dissolution of the
hydroxyapatite.
Soils in the Great Plains have
mainly
Ca as
the cation in the solution
phase
so that
hydroxyapatite weathering
is determined
by
the mass ac-
tion
chemistry
of Ca and
PO4
ions. The
objective
of this
study
is to
propose
mechanisms for the
chemical
decomposition
or
preservation
of bone in
archaeological
soils.
E. M. White, Plant Science
Department (Soils),
South Dakota State
University, Brookings,
SD 57006
L. A. Hannus, Sociology Department (Archaeology),
South Dakota State
University, Brookings,
SD 57006
Copyright
? 1983
by
the
Society
for American
Archaeology
0002-7316/83/020316-07$1.20/1
316
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REPORTS
METHODS AND SAMPLE SITES
Bone
fragments
were collected from excavations at
archaeological
sites at Oakwood Lake
(39BK7),
Belle Fourche
(39BU2)
and near the
Lange-Ferguson
site
(39SH33)
from a hearth
former-
ly
buried in calcareous alluvium. All bone
fragments
are from
large mammals,
presumably bison,
which was the dominant
species
at all sites. In
addition,
modern
samples
were collected from the
remains of cows that had drowned two
years
earlier near the
Lange-Ferguson
site.
The Oakwood Lake site
(E
1/2 SE 1/4 NE 1/4 sec
7, T111N, R51W, Brookings County, South
Dakota)
is a three-sided knoll bordered
by
lakes on the west and north and a
swamp
to
the
southeast. The knoll is a kame in Late Wisconsin
(Cary?)
dead ice moraine that was
deposited
in a
preglacial valley.
The area is
nearly
isolated
by
water
except
for the
swamp
and a narrow
tombolo-like
disintegration ridge (Flint 1971)
that extends to an island which in turn is connected
to the shore
by
a second
disintegration ridge.
Because of isolation from fire and the
proximity
to
groundwater,
the area
supported
forest
during
the first
part
of the Holocene and a forest soil
(White
et al.
1969) developed.
Forest soils
characteristically
have a
thin,
dark-colored Al
horizon
underlain
by
a
light-colored platy
A2 horizon and a B horizon with
prismatic
structure that is bet-
ter
developed
than that which occurs in
prairie
soils of an
equivalent age.
The forest soil was the
surface at the beginning of the first habitation; abitation; about A.D. 300 to 600
during the Middle Woodland
period. During and after this habitation, approximately a meter of calcareous eolian sediment
was blown from the
adjacent lake beach and bank. The eolian sediment contains the cultural
horizon and the bones. The lake level, higher during the first
part of the Holocene, decreased
when the outlet stream eroded a
deeper channel. Mixed prairie, probably
with trees
along
the
beach, was dominant
during the second habitation
by horticultural
people after A.D. 1000. More
recently, forest has
expanded into
prairie, possibly because the
precipitation (518 mm [20.4 in-
ches]) is
greater.
The Belle Fourche site
(NW 1/4 SE 1/4 sec 5, T8N, R2E, Butte
County, South
Dakota)
is on a
Pleistocene-age terrace, about 9 m above the Belle Fourche River. Graneros shale, which
underlies the terrace alluvium, is a limb of the Black Hills dome which has been truncated
by ero-
sion. The Dakota
(Lakota) sandstone
hogback lies to the south of the site which is in the transition
zone between the semiarid
plains to the north and the more more humid, forested Black Hills to the
south. Annual
precipitation varies and is and is
commonly reported to be 380 mm
(15 inches), but the
1900-1970
average is about 444 mm
(17.5 inches). A few
ponderosa pine grow along the
escarp-
ment at the
edge of the
floodplain and in favorable
slopes in the
adjacent upland. Because the soil
morphology formed under forest
(White et al.
1969), the area must have been
dominantly forest
when it was inhabited about 1,000 years ago, although it is
prairie today. The cultural horizon
from which the bone
samples were taken is in a 10-15-cm thick eolian-silt
layer which was de-
rived from either the
adjacent floodplain when
vegetation was
sparse or from
point bars
along the
channel. The stream is perennial
today and,
presumably, it would have had a
larger discharge
when forests were more extensive and the climate more humid.
The hearth near the
Lange-Ferguson site
(NW 1/4 SW 1/4 SW 1/4 sec 22, T39N, R45W, Shan-
non
County, South
Dakota) was
recently exposed by erosion of a cliff, 3-4 m
high, formed in
unweathered calcareous alluvium eroded from an
adjacent "badland wall" of
Tertiary siltstone.
Badland basins, which formed
by erosion of
Tertiary-age White River beds, had
only a thin
discontinuous alluvial mantle in the last
part of the
Pleistocene, some 10,000 years ago. At that
time, boreal
vegetation protected steep slopes from erosion so that soils could form. The
weakly
developed soils were eroded and the sediment was
deposited in the
valleys when
prairie became
dominant. This alluviation continued
during the
Hypsithermal and has been
replaced more
recently by rapid erosion with intermittent
filling. The hearth and bones
probably were buried
by
calcareous alluvium that filled a dissected area 1,000 to 3,000 years ago. Intermittent streams in
the area flow
only during rainstorms or when snow melts; they can
change rapidly from
aggrada-
tion to degradation. The annual
precipitation is about 381 mm
(15 inches) and
prairie is dominant
with a few trees
along streams or in favorable
upland positions. Because of the low
precipitation,
slow
leaching, and the short
length of time for soil
formation, soils formed on the alluvial fill have
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AMERICAN ANTIQUITY
very
thin dark-colored
surfaces,
which
usually
are calcareous. The alluvium
probably
was
deposited
near the end of the
Hypsithermal,
but the hearth has not been dated. Soil
samples
were
collected at the sites for
pH
determination with a
glass-electrode pH
meter.
Bone from Oakwood Lake was examined under the
microscope
and classified
by
a
relative,
visual
comparison according
to the nature of the
fragment (cancellous tissue,
dense
compact
outer
part,
or
both), weathering (on
a scale
increasing
from 1
through 8), porosity (1 increasing
through 4),
and charcoal amount in surface
(0, few,
or
many
black
flakes).
The bone was
ground
in
a
micromill,
0.5
g digested
in nitric and
perchloric acid,
and total Ca and P
determined, respec-
tively, by
flame
photometry (Jackson 1958)
and the
colorimetric, molybdate blue,
ascorbic acid
procedure (Watanabe
and Olsen
1965). Organic
matter in the bone was estimated with the
titrimetric
Walkley-Black technique
(Jackson
1958)
that oxidizes
organic
matter in a chromic-
sulfuric acid
system.
The
presence
of carbonates in the bones was estimated
visually by
ef-
fervescence
(Soil Survey
Staff
1951:140,
238)
as observed with a binocular
microscope. Through
a
microscope,
effervescence from small carbonate
fragments
can be observed and
separated
from
bubbling
caused
by
air
displacement
from the bone. Bones from Belle Fourche were
classified as to the bone
part, porosity,
and
superficial
charcoal amount. Bone from the Belle
Fourche and
Lange-Ferguson
areas were
analyzed
for
Ca,
P. and
organic
matter contents.
RESULTS AND DISCUSSION
Oakwood Lake Site
(39BK7)
Bone
hydroxyapatite
contains about 18.5% P and 39.9% Ca. If bone is 70% mineral (Matthews
et al. 1973:188),
unweathered bone should contain 12.95% P and 27.9% Ca. Thus, the theoretical
Ca/P ratio should be 2.15; however, the ratio ranged from 0.97 to 6.89 for the bone at the Oakwood
Lake site
(Table
1). Ratios larger than 2.16 were found only with bone that had a weathering scale
value of 3 or less (Table 1) except for sample 17. The mean Ca/P ratio was 4.09 for samples
2
through 8 and 1.67 for the other
samples.
Bone in
samples
2 through 8 apparently
had been en-
riched in Ca while the other
samples, except for 17, have been impoverished
of Ca. The enriched
samples
may
have been located in the soil zone of
CaCO3
accumulation or below a limestone
peb-
ble where
CaCO3
could
precipitate. Limestone pebbles
in the soil
frequently
have
secondary
CaCO3 pendants on the lower side even though the matrix soil is
slightly
acid. Conversion of
hydroxyapatite
to dahllite [Ca10
(PO4)
CO03],
the apatite common in fossil bone, would not
change
the ratio significantly.
Addition of
CaCO3
would increase the ratio. Effervescence with HCl was
largest
from
samples ground to a small size, even from the
relatively
unweathered cow bones.
This effervescence was not caused by
the evolution of CO2 during the conversion of
CaCO3
to the
CaC12 but was caused
by
the
displacement
of air from the small Haversian canals that permeate
bone. Effervescence from discrete masses of carbonates was not observed, and it is unlikely that
the effervescence was from thin coatings of carbonates in the Haversian canals. In nature, very
small carbonate crystals are unstable and tend to dissolve (Krauskopf 1967) particularly
where
the bicarbonate ion concentration is
greater than in other parts
of the system.
The higher bicar-
bonate concentration would arise from the CO2 released from
collagen
decomposition. Car-
bonate, as a substituent for PO4 ions in the structure, increases apatite solubility because of "its
weakening effect on the bonds in the structure"
(Le
Geros et al. 1967). If
CO3
ions did substitute
for PO4 ions in the structure, the Ca/P ratio would be larger than 2.15. Therefore, samples with a
mean Ca/P ratio of 1.63 must have had Ca replaced
by
protons.
Posner
(1960)
reported that low Ca
hydroxyapatite
occurs in bone, and the Ca/P weight ratio
may
be as low as 1.82 instead of the
theoretical 2.15 ratio. The low Ca
hydroxyapatite
will adsorb bases and release protons
if Ca or
another suitable cation is added.
The different bone porosity groups did not have significantly
different Ca/P ratios
by
analysis
of
variance. Thus, weathering was not directly related to
pore
size. Logically, weathering should in-
crease as the
pore
size increases so that solutions could flow through the bone. Groupings
accord-
ing
to the amount of superficial
charcoal observed also did not have a significant effect on the
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No.
2,19831
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REPORTS
Table 1. Percent
Organic Matter, Ca, and P in Bone Collected
Randomly
from the Oakwood Lake
Archaeologic
Site
(39BK7)
and Bone
Weathering, Porosity
and Charcoal Residue.
Sample
Bone Bone Characteristicsb P Ca
Organic Ca/P
Number Parta
Weathering Porosity
Charcoal Percent Matter Ratio
1 OM 1 2 F 16.0 25.5 8.09 1.59
2 M 1 2 M 8.3 26.5 8.08 3.19
3 M 1 1 0 8.8 26.5 8.00 3.01
4 O 2 2 F 3.7 25.5 _c 6.89
5 0 2 2 F 4.1 22.0 7.61 5.37
6 0 2 2 M 4.4 22.0
-
5.00
7 OM 3 2 F 10.1 24.0 8.04 2.38
8 0 3 2 F 8.1 23.0 8.51 2.84
9 0 3 2 F 15.0 14.6
-
.97
10 OM 4 3 F 15.0 24.9
-
1.66
11 0 4 2 F 12.5 27.0 8.75 2.16
12 OM 4 2 F 15.3 27.0 8.30 1.76
13 0 5 3 F 12.0 21.0 8.14 1.75
14 0 5 2 F 15.6 27.0
-
1.73
15 0 5 3 M 12.7 23.0
-
1.81
16 0 6 3 M 14.8 26.5 8.87 1.79
17 M 6 2 0 11.4 26.5
-
2.32
18 OM 6 3 F 15.0 23.0 8.36 1.53
19 M 7 3 F 15.0 23.0 8.27 1.53
20 0 7 2 F 15.6 31.6
-
2.02
21 0 7 4 0 15.1 22.4
-
1.48
22 M 8 3 0 13.6 21.0 8.83 1.54
23 OM 8 3 F 15.0 21.0 8.79 1.41
24 OM 8 2 F 15.3 21.0 8.05 1.37
Means 12.2 24.0 8.31 2.37
a
OM
equals
outer
part
of bone and cancellous
tissue,
0
=
outer
part,
M = cancellous tissue.
b
Weathering:
1
=
slight
to 8
=
very weathered; Porosity:
1
=
none,
2
=
powder-size,
3
=
salt-size,
4 =
granular;
Charcoal: 0
=
none,
F = few
flakes,
M
=
many
flakes in bone surface.
c
Insufficient
sample
to determine
organic
matter.
Ca/P ratio.
Thus,
either contact with fire did not accelerate
weathering
or charcoal
presence
on
the bone's surface did not indicate a fire treatment.
The
pH
of the eolian mantle at the Oakwood Lake site
ranges
from about 6 to 7.5.
Hydroxy-
apatite
is
relatively
insoluble at the
higher pH,
but the
solubility
increases as the
pH
decreases to
6.5 or
6, and the
solubility
increases
rapidly
below a
pH
of 6
(Lindsay
1979:
181-182). Leaching
of
Ca has occurred because limestone
pebbles
in the noncalcareous eolian mantle are
pitted.
Limestone
weathering
must have occurred when the soil solution was undersaturated with
Ca,
and these same solutions
may
have weathered the bone. Soil beneath the mantle was
developed
under forest and has a
pH
of 5.6 to 5.7. This
pH may originally
have been lower but was increased
by
the
deposition
of Ca leached from the
overlying
eolian mantle. Calcium carbonates must be ac-
cumulating
in the subsoil
today
because
hackberry
seeds had been calcified in the lower
part
of
the mantle at one location
although
the matrix soil is not
strongly
calcareous.
Thus,
the
pH
of both
the buried soil and the
anthropic
zone
probably
was more acid when most of the bone was first
buried. Most of the
weathering may
have occurred before the
upper layers
of the calcareous
eolian sediment were
deposited.
If the Ca or P
percentages
of the 16 more
highly
weathered bone
samples (samples
9
through 24)
are divided
by
the theoretical Ca or P
amounts, the relative removal of Ca and P can be estimated.
The value for Ca is lower
(0.85)
than the value of P
(1.11).
If the estimated
organic
matter content
(Table 1)
is considered in the
calculation,
the ratios are 0.95 and 1.23 for Ca and
P,
respectively.
Ca
apparently
has been
preferentially
leached.
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AMERICAN ANTIQUITY
Belle Fourche Site
(39BU2)
The mean
percentages
of Ca and P
(Table 2)
are similar to those found for the Oakwood Lake
site. The mean Ca/P ratio is 1.77 and
only
two values (2.39 and
2.18)
exceed the 2.15 theoretical
ratio for
hydroxyapatite.
The bone is in a thin eolian
mantle,
10 to 15 cm
thick, that is underlain
by
a forested soil. The flux of Ca
cycled through
the eolian mantle with the bone
probably
has been
less than that at the Oakwood Lake site where a thicker calcareous eolian mantle has accumu-
lated. The bone is in the
superficial layer
where
biological activity, organic
acid
production,
and
leaching
from small rainstorms are
greater
than in the lower soil
layers.
In the
subsoil,
Ca
leached from the
upper layers
is
deposited
to form
secondary
CaCO3
which
may
cause Ca enrich-
ment of the bone.
Weathering
of bone is more active near the surface of the soil at the Belle
Fourche site than for the bone buried to a
greater depth
at the Oakwood Lake site. The initial
habitation at Belle Fourche
probably
was more recent than
1,000 years
B.P. in
comparison
to
shortly
before 1750 + 50
years
B.P. for the Oakwood Lake site.
Thus, weathering
at the two sites
is difficult to
compare
because of the time factor and because the climate is drier and
leaching
less
rapid
at Belle Fourche. The Ca/P ratio was not correlated with the
part
of the
bone, porosity,
or charcoal scale
groupings.
Lange-Ferguson (39SH33)
Area
Samples
of
relatively
unweathered cow bones
and, presumably,
buffalo bones from hearths
that were buried beneath
sediment,
have a Ca/P ratio of 2.16 and 2.18
(Table 3). They probably
contain unweathered
hydroxyapatite.
However,
the
prehistoric
bones were in a deteriorated
state even
though
the Ca/P ratio of 2.18 would indicate Ca has not been
preferentially
leached.
Weathering apparently
had
occurred,
and the Ca/P ratio decreased and increased, respectively,
first as Ca was leached from the bone and second as it was added to the bone
by
soil water
moving
through
the
enclosing
calcareous sediment and bone.
The P content of the unweathered cow bones is much lower than the amount one could
expect
if
"Living
bone consists of about 65-70% mineral"
(Matthews
et al.
1973)
and if the mineral
part
was
mainly hydroxyapatite
(Posner 1960). Hydroxyapatite
contains about 18.5% P.
Thus,
the P
Table 2. Percent
Organic
Matter, Ca, and P in Bone Collected at the Belle Fourche
Archaeological
Site
(39BU2)
and Bone
Porosity
and Charcoal Residue.u
Sample
Bone Bone Characteristicb P Ca
Organic
Ca/P
Number Parta
Porosity
Charcoal Percent Matter Ratio
1 0 1 F 12.4 22.5 10.0 1.81
2 0 2 F 11.0 22.5 - 2.04
3 0 1 0 14.5 22.5 - 1.55
4 0 2 F 14.0 17.5 - 1.25
5 0 2 F 9.6 23.0 10.1 2.39
6 0 1 0 13.7 23.0 11.1 1.68
7 OM 2 F 14.6 23.0 10.4 1.57
8 OM 1 F 13.9 24.5 10.1 1.76
9 0 2 F 16.2 24.5 - 1.51
10 0 1 F 14.9 20.5 10.5 1.38
11 M 2 0 11.7 25.5 - 2.18
12 M 2 F 16.2 31.9
- 1.97
13 M 2 0 15.4 26.1 - 1.69
14 M 2 0 11.5 23.7 - 2.06
15 0 2 F 14.7 24.5 10.1 1.66
16 0 2 F 13.1 24.0 10.3 1.83
Means 13.6 23.7 10.3 1.77
d
See Table 1 for footnote
legend.
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[Vol. 48,
No.
2,1983]
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REPORTS
Table 3. Percent
Organic Matter, Ca, and P in Cow Bone
and in Bone Collected from Buried Hearths
in the Badlands near
Archaeological
Site
(39SH33).
Sample
P Ca
Organic
Ca/P
Number Percent Matter Ratio
Cow bones
(unweathered)
1 12.4 12.0 22.3 0.97
2 9.9 20.5 22.2 2.07
3 5.7 20.5 22.5 3.59
4 8.8 19.0 22.9 2.16
5 11.0 22.0 22.8 2.00
Means 9.56 18.8 22.5 2.16
Bones from hearths
1 8.1 24.5 20.7 3.02
2 11.6 24.5 20.1 2.11
3 11.7 24.5 20.6 2.09
4 11.5 24.5 20.7 2.13
5 11.0 24.5 20.6 2.22
6 13.6 24.5
-
1.80
7 5.6 12.0 -
2.14
8 12.0 23.0
-
1.92
Means 10.64 22.75 20.5 2.18
content of bone that contains 30 to 35%
organic
material should be 12 to 14%. In
comparison,
Sauchelli
(1965) reported
the P contents are 9.4% for raw bone
meal,
14.4% for steamed bone
meal,
15.2% for
spent
bone
char,
and 17.7% for bone ash. The 9.4% value is similar to the 9.6% P
content of the cow
bone,
and the contents after
steaming, charring,
and
ashing
are similar to the
values found for bone collected at the Oakwood Lake site and
probably
result from the loss of col-
lagen.
The 17.7% P for bone ash is about 96% of the 18.5% P content of
hydroxyapatite.
Obvious-
ly,
some
inorganic impurities
would occur in bone.
PROPOSED CHEMICAL WEATHERING SEQUENCE FOR
BONE ENCLOSED IN ARCHAEOLOGICAL SOILS
Chemical
weathering
of bone in South Dakota soils
probably
is initiated
by
acids created as
microorganisms decompose collagen.
Protons from
organic
and carbonic acids
replace
some Ca
in the
hydroxyapatite
structure of bone without
destroying
it. Because of the loss of
organic
material
(Tables 1, 2,
and
3)
and
Ca,
the
average
P
percentage
in bone increased from 9.6% in
unweathered cow bone to 10.6% for the Badlands sites to 12.2% for the Oakwood Lake site and
to 13.6% for the Belle Fourche site.
Hydroxyapatite weathering apparently
can occur inside bone
buried in calcareous sediment because it is not in
complete equilibrium
with the soil. After col-
lagen decomposition
and
CO2 production decrease,
the
CO2 partial pressure
inside the bone
would decrease so that the solution bicarbonate and Ca activities also would decrease. This
would reduce the
gradient
for Ca diffusion out into the soil. Ca in calcareous soils then could dif-
fuse back into the bone and
replace protons
from
hydroxyapatite
to stabilize the
partially
weathered bone. An excess of Ca
may
be added
during
this
stage.
Bone
weathering
can be described as
overlapping
reactions that are controlled
by water, acid,
oxygen,
and Ca contents in the bone and soil.
1. Bone
collagen
is
decomposed by microorganisms
when water and
oxygen
are
present
to form
C02, HCO3
ions, and H
ions,
which in turn react with
321
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AMERICAN ANTIQUITY
2.
Ca5(P04)30H
to form
(Ca5_xH2x) (P04)3(OH)
and Ca ions, which can then react further either
as
3.
C02,
HC03
ions,
and H ions continue to react with the
hydrogen-enriched hydroxyapatite
to
decompose
it to Ca and
HP04 ions,
or
4. Ca ions from the soil solution
replace protons
from the
hydrogen-enriched hydroxyapatite
to
stop
or retard the dissolution of the bone.
The first two reactions could occur inside the bone and are
dependent
on
collagen decomposi-
tion and
independent
of
pH
and ions in the soil
solution,
but the third reaction would
predominate
in acid soils and the fourth in calcareous soils and be
dependent
on soil
properties.
Acknowledgments.
Contribution from the South Dakota
Agricultural Experiment Station, Journal
Paper
Number 1772.
REFERENCES CITED
Behrensmeyer,
A. K.
1978
Taphonomic
and
Ecologic
Information from Bone
Weathering. Paleobiology
4:150-162.
Flint,
R. F.
1971 Glacial and
Quaternary Geology. Wiley,
New York.
Jackson,
M. L.
1958 Soil Chemical
Analysis. Prentice-Hall, Englewood Cliffs, N.J.
Krauskopf,
K. B.
1967 Introduction to
Geochemistry. McGraw-Hill,
New York.
Le
Geros,
R.
Z.,
0. R.
Trantz, J. P. Le
Geros, and E. Klein
1967
Apatite Crystallites:
Effects of Carbonate on
Morphology.
Science 155:1409-1411.
Lindsay,
W. L.
1979 Chemical
Equilibria
in Soils.
Wiley,
New York.
Matthews, J. L., J. H.
Martin, J.
W.
Kennedy, III, and E.
J.
Collins
1973 An Ultrastructural
Study
of Calcium and
Phosphate Deposition
and
Exchange
in Tissues. In Hard
Tissues, Growth,
Repair,
and Remineralization. Ciba Foundation
Symposium 11(n.s.):187-211.
Elsevier,
New York.
Posner,
A. S.
1960 The nature of the
Inorganic
Phase in Calcified Tissue. In
Calcification
in
Biological Systems,
edited
by
R. F.
Sognnaes, pp.
373-394. American Association for the Advancement of Science Publication 64.
Washington,
D.C.
Sauchelli,
V.
1965
Phosphate
in
Agriculture. Reinhold,
New York.
Soil
Survey
Staff
1951 Soil
Survey
Manual. U.S.
Department
of
Agriculture
Handbook 18.
Washington,
D.C.
Watanabe,
F.
S.,
and S. R. Olsen
1965 Test of an Ascorbic Acid Method for
Determining Phosphorus
in Water and
NaHCO3
Extracts from
Soil.
Proceedings of
the Soil Science
Society of
America 29:677-678.
White,
E.
M., J.
R.
Johnson,
and
J.
T. Nichols
1969 Prairie-forest Transition Soils of the South Dakota Black Hills.
Proceedings of
the Soil Science So-
ciety of
America 33:932-936.
322
[Vol. 48,
No.
2,1983]
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