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1 Apatite: Following the movements of ancient humans and mastodons 1 Revision 2 2 3 Matthew J. Kohn 4 Department of Geosciences 5 Boise State University 6 Boise, ID 83725 7 [email protected] 8 9 Abstract: 10 Apatite, found in the teeth and bones of animals and humans, records dietary changes. Analysis 11 of the isotopes of strontium (Sr), combined with geological maps of surface rock type, can be 12 used to reconstruct the places where prehistoric humans and mastodons once lived many 13 thousands of years ago. 14 15 Apatite is a mineral that gives structure to bones and teeth, and can be used to determine where 16 you have traveled based on what you have eaten – apatite records your appetite! Apatite is the 17 most abundant mineral in your body and is composed primary of calcium (Ca) and phosphate 18 (PO 4 ) that are bound together in a rigid crystalline framework (Fig. 1). Joined together with 19 collagen (your body’s most abundant protein), tiny apatite crystals provide the stiffness in bones 20 to support your body and the hardness in teeth to eat tough foods. One reason that we find fossil 21 skeletons of dinosaurs today is because they contain apatite, which is readily preserved for 22 millions of years. 23

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Apatite: Following the movements of ancient humans and mastodons 1

Revision 2 2

3

Matthew J. Kohn 4

Department of Geosciences 5

Boise State University 6

Boise, ID 83725 7

[email protected] 8

9

Abstract: 10

Apatite, found in the teeth and bones of animals and humans, records dietary changes. Analysis 11

of the isotopes of strontium (Sr), combined with geological maps of surface rock type, can be 12

used to reconstruct the places where prehistoric humans and mastodons once lived many 13

thousands of years ago. 14

15

Apatite is a mineral that gives structure to bones and teeth, and can be used to determine where 16

you have traveled based on what you have eaten – apatite records your appetite! Apatite is the 17

most abundant mineral in your body and is composed primary of calcium (Ca) and phosphate 18

(PO4) that are bound together in a rigid crystalline framework (Fig. 1). Joined together with 19

collagen (your body’s most abundant protein), tiny apatite crystals provide the stiffness in bones 20

to support your body and the hardness in teeth to eat tough foods. One reason that we find fossil 21

skeletons of dinosaurs today is because they contain apatite, which is readily preserved for 22

millions of years. 23

2

But apatite is more than just a strong mineral. The ability for elements to substitute in trace 24

quantities for calcium (Ca) and hydroxyl (OH) in apatite (Fig. 1) can provide paleontologists and 25

archeologists with a life-long record of body chemistry. Trace amounts of the element strontium 26

(Sr) provide a special tool for tracking ancient animal movements through analysis of the ratio of 27

two different strontium isotopes1 – 87Sr and 86Sr. So, how does this work? Geochemically, “you 28

are what you eat”, meaning that your body’s chemistry, including the apatite in your skeleton, 29

reflects the composition of the food you eat and water you drink. The food and water that you 30

consume contain trace amounts of the local Sr, and the relative amounts of 87Sr vs. 86Sr 31

geochemically matches local soils and geology because plants take up Sr (and other elements), 32

animals eat plants, and humans eat plants and animals with their loads of Sr. The ratio of 87Sr to 33

86Sr (symbolized by 87Sr/86Sr1) of local geology depends on rock type: old igneous and 34

metamorphic rocks have high 87Sr/86Sr (meaning there is more of the 87Sr isotope relative to 35

86Sr), whereas limestones and young volcanic rocks have low 87Sr/86Sr. So, if an animal moves 36

around during its lifetime, say between areas underlain by limestone vs. old granite where food 37

and water 87Sr/86Sr values are different, the animal’s 87Sr/86Sr ratio will change correspondingly 38

and be recorded in its apatite. These differences, captured in tiny samples of apatite, can be 39

easily measured by a mass spectrometer1. 40

41

Archeologists use these types of micro-Sr isotope changes in bioapatite to reveal ancient human 42

movements. The key here is that different tissues, such as the bioapatite in bones and teeth, grow 43

and match sequential changes in chemistry that occur at different times, much in the same 44

manner that tree rings, for example, grow at different times. So by analyzing different tissues, 45

1 For further detail on these terms, see Nitty Gritty Details at the end of this article

3

and knowing when they equilibrate with the body, an isotopic history of location relative to soil 46

with different 87Sr/86Sr can be developed. A famous application involves “Ötzi,” a mummified47

~46 year-old man who lived about 5000 years ago in the central European Alps (Müller et al., 48

2003). Analysis of his teeth, bones, and intestinal contents reveal that he generally lived within 49

~60 km of the discovery site along Alpine valleys to the south that are underlain by old 50

metamorphic rocks known as gneisses and phyllites, but he also moved around within that area 51

(Fig. 2). Such analyses provide clues about the prehistoric lifestyle of the only human we have 52

found from that time. 53

54

Another study was paleontological. Sr isotope zoning within a fossilized mastodon1 tooth from 55

Florida revealed the annual migration patterns of these elephant cousins (Fig. 2; Hoppe et al., 56

1999), which would have been impossible to figure out any other way. Teeth form from top to 57

bottom (Fig. 2B). In large herbivore teeth, mineralization can require more than one year to 58

complete. So by measuring zoning in teeth, we can identify where an animal lived seasonally, 59

sometimes over multiple years. Zoning in the tooth (Fig. 3) shows that this mastodon mostly 60

lived in areas with moderate 87Sr/86Sr, but occasionally migrated to areas with lower and higher 61

87Sr/86Sr. Local geologic variations in 87Sr/86Sr show that these animals must have migrated at62

least 100 km each year, and perhaps more than 500 km. 63

64

Apatite’s ability to record the geochemistry of past diets provides an important way to study the 65

life history of humans and other animals long after their death. This information helps us 66

evaluate hypotheses about how human cultures evolved, and how ecosystems functioned in the 67

past. 68

4

69

Acknowledgements: 70

This work was supported by National Science Foundation grant EAR1349749. Thanks to Steve 71

Shirey for initiating this project, teachers Tanya Gordon and Julie Ekhoff for comments on an 72

early version, and Dave Mogk, Holly Godsey, and Alex Speer for reviews. 73

74

References 75

Hoppe, K.A., Koch, P.L., Carlson, R.W., and Webb, S.D. (1999) Tracking mammoths and 76

mastodons: reconstruction of migratory behavior using strontium isotope ratios. Geology, 77

27(5), 439-442. 78

Müller, W., Fricke, H., Halliday, A.N., McCulloch, M.T., and Wartho, J.-A. (2003) Origin and 79

migration of the Alpine Iceman. Science, 302, 862-866. 80

See also: 81

82 [1] Elements June 2015 – Volume 11 Number 3 Apatite: A Mineral for All Seasons

[2] Lithographie Monograph No. 17: Apatite - The Great Pretender83

84

85

86

87

88

<http://www.minsocam.org/msa/Lithographie/#Apatite>

Figure 1. Atomic arrangement of apatite, showing locations of calcium (Ca1 and Ca2 sites),

hydroxyl (OH), phosphorus (P) and oxygen (O). Legend shows common elemental substitutions.

Notice that Sr can substitute for Ca. Image and sketch of apatite crystal from a marble from

Canada illustrate underlying symmetry. 89

90

5

Figure 2. Location of Ötzi, a ~5000 year old mummy in the Alps and Sr isotope data that help 91

identify where he lived as a child and as an adult. (A) Different rock types in the region and 92

possible locations where Ötzi lived, based on Sr isotope data. (B) Sr isotope data for materials 93

that record different times in Ötzi’s life: different teeth (childhood), different types of bone 94

(adult), and stomach contents (just prior to death). Values of 87Sr/86Sr discriminate limestone95

(low 87Sr/86Sr) from gneiss and phyllite (high 87Sr/86Sr). Colors correspond with rock types in96

Fig. 2A. Insets show cross-sections of teeth and bone, and timing of growth (teeth) or 97

recrystallization (bone). 98

99

Figure 3. Results of study of Hoppe et al. (1999). Colors correspond with rock types. (A) 100

Southeastern US, showing regions of higher (dark red) vs. lower (light yellow) 87Sr/86Sr. (B)101

Sketch of mastodon lower molar tooth, showing shape, growth direction of a single cusp, and 102

typical sampling strategy used in other studies (black bands, representing the tracks of a drill; 103

Hoppe et al. (1999) used a somewhat different approach based on the same principles). US 104

quarter (similar in size to a euro) for scale. Gray areas on top of four cusps are facets produced 105

by grinding against opposing molars. Inset compares size of mastodon vs. human. (C) Sr isotope 106

zoning in mastodon tooth showing that this animal must have migrated seasonally in the region, 107

possibly as indicated by arrows. Rise in 87Sr/86Sr represents movement to regions underlain by108

igneous and metamorphic rocks, and dip in 87Sr/86Sr represents movement to regions underlain109

by younger sedimentary rocks. 110

111

Nitty Gritty Details: 112

6

Isotopes: Isotopes refer to the different masses of the atoms of an element. The nucleus of a 113

specific element always contains the same number of protons, equal to its atomic number, but it 114

can contain a different number of neutrons. For example, all Sr atoms contain 38 protons, but the 115

four natural varieties can contain 46, 48, 49, or 50 neutrons, making the four isotopes, 84Sr, 86Sr, 116

87Sr, and 88Sr. The superscripts represent the number of protons (38) plus the number of neutrons 117

(46, 48, etc.). The ratio 87Sr/86Sr (“Strontium eighty-seven – eighty-six”) is commonly used as a 118

tracer of rock age or type. 119

Why we use 87

Sr/86

Sr: Although four isotopes of Sr are stable, so do not radioactively decay, the 120

slow decay of radioactive 87Rb makes extra 87Sr. Therefore, rocks can develop a high 87Sr/86Sr if 121

they are old (lots of time for 87Rb to decay), and/or have high Rb contents (shales and granites or 122

their metamorphic equivalents – phyllites, schists and gneisses). Rocks can have low 87Sr/86Sr if 123

they have low Rb, such as limestones and/or basalts, or are very young. Analyzing 87Sr/86Sr124

allows us to discriminate whether an animal got its food and water from an area whose bedrock 125

was old metamorphic and igneous rocks (high 87Sr/86Sr) vs. young sedimentary rocks (low126

87Sr/86Sr).127

Mass spectrometer: A mass spectrometer is a modern analytical instrument that separates atoms 128

with different masses and allows us to measure the amount of 87Sr and 86Sr in a material.129

Mastodon or Mammoth?: Both are members of the order Proboscidea, which included many 130

different representatives in the past, but now is populated solely by elephants. Mastodons had 131

lumpy teeth and ate a lot of leaves and twigs. Mammoths had banded teeth and preferred eating 132

grass. Both died out at the end of the last Ice Age. 133

OH

O

Cl, F

Na, Mg, Sr, Ba

Ca2

Ca1

P C

Figure 1, apatite

Canine enamel

Lime-stone

Gneiss

PhylliteCanine dentine

Enamel(~3 yrs) Enamel

(4-5 yrs)

Canine Premolar Trabecular bone:~10 yrs before death

Cortical bone:~20 yrs before death

Dentine(3-4 yrs)

1st, 2nd premolarenamel

CorticalBone

Trabecularbone Intestinal

Content

87S

r/86S

r

0.721

0.720

0.719

0.718

0.717

0.716

0.715

0.714

0 10 20 30 40 50Biological age (years)

Figure 2, apatite

Austria

Italy

25 kmBolzano

DiscoverySite

PossibleChildhood

PossibleAdulthood

Italy

Switz-erland

Germany

Austria

GneissPhylliteLimestoneVolcanicsGraniteRiver

Innsbruck

A B

ttinnaalatin ltetessetesttInnIntoonneneeonebbbotitiCCCC entetenntteContonontn nentt ne toonoC ntCCCCCCCCacalartic

eeal

ea

onotnene

ro

ccoCoCoCCoB

CBBBo

Coo

Figure 3, apatite

growth

direction

Older

(Y1)

Younger

(Y2)

~5 cm

MastodonSite

FL

GAAL

Igneous andMetamorphic Older sedimentary

Younger sedimentary

87S

r/86S

r

0.707

0.709

0.711

0.713

Position along tooth

YoungerOlder

Year 1 Year 2

100 km?

SC

???????????

LAA AAAGAGAGGAAGG SSCSCSSAAAALLAALAL AAAGAAGGGAAGGGAAAA SSSCSSSCSSSSSCCS A B

C