Sedimentation Rate of Salt Determined by Micrometeorite Analysis

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Master's Theses Graduate College

4-1983

James Matthew Barnett

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This Masters Thesis-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Master's Theses by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. SEDIMENTATION RATE OF SALT DETERMINED BY MICROMETEORITE ANALYSIS

James Matthew Barnett

A Thesis . Submitted to the Faculty of The Graduate College in partial fulfillment of the requirements for the Degree of Master of Science Department of Geology

Western Michigan University Kalamazoo, Michigan April 1983

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. SEDIMENTATION RATE OF SALT DETERMINED BY MICROMETEORITE ANALYSIS

James Matthew Barnett, M.S.

Western Michigan University, 1983

The sedimentation rate of the A-l Evaporite of Michigan was

determined by analysis of micrometeorites found as inclusions in

the halite deposit. The samples were obtained from the Dow Chemical

Company salt well number eight. The residue from the dissolved salt

was magnetically separated and later analyzed by Particle Induced

X-ray Emission ( PIXE), X-ray diffraction, and microprobe techniques.

The amount of extraterrestrial material was determined from the

quantity of nickel present.

A sedimentation rate of .01 to .4 centimeters per year was

calculated for the salt based on a constant influx rate of meteoritic 4 material of 1 x 10 tons per year. This sedimentation rate is much

slower than previously reported sedimentation rates for salt. This

relatively slow sedimentation rate and the close association of

hydrocarbons with salt suggests that the original hydrocarbon content

o f petroleum-producing evaporite basins may be much greater than

previously believed.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS

I would like to thank the following without whom this work

would have never been completed. I would fir s t like to thank Dr. W.

Thomas Straw for the idea of this study, and his helpful criticism

as my thesis advisor. Thanks also go to Dr. William B. Harrison I I I

and Dr. John Grace for th eir advice and th eir patience. I would

like to thank the Graduate College for their financial support, Dr.

Steve Ferguson (Western Michigan University) for the PIXE analysis,

Dr. Robert Eisenberg (Western Michigan University) for the use of

the centrifuge, Vivian Schull (Michigan State University) for the

microprobe analysis, Robert Havira (Western Michigan University) for

help in the technical areas and with the photography, Stu McDonald * • (University of Michigan) for aquisition of the core, and to John T.

Parr (Analytical Science Corporation) and Dr. Donald E. Brownlee

(University of Washington) for their advice on the retrieval and

preparation of micrometeorites.

Heartfelt thanks must also go to Dr. Gilbert Klapper (University

of Iowa) for believing in me when no one else would; Kathy Fulker

(Conoco Oil Company) for her unfaltering support of my work; my

folks, T il and Norm, for both economic and mental support; my sister,

Rachel, for ignoring my mess; B ill and Suzanne Gierke and B ill and

Linda Harrison for putting me up; Art and Kathy Williams for putting

up with me; Carol Harkness and family for the typing and the friend

ship; and to a ll the librarians at Western Michigan, the University

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. of Michigan, and the University of Illin o is who helped immensely.

I would like to dedicate this work to Halle, my youngest, whose

death and rny pride were the driving force in the final compilation

o f this work.

James Matthew Barnett

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University Micrcxilms International 300 N. Zeeb Road Ann Arbor, Ml 48106

BARNETT, JAMES MATTHEW

SEDIMENTATION RATE OF SALT DETERMINED BY MICROMETEORITE ANALYSIS

WESTERN MICHIGAN UNIVERSITY M.S. 1983

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ACKNOWLEDGEMENTS ...... ii

LIST OF FIGURES ...... vi

LIST OF TABLES ...... v ii

INTRODUCTION TO EVAPORITES ...... 1

Economic Significance of Evaporites ...... 1

Previous Work...... 4

Geochemistry ...... 5

Laminations in Evaporites ...... 8

Geological Setting ...... 13

Michigan Basin Model ...... 17

A-l Evaporite Deposition...... 18

INTRODUCTION TO MICROMETEORITES ...... 21

Previous Work ...... 21

Ori gi n of the Spheres ...... * 24

Volcanic O r i g i n ...... 25

Industrial Origin ...... 26

Biologic Origin ...... 26

Inorganic Precipitation ...... 27

Extraterrestrial Origin ...... 27

MICROMETEORITES IN SEDIMENTS ...... 30

Laboratory Procedure ...... 32

Non-Magnetic Fraction ...... 34

Magnetic Fraction ...... 34

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. X-Ray Diffraction Analysis ...... 37

Microprobe Analysis ...... 37

RESULTS ...... , 39

PIXE Results ...... 39

X-Ray Results ...... 47

Microprobe Results...... 48

SUMMARY ...... 49

Discussion ...... 49

Influx ...... 51

Differential Transport ...... 52

Calculations ...... 53

CONCLUSIONS ...... 56

APPENDIX A: Petrographic Descriptions and Photographs of Core Samples ...... 58

APPENDIX B: Weight of Samples ...... 66

APPENDIX C: Total PIXE Results ...... 67

APPENDIX D: PIXE Results Versus Meteorite Composition . . . 73

BIBLIOGRAPHY ...... 75

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF FIGURES

Fi gure Page

1. Location of Dow Chemical Company well and thickness of A-1 Evaporite ...... 14

2. Strati graphic col umn ...... 16

3. Micrometeorite in salt sample 8568 ...... 22

4. Micrometeorites showing possible alteration .... 22

5. Frantz magnetic separator set-up ...... 33

6. Typical PIXE pellet for analysis of the non-magnetic fraction ...... 33

7. Apparatus used to make PIXE targets for the magnetic fraction ...... 35

8. Individual column used in making PIXE targets . . . 36

9. Cross-section of PIXE target ...... 3 6

10. Iron variation in the samples ...... 4 0

11. Nickel variation in the samples ...... 41

12. Copper variation in the sam p les...... 42

13. Zinc variation in the samples ...... 43

14. Sedimentation rates of the samples ...... 55

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES

Table Page

1. PIXE results of the magnetic fraction ...... 44

2. Constants used for sedimentation rate determinations ...... 53

3. Amount of extraterrestrial material in the samples ...... 54

v ii

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. INTRODUCTION TO EVAPORITES

Marine evaporites are known from virtu ally every geologic

period of the Phanerozoic (Schmalz, 1969), and are relatively

abundant sediments in the geologic column (Krumbein, 1951). Even

though they are relatively common, their deposition is incompletely

understood. The problems associated with such an understanding w ill

be discussed at length.

According to Holser (1979a) the important minerals present in

marine evaporite deposits and th eir order of precipitation are

calcite and dolomite, gypsum and anhydrite, halite, and certain

potassium and magnesium-bearing minerals (usually sylvite and

carn allite). The present study is mainly concerned with halite and

its rate of deposition. To understand the deatai.ls.of halite

deposition one must understand the physical-chemical framework

required for evaporite deposition in general.

Economic Significance of Evaporites

Evaporite deposits are economically significant for several

reasons. They are the most important supply of the world's

requirement of the following elements: alkali elements, sodium and

potassium; and halogens, chlorine and bromine (Selley, 1978).

Evaporites also appear to play an important part in the generation

and accumulation of o il. Moody (1959) pointed out that 44 percent

of major petroleum-producing areas show significant association

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. between evaporites and petroleum reserves. Kozary et

suggested that this association is due to one or more of the

following reasons: environmental factors common to both (for

instance, reducing conditions), variety of structural traps related

to salt mobility, and the excellence of evaporites as sealing and

cover strata.

Peterson and Hite (1969) discussed several reasons why the

Paradox Basin evaporites are associated with hydrocarbons. Several

of the reasons could easily be applied to the Michigan Basin. They

are: conditions were optimal for accumulation and preservation of

organic matter, a large part of the organic matter was transformed

to hydrocarbons, dolomitization occurred increasing porosity, and

possible salt tectonism which could fracture the adjacent rocks

(which would also increase porosity).

Peterson and Hite (1969) suggested that hydrocarbon inclusions

in halite imply in situ generation and are relatively common (as in

the Michigan Basin). These inclusions also suggest that the hydro

carbons found in the basin may be predepositional and may have been

in solution in the brine, or they may be the breakdown products of

organic compounds which were in solution in the brine (Peterson and

Hite, 1969).

Several factors control the association of evaporites and the

accumulation of organic matter. One of them is the fact that because

evaporite facies have a high salinity only a few species are able to

survive, but those that can tolerate the high salinities exist in

great profusion (Kirkland and Evans, 1981). Peterson and Hite

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. (1969) also addressed this phenomena when they pointed out that

oceanic circulation patterns which bring about the deposition of

evaporites also function to cause the accumulation of organic

matter. I f the currently accepted model of the Michigan Basin is

correct and a broad, shallow shelf encircled the basin, then water

moving over the shelf should have had a higher organic matter

content due to the great productivity in the warm, well-lighted

waters of the shelf. The organic matter thus produced could have

been swept into the basin (Peterson and Hite, 1969).

Evaporites not only play a role in the accumulation of organic

matter, but also play an important part in the subsequent breakdown

of organic matter which makes them a possible source rock. Peterson

and Hite (1969) suggested that the evaporite environment may play

a direct role in hydrocarbon generation and accumulation. They

arrived at this conclusion because certain basins with large

accumulations of petroleum apparently contain no source beds (Kirk

land and Evans, 1981). i * As brine concentration increases stratificatio n of the brine

occurs. This creates reducing conditions in the bottom waters

which preserves organic matter. With this preservation and subse

quent alteration of organic matter to hydrocarbons, a rich source

rock may result (Kirkland and Evans, 1981). If evaporites can

truly be considered a good source rock, then several prerequisites

must occur. Woolnough (1937) discussed these prerequisites, and

none of them seem to conflict with the present interpretation of

the Michigan Basin. The prerequisites are as follows: the organic

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. matter should not be excessively diluted by sediment; the organic

matter should be the type that readily yields o il; the organic

matter should not suffer complete microbial destruction during

sedimentation and early diagenesis; and the organic matter should

be diagenetically changed to oil (Kirkland and Evans, 1981).

Previous Work

The earliest work done on evaporite sediments was that of

Usiglio in 1849. He allowed five lite rs of Mediterranean Sea water

to dessicate while taking note of the minerals that formed and the

sequence in which they formed. A similar experiment was performed

by Van't Hoff and Weigert in 1901 (Selly, 1978).

These studies demonstrated the two main facts that have since

been a problem in understanding the deposition of evaporites.

These facts are: (1) inconceivable quantities of seawater would be

necessary to form the observed volumes of evaporites (assuming the

simple "evaporating dish" model), and'(2) evaporite assemblages in

the rock record d iffe r from those produced by simple evaporation of

seawater (Selley, 1978).

The geochemistry of marine evaporites was best summarized by

Holser (1979a, 1979b). Previous to this work, Clarke (1924) and

Stewart (1963) were often cited as authoring the most important

geochemical works concerning evaporites.

Two important papers concerning the A-l Evaporite of Michigan

are those of Dell wig (1955) and Matthews and Egleson (1974).

Dellwig dealt mainly with the petrology of the A-l Evaporite, while

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Matthews and Egleson discussed the presence and implications of

potash in the A -l Evaporite. Their model of evaporite deposition

in the Michigan Basin is one of the best in the literatu re.

General work on evaporites have been done by a number of

people in recent years. Hsu (1972a) presented a good discussion and

review of the models of evaporite deposition. Hardie and Eugster

(1971) and Shaw (1977) discussed and advocated a shallow-water

formation model, whereas Schmalz (1969) expounded a deep-water

formation model. Another important point of view is that of

Shearman (1966, 1970b). He thought that alteration played an

important part in halite deposits. »

Geochemistry

A complete understanding of evaporite deposition is d iffic u lt

because the axiom of uniforitarianism "the present is the key to

the past", does not help when one considers thick halite deposits

because there is no "present" (Dellwig and Evans, 1969).

Even though much work has been done since Branson (1915)

stated four major problems of thick salt deposits, questions

concerning these problems remain. The problems Branson (1915)

mentioned are as follows: (1) i f a simple evaporating model is

imposed, then the extremely great depth of water required must be

explained; (2) lack of alteration in the salt; (3) thick deposits

of salt that are not underlain by gypsum; and (4) the absence of

fossils in the deposits.

It is now generally accepted that salt deposits were not

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. formed simply by an evaporating dish model. Abandonment of this

idea and the concept of refluxion of less concentrated brine (King,

1947) obviates problem three. The lack of fossils in salt deposits

may be explained by the fact that animals that can survive high

salinities today do not generally have hard parts and could not be

easily preserved in the rock record. I f animals were present when

the A-l Evaporite was being deposited, then they lik e ly lacked hard

parts. Not much light has been shed on the lack of alteration in

salt. Although it is generally assumed that not much alteration or

diagenesis has occurred in thick bedded salt deposits. Shearman

(1966, 1970b) has been an advocate for diagenesis of salt deposits

as a rule, rather than an exception, but this idea is not widely

accepted.

I t is generally accepted that evaporitic limestones and

dolostones, calcium sulfate (anhydrite and gypsum), h alite, and

minor amounts of potassium salts represent deposits from seawater

under restricted environmental conditions (Krumbein, 1951). These

deposits commonly form when a body of seawater is restricted from

free circulation. Along with restricted circulation, high net

evaporation rates are usually imposed, and clastic influx is

generally low. Hardie-and Eugster (1971) mentioned that in the

later stages of evaporation, leading to halite and potash deposits,

it appears that direct jn_ situ precipitation from brines becomes

more important and clastic processes diminish. As the water

evaporates a brine forms which continues to be reduced in volume.

The concentration of certain ions increases until the solubility

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. product is reached. When the solubility product is reached, the

mineral precipitates. Salts precipitate in a sequence that is

mainly dependent on relative so lu b ilities, temperature, and pressure.

As each mineral precipitates, a new mineral facies is formed. A

facies in evaporites is distinguished not by the proportion of the

minerals, but by the first appearance of a mineral. For instance,

to be in the halite facies, a rock is required to contain any

amount of halite (Holser, 1979b).

The conditions and rates of reaction change almost continuously

as seawater evaporates. This must be considered when analyzing

geochemical data. The shortcomings of most work in the geochemistry

of evaporites appears to be two-fold: i t is not always possible to

recreate natural environments in the laboratory (especially when

those conditions do not exist today), and many times analyses tend

to simplify conditions to the point where any results are meaning

less. A number of factors should be considered when studying

evaporites, these include: as seawater evaporates and brine density

increases, the evaporation rate decreases due to a change in heats

of solution (Stearn and Smith, 1920); once saturation of the brine

has been reached, the rate of precipitation of the mineral is simply

related to the rate of evaporation of the water (Holser, 1979b); i f

the brine is concentrated to the point where evaporation equals the

vapor pressure of the water in a ir , evaporation stops altogether

(Holser, 1979b); and incoming solar radiation increases brine

temperature faster than normal seawater. This effect is accentuated

if a layer of fresh-water overlies the brine. The fresh-water does

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. not absorb the ultraviolet as effectively as the brine, but can

absorb the far infrared. This creates a "greenhouse effect" that

heats the brine rapidly as demonstrated by Hudec and Sonnenfeld

(1974) in La Rogues, Venazuela.

During the Phanerozoic most elements in seawater have remained

relatively constant (Holser, 1979b). Rubey (1951) suggested that

the composition of seawater in the Salina was essentially that of

modern seawater. This was discussed by Holland (1972) when he noted

that the constancy of the mineralogy of evaporites (and the order in

which they form) has not changed through geologic time. The

composition of ancient seas was determined by Holser (1963) who

studied the brines entrapped in microscopic cavities in halite. He

determined that the entrapped brines had the same ionic ratios as

present evaporating seawater.

Laminations in Evaporites

Kay (1955) noted that many sediments are layered, but i f i t is

assumed that such layers accumulate annually then the depositional

time must be unreasonably short. A formation of sedimentary rock

is not a steady accumulation of detritus, but the end result of

preservation of layers formed in short periods separated by long

spans of sparse or no deposition (Kay, 1955).

German geologists refer to the relatively thick halite bands

separated by paper-thin anhydrite as ".iahresringe" (Selley, 1978).

These anhydrite laminations may have associated dolomite and/or

organic matter (Dellwig, 1955). A wide range of thicknesses exist

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. in these layered halite rocks (Dellwig, 1955; Kaufman and Slawson,

1950). Dellwig (1955) reported the halite layers to range from

.4 to 8 centimeters in the Michigan Basin. Briggs and Lucas (1954)

reported the average halite layer to be 20 millimeters thick, with

the anhydrite laminae averaging .5 millimeter. Dellwig (1955)

discussed banded salt deposition in the Michigan Basin. He

concluded that there was no uniform (or cyclic) relationship between

the laminae and the salt. The depositional surfaces at the base of

the laminae ranged from smooth to highly irregular. The smooth

surfaces appear to be due to solution effects. Carbonaceous

material and pyrite were both associated with the laminae, but

dust-like and extremely fine dendritic masses of hematite are

associated with the salt layers (Dellwig, 1955). Some pyrite

crystals are contained within the s a lt, but Dellwig presumed that

they had settled out of newly deposited laminae. This may actually

represent the alteration of extraterrestrial dust particles.

Krumbein and Garrels (1952) showed that for anhydrite deposi

tion to occur a basin must establish reducing conditions. Such

conditions can occur when seawater influxes into the basin, and

may explain why a majority of the pyrite is associated with

laminae.

Kaufman and Slawson (1950) stated that l i t t l e lig h t had been

shed on whether or not the laminae were annual or seasonal. This

statement seems to be valid today. Much has been written on the

nature of the laminations, but very l i t t l e has been widely accepted

as a possible mechanism for their origin.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Udden (1924) was one of the fir s t to study laminations in

evaporites. He studied laminations in anhydrite and observed that

the laminations may be due to periodic refreshening o f the brine.

Many others have since come to the same conclusions that these

laminations are due to the presence of less concentrated waters in

the basin (Briggs and Lucas, 1954; Dellwig, 1955; Krumbein, 1951;

Schmalz, 1969; Wardlaw and Schwerdtner, 1966). Zen (1960) pointed

out that monomineralic deposits of evaporites hundreds of feet

thick require that the hydrologic, climatic, and bottom conditions

remain the same (more or less) for a long period of time. The

interlaminations show that periodic fluctuations of environmental

conditions can occur.

Dellwig (1955) stated that the laminae deposition is indepen

dent of the deposition of the associated salt. Wardlaw and

Schwerdtner (1966) noted that the change from halite deposition to

anhydrite deposition.must be due to a change in the basin waters

at the time of deposition. Such changes in basin water could have

been caused by either changes in temperature or composition of the

basin water.

The jahresringe concept does not adequately explain the layers

within layered evaporitic rocks that are much too thick to have

been deposited in a single year. Adams (1944) reported that the

thickness of an individual jahresringe could be as great as four

feet. Some of these excessively thick jahresringe have the same

two-layer structure that the thinner ones have, so they must be

amendable to the same explanation (Shaw, 1977).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 11

The jahresringe concept, i f correct, is a major problem in

the shallow-water model of evaporite origin. The amount of subsi

dence required to keep the basin as a negative feature (and not

f i l l up with sediments) is approximately five centimeters per year

(Selley, 1978). Such a rate of subsidence is greatly in excess of

even the most diastropic setting (Selley, 1978). I f the concept of

jahresringe is correct, the basin must have originally been deep

(Selley, 1978).

Most of the literatu re on laminae have approached the problem

as if the jahresringe concept is false, and that the evaporites

formed in shallow water. I f the jahresringe concept is proven false,

this does not neccesarily disprove a deep-water hypothesis. Shaw

(1977) said that laminations could form in either deep, or shallow

water, and that they give no evidence to support either one.

Although the fact remains that i f these layers are actually annual

deposits, then the shal1ow-water advocates are faced with a problem

in explaining the subsidence in the basin.

Kaufman and Slawson (1950) pointed out that the vertical

spacings of the anhydrite laminae varied with no regularity. Dellwig

(1955) explained that the thickness of these layers gave only a rough

approximation of the salt deposited annually. He thought that a •

single season of high temperatures might bring about solution of the

salt previously deposited, and that severe storms might disrupt the

brine density stratification which would affect the layer's thick

ness. Dellwig (1955) also thought that i f seawater flowed into the

basin that its affect would vary considerably with the season during

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. which i t was added. The idea that these laminations are not annual

was best argued by Shaw (1977).

Kaufman and Slawson (1950) noted that within the bands of

halite there are commonly thin lamellae of anhydrite which are

not associated with the thicker jahresringe laminae. They took

this to mean that the environmental changes were much more frequent

than that suggested by the dark bands (jahresringe laminae). This

increases the doubt that these laminae are truly annual. Anderson

and Kirkland (1966) in looking at banded gypsum noted that one

cannot in fer the thickness of an anhydrite layer i f he knows the

thickness of the adjacent layer. This is in contrast to the

relationships in true varves where a thick summer layer implied

a thin winter layer (Shaw, 1977). There is also a problem with

"extra layers" in some of these banded evaporites (Shaw, 1977).

These "extra layers" are better explained i f we accept that the

alternations of evaporites are due to alternations of evaporite

environments without annual control (Shaw, 1977). Hardie and

Eugster (1971) studied the Gessoso-Solfifera Formation which

consists of laminated gypsum and concluded that current transport

and deposition (rather than annual precipitation) were the dominant

depositional processes. They thought the laminae represented storm

layer deposits.

Along with Hardie and Eugster (1971), Braitsch (1963), Phleger

(1969), and Shaw (1977) concluded that these layers do not represent

annual deposits.

I t must be kept in mind when studying laminated evaporites

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. (whether they be anhydrite, gypsum, or halite) that the interpre

tation of these laminae as being annual accumulations is based on

the requirement that every lamination is seasonally controlled, and

i f some laminae are determined to reflect more than one year's

deposition, then the entire argument for these laminae to be

considered varves collapses (Shaw, 1977).

Geological Setting

The Michigan Basin (Figure 1) is a broad structural and

sedimentary basin some 450 miles in diameter (P irtle , 1932). It

has a slight elongation in a northwest-southeast direction that is

more evident in the older formations, and the younger formations

show a more circular form (P irtle , 1932). The rocks dip toward

the center of the basin at approximately 30 to 35 feet per mile

(Pirtle, 1932).

The Early Silurian (Alexandrian) sediments of the basin

represent normal marine conditions over a relatively undifferen

tiated shelf, although Upper Ordovician deposits in the basin do

thicken towards the center of the basin (personal communication,

W. Thomas Straw). Dellwig (1955) stated that the basin was isolated

in the Middle Silurian (Niagaran). Pronounced negative tendencies

occurred in the basin, a peripheral reef complex developed, and a

penesaline environment was established (Sloss, 1953).

In the late Middle Silurain the basin attained its maximum

re lie f (Droste and Shaver, 1977). Penesaline, saline, and hyper-

saline environments all existed. These environments were p a rtially

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 14

200

300

DOW WELL NO. 8

100

SCALE (m iles)

Figure 1. Location of Dow Chemical Company salt well No. 8 and approximate thickness of the A-l Evaporite of the Michigan Basin (a fter Mesolell a et a ! ., 1974).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission due to the reef complex surrounding the basin (Sloss, 1953). During

this time the basin was characterized by deposition of alternating

evaporites and carbonates (Droste and Shaver, 1982). The evaporites

deposited during the late Middle Silurian are the earliest Silurian

evaporites deposited in the basin (Dellwig, 1955). These evaporites

are the units that w ill be investigated in this study. The Salina

Group is a sequence of evaporites, carbonates, argillaceous carbon

ates, and shales (Elowski, 1980), and encompasses strata from the

base of the A-l Evaporite to the top of the G-Shale (Figure 2). In

Late Cayugan time the basin was fille d and there was renewed spread

of open-circulation of marine waters over previously differentiated

areas (Droste and Shaver, 1977).

In the center of the basin, the A-l Evaporite is the lowest

unit in the Salina with a depth of slightly more than 9,500 feet

(Dellwig, 1955). The A -l Evaporite generally overlies the Niagaran

throughout the Michigan Basin, but where the A-l Evaporite is not

present the A-l Carbonate lies directly on the Niagaran (Elowski,

1980). The A-l Evaporite is composed of the A-l Salt and the A-l

Anhydrite, although they do not coexist everywhere in the basin

(Elowski, 1980). The thickest section of the A-l Evaporite (maximum

thickness of 500 feet, Matthews, 1970) are almost entirely salt with

a small amount of anhydrite at the base (Elowski, 1980).

The A-l Evaporite is overlain by the A-l Carbonate, which is

in turn by the A-2 Evaporite. The A-2 Evaporite is overlain by the

A-2 Carbonate which is overlain by the B-Salt which is predominately

salt (Figure 2).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 22

Figure 3. Micrometeorite from salt sample 8568 residue (x40).

Figure 4. Micrometeorites showing possible alteration to magnetite crystals from salt sample 8150 residue (x45).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 16

'DOMINANT LITHOSTRATIGRAPHIC UNIT LITHOLOGY

BASS ISLANDS GROUP (UNDIFFERENTIATED)

G-SHALE

'< F-EVAPORITE 1 O'

E-UNIT

a. D-EVAPORITE

C-SHALE

B-EVAPORITE

A-2 CARBONATE

A-2 EVAPORITE

Q£ A-l CARBONATE

00 A-l EVAPORITE a

NIAGARA GROUP (UNDIFFERENTIATED)

Figure 2. Strati graphic column.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Most of the samples processed were from the A-l Evaporite,

although some of the samples were from the A-2 Evaporite and the

B-Salt.

Michigan Basin Model

Lucas (1954) concluded that the A-l Evaporite was deposited

in a basin that had a water depth of at least 130 feet. With a

depth this great most of the basin would have been under the affect

of both density and thermal stratificatio n (Lucas, 1954).

The environmental control of the Michigan Basin was mainly

due to the ring of reefs that surrounded i t (Krumbein, 1951).

This reef bank restricted the Michigan Basin from open marine

conditions. Briggs and Pollack (1967) in using a computer simulated

deposition model concluded that a model incorporating radial influx

around the entire Michigan Basin approximated the depositional

bull's-eye pattern that is present. Sloss (1953) stated that the

cratonic basins are usually subsiding while evaporite deposition

is taking place, particularly when the volumetrically large

evaporite deposits are being produced. Krumbein (1951) explained

that rings of reefs may form along the edges of a basin undergoing

subsidence, which would re s tric t the inner basin from the open sea

except through narrow inlets. These concepts, radial influx,

subsiding basin, and a ring of leaky reefs around the periphery of

the basin a ll appear to be applicable to the Michigan Basin.

Although there were a number of environments present in the Michigan

Basin during the Silurian, the ones of most interest in this study

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 18 are the saline and supersaline (hypersaline). Sloss (1953) defined

the saline environment as the environment which precipitates

chlorides, while carbonate deposition is minimal to nonexistent.

This represents a restricted environment. The supersaline environ

ment was defined as that environment in which restriction is so

complete that potash salts are deposited. The existence of this

environment in the Silurian rocks of the Michigan Basin was fir s t

recognized in the A-l Evaporite by Anderson and Egleson in 1966

(Matthews and Egleson, 1974), although i t had been postulated by

Grabau in 1915.

There are noticeable differences between the A-l salt deposited

around the edges of the Michigan Basin, and the salt deposited in

and near the basin center. The most pronounced difference is the

presence of clear salt-cloudy salt banding in the center of the

basin, but i t is noticeably absent from the basin margin deposits

(Dellwig, 1955; Dellwig and Evans, 1969). Although the marginal

salt does not have the clear salt-cloudy s a lt banding, i t does

contain minor unconformities, ripple marks, and well-defined

anhydrite-dolomite laminae (Dellwig and Evans, 1969). The anhydrite—

dolomite laminae in the center of the basin are neither as thick,

nor nearly as well-defined as those of the basin margin.

A-l Evaporite Deposition

The A -l Evaporite was deposited in a basin that was undergoing

subsidence. The center of the basin was covered by at least 130 feet

of water (Lucas, 1954) during most of A-l Evaporite deposition. The

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. maximum depth of the basin during Salina time is d iffic u lt to

determine due to the lack of time lines through the reefs and evap

orites, but a maximum depth o f less than 1,000 feet is presumed.

Matthews and Egleson (1974) thought the later salts were deposited

in a shallower basin than the A-l salt because they believed that

the basin was progressively fillin g with sediments. These later

salts (A-2 salt, B-salt, D-salt, and F-salts) show low bromine

contents which Matthews and Egleson (1974) thought represented

"re-dissolved, second generation, bromine-deficient halite", which

had been derived from preceding evaporite cycles.

A-l Evaporite deposition has been termed "cyclic" (Dellwig,

1955; Matthews and Egleson,. 1974). A complete evaporite cycle

requires a dessication phase to deposit increasingly soluble

minerals, and a dilutional phase (due to an influx of less saline

water) which precipitates minerals in order of decreasing solubility

(Matthews and Egleson, 1974; Stewart, 1963). During a complete

evaporite cycle the most soluble salts should be precipitated in the

middle of the cycle. The soluble salts are found in the middle of

the A-l Evaporite in a lenticular-shaped deposit (except in the north

and northeast) surrounded almost entirely by halite (Matthews and

Egleson, 1974). In the north and northeasterly sections of the basin

the potash lens is overlain directly by A-l Carbonate. Matthews and

Egleson (1974) thought that this unconformity was due to dilution

of the brines within the basin, and concomitant solution of the

potash lens. They thought this dilution coincided with the fir s t

signs of refluxion in the basin. This dilution coupled with

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. refluxion of brine containing potash salts reversed the cycle to

halite deposition. Matthews and Egleson (1974) thought a rise in

sea level "trapped" the halite-depositing brine by covering the

enriched brine with water and halting the evaporation of the brine.

This allowed carbonate (A-l Carbonate) deposition to occur.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. INTRODUCTION TO MICROMETEORITES

Nordenskjold (1874) was apparently the firs t person to publish

information concerning micrometeorites, but perhaps the firs t

important work was the collection in 1876 of micrometeorites by

Murray while on the H.M.S. Challenger expedition. Murray and Renard

(1883, 1891) suggested that these materials represented ablation

debris from meteoroids as they entered the atmosphere. Murray and

Renard (1891) separated the spheroids into two distinct groups.

They assigned shiny, black spheroids composed mostly of magnetite

to type I (Figures 3 and 4 ). Brown spheroids which they thought

appeared to have been formed by the ablation of stony meteoroids

were assigned to type S (Brownlee, 1979). The spheroids investigated

in the present study were the magnetic fraction of type S spheroids

and type I spheres.

Previous Work

Very l i t t l e work was done from the time of Murray and Renard's

(1891) work to the middle of the twentienth century. Interest was

renewed following a paper by Whipple (1950) in which he mathe

matically predicted the existence of micrometeorites. Scientists

from Sweden and Denmark collected micrometeorites from sea sediments

in the 1950's and research concerning these "cosmic" spheres

accelerated rapidly (Brownlee, 1979).

Many collections of micrometeorites have been made since 1950,

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. and a number of collection methods have been employed: (1) The

micrometeorites were gathered while they were s t ill in the

atmosphere by balloon, airplane, or satellite. The following

investigators used this technique: Carr, 1970; Crozier, 1962;

Kornblum, 1969b; Fireman and Kistner, 1961; Hodge and Wildt, 1958;

A1 e-xander et al_., 1973; Brownlee et a l., 1968; Parkin e rta K , 1959;

and Rajan et al_., 1977. (2) The spheroids were collected from

polar ice. This was done by: Marshall, 1959; Schmidt, 1963a, 1964;

Brocas and Picciotto, 1967; Giovinetto and Schmidt, 1965;

Frederiksson and Martin, 1963; Thiel and Schmidt, 1961; and Hodge

et a l., 1964. (3) Micrometeorites were extracted from marine

sediments by: Finkelman, 1970, 1972; Frederiksson, 1956; Opik, 1955;

Skolnick, 1961; Frederiksson and Martin, 1963; Hunter and Parkin,

1960; Laevastu and Mellis, 1955; Millard and Finkelman, 1970;

Petersson and Fredriksson, 1958; Blanchard et a]_., 1980; Bruun et a l.

1955; Ganapathy et a]_., 1978; and Grjebine et , 1964. (4) Micro

meteorites were extracted from consolidated sediments by: Crozier,

1960; Erskine, 1959; Mutch, 1964a, 1966; Parr, 1966; Hunter and

Parkin, 1961; Ivanov and Florenskiy, 1968; and Marvin and Einaudi,

1967.

Several studies comparing the spheres to other materials have

been done. Handy and Davidson (1953) considered the black magnetic

spheres collected from rainwater to be mostly fly-ash but thought

the presence of nickel in other spheres suggested extraterres

tria l ity.

Hodge and Wright (1964a), Wright and Hodge (1965) and Del Monte

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. et al_. (1975) compared presumed extraterrestrial spheres to black

magnetic spheres found in volcanic material. They concluded that

due to aluminum depletion in the extraterrestrial spheres, and

structural differences in crystallography that the volcanic spheres

are neither "morphologically nor structurally analogous".

Influx of extraterrestrial material has been reported by:

Crozier, 1961; M illard, 1963; Millman, 1975; Schmidt, 1963a;

Thomsen, 1953; Yokoyama, 1968; Brocas and Picciotto, 1967; Hodge

and Wright, 1968; and Parkin and T ille s , 1968.

Most authors have discussed some aspect of the chemical

composition of meteorites. The following papers deal primarily

with the composition of micrometeorites: Merrihue, 1964; Blanchard

and Cunningham, 1974; Blanchard and Davis, 1978; Castaing and

Frederiksson, 1958; Fechtig and Utech, 1964; Lai and Venkatavaradan,

1967; Millard and Finkelman, 1970; Schmidt and K eil, 1966; Wright

and Hodge, 1964; Brownlee et a l., 1974; Del Monte et al_., 1975;

Ganapathy et a l., 1978; Hodge et a l., 1967; Rajan et a]_., 1977;

Shimamura et a l., 1977; Smales et a l., 1958; and Wright et a l.,

1963.

Origin of the Spheres

The studies done in the last th irty years have suggested

several origins for the black magnetic spherules of the type

considered in this study. The suggested origins are: volcanic,

industrial fly-ash, biologic, inorganic precipitation, and

extraterrestrial. It is possible that some of them may originate

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. from other sources that have not been recognized as of this time.

Volcanic Origin

In studying volcanic ash Del Monte et al_. (1975) found neither

solid nor hollow magnetic spheres. This follows Wright and Hodge's

(1965) observation that magnetic spheres are rare in volcanic

deposits.

Murray and Renard (1883) noted that the more remote a

collection site was from the volcanic source, the higher the ratio

of non-magnetic fraction to magnetite. There is no known volcanic

activity in the proximity of the Michigan Basin during the Salina

deposition (Dott and Batten, 1976). Mutch (1964a, 1966) thought

that a large component of volcanic dust should be associated with

the spheres i f they are truly volcanic. The composition of the

tephra studied by Wright and Hodge (1965) and Mutch (1964b) does

not appear to be similar to the insoluble residue from the salt of

this study.

Wright and Hodge (1965) and Del Monte et al_. (1975) thought

the differences in chemical composition (depletion of aluminum in

extraterrestrial spheres), structural differences (extraterres

trial spheres usually being more spherical), and mineralogical

characteristic differences (the extraterrestrial spheres show

signs of being supercooled) between the extraterrestrial spheres

and the volcanic material was sufficient evidence to reject a

volcanic origin. Del Monte etal_. (1975) also pointed out that

thermodynamically the spheres could not be formed by volcanic

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. activity. For these reasons a volcanic source is rejected for

the spheres from the A-l Salt.

Industrial Origin

An industrial source is ruled out for the spheres in this

study because contaminants from industrial processes do not have

the same composition as the extraterrestrial spheres (Wright and

Hodge, 1964). The sediments are also approximately 400 million

years old, this lim its any industrial contaminants to be due to

sample preparation. Any industrial contaminants would have to be

introduced to the sample a fte r, or during, the actual coring

procedure.

Biologic Origin

Biologic activity could be responsible for the formation of

the spheres. Murray and Renard (1883) mentioned that reduction of

iron oxide into metallic iron may be due to biologic a c tiv ity , but

no biologic agent for the formation of predominately magnetite

spheres appears to exist (although biologic activity can form

pyrite spheres (Vallentyne, 1963)). The reason biologic activity

is not considered to be the source of these spheres is due mainly

to the overwhelming evidence that suggests an extraterrestrial

origin, but biologic creation of these spheres can not be completely

ruled out.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 27 Inorganic Precipitation

I f the spheres actually represent inorganic precipitation, then

the depositional environment would have had to have been saturated

with respect to magnetite (or some other form of iron which could be

altered to magnetite). No explanation of this phenomenon has yet

been proposed. For this reason inorganic precipitation at the site

of deposition has been ruled out.

The magnetite could have formed in another terrestrial environ

ment and have been transported to the depositional site. Parr

(1966) discussed this concept, but stated that detrital magnetite

is not as spherical as these objects. He also mentioned that

magnetite tends to form subhedral forms. The subhedral and euhedral

forms present in the residue may actually be stages in the alteration

of the extraterrestrial dust (Parr, 1966).

Extraterrestrial Origin

S m alesetji!. (1958) investigated the nickel/cobalt, nickel/

copper, copper/cobalt, and nickel/iron ratios and decided that the

samples from sea sediments resembled meteoritic material, but

samples collected from the roof of a building and recent river

sands did not. Others including Castaing and Frederiksson, 1958;

Millard and Finkelman, 1970; and Blanchard and Davis, 1978 used

transitional metal abundances to determine that the spheres are

actually extraterrestrial.

Brownlee et a l . (1975) compared ablation material from

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. a r tific ia lly ablated olivine (Fogg) to that of natural fusion

crusts of meteorites. Their study demonstrated a method for

the formation of spheroids, and showed that the mineralogy of the

by-products is the same as that o f the spheres. Schmidt and Keil

(1966) stated that the presence of meteoritic quantities of nickel

pointed to an extraterrestrial source. Marvin and Einaudi (1967)

noted the presence of wustite in spheres. Wustite is known only

from extraterrestrial material and recent industrial sources.

The primary crite ria for the extraterrestriality of iron-nickel

particles was reported by Finkelman (1972) and Blanchard and Davis

(1978). They are: (1) iron, nickel, and cobalt ratios are

compatible with meteorites; (2) metallic iron and n.ickel are present

(3) wustite is present; and (4) for nickel-iron spheres, titanium,

manganese, and chromium are depleted with respect to meteoritic

abundances. However, Blanchard and Davis (1978) noted that none

of these parameters can be used alone to prove extraterrestriality.

Additionally, the absence o f nickel cannot be taken as proof of

non-extraterrestriality (El Goresy, 1968; Fechtig and Utech, 1964;

Millard and Finkelman, 1970), because many of the analyses that have

been run only give the composition of the outer shell which is

usually depleted in nickel (Fechtig and Utech, 1964; Wright and

Hodge, 1964). This lack o f nickel, particularly in the shell of the

sphere, may be explained by the fact that nickel and cobalt are

depleted in the magnetite phase formed during ablation.

Fechtig and Utech (1964) explained that segregation of nickel

to the core with iron being enriched in the shell was due to rapid

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. heating followed by quenching during flig h t through the atmosphere.

This segregation is further explained by the fact that iron oxidizes

more rapidly than nickel and should be found in high concentrations

in the shell (Blanchard et al_., 1980). Randohr (1967) and Buchwald

(1975) stated that the fusion crusts of iron-meteorites are composed

predominately of magnetite with minor amounts of wustite and rarely

hematite.

The lack of nickel in some samples may be explained by the

dissolution of the nickel-iron core (Fechtig and Utech, 1964) which

would be a source for the abundant "hollow" spheres noted in some

collections (Bruun et a l., 1955; Hunter and Parkin, 1960).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. MICROMETEORITES IN SEDIMENTS

Mutch (1964a) and Ivanov and Florenskiy (1968) completed

studies of micrometeorites in salt in the mid-1960's. Both studies

considered the laminations in halite as representing annual deposits.

From this assumption they derived the influx of extraterrestrial

material. Mutch calculated the influx to be 1.4 x 10^ to 1 x 109

metric tons per year, Ivanov and Florenskiy arrived at 1.0 to

1.1 x 105 metric tons per year for the influx. Mutch used a

deposition rate of five centimeters per year for s a lt, while Ivanov

and Florenskiy used "annual" layers which ranged in thickness from

twelve to eighteen centimeters.

The studies were both done by optically picking out each

spheroid. This technique was used by Parr (1966) in Grenvillian

meta-sediments and was described as being very time consuming

(personal communication, J.T. Parr, 1982). An objective of the

present study is to determine a sedimentation rate for salt in the

A-l Evaporite without assuming the laminations were varves, and to

avoid the optical sorting of the particles for examination used in

previous micrometeorite studies.

Ivanov and Florenskiy (1968) decided to use salt instead of

other sediments for several reasons. Namely: (1) micrometeorites

are easily identified in salt; (2) micrometeorites are easily

separated from the salt; and (3) the salt contains l i t t l e detrital

material. These were basically the same reasons Mutch (1964a)

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 31 chose salt over other types of sediments, but he also included the

fact that salt is presumed to be formed at the site of deposition

(rather than being transported to the s ite ).

Mutch (1964a) assumed that since the sedimentation rate for

salt was so high, that water-transported terrestrial detrital

material would not be a significant component of the residue. He

did imply that wind-blown material may, or may not, be a significant

portion of the residue. Mutch also thought that the magnetite

present had not been altered very much as he assumed that i t did

not spend much time in the brine before i t was deposited within

the salt. This must also be based on the further assumption that

no alteration has occurred due to migration of brines. This assump

tion may not be to tally accurate. Moreover, Mutch (1964a) considered

the faceted magnetite grains to be te rre s tria lly derived. Such may

not be the case as they may represent alteration of extraterrestrial

spheres.(Parr, 1966).

Mutch noted three types of "possible extraterrestrial material"

in the salts he studied. They consisted of: hollow spheres, solid

spheresr, and irregular particles. Although only two samples of

hollow spherules were chemically analyzed, neither showed traces of

nickel (Mutch, 1964a).

Ivanov and Florenskiy (1968) concluded that since the Lower

Permian the influx of extraterrestrial material has been relatively

constant. Parr (1966) expanded on this to say that the influx has

remained constant since Precambrian time. He also pointed out, as

others implied before, that there is an indirect correlation

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 32

between particle size and the number of particles present. Smaller

particles are more abundant than those of larger sizes (Parr, 1966).

Laboratory Procedure

The samples used in the present study are from the Dow Chemical

Comapny salt well number eight, located SE% SW% SW*j, sec. 21, T.14N.,

R2E Midland County, Michigan (Figure 1). Data on the core is in

Appendix A.

The samples from the core were in itia lly weighed, and were then

rinsed with d is tille d water to remove any flakes of metal associated,

with the actual coring procedure. The samples were then dissolved

in five gallons of water purified by reverse-osmosis. When dissolved

most of the samples le f t a fine residue, and no mechanical breakdown

of the residue was necessary to run i t through the centrifuge. A

Sorval RC2-B centrifuge from the Department of Biomedical Sciences

at Western Michigan University was used under the supervision of

Dr. Robert Eisenberg. I f the sample did not disaggregate completely,

then the brine was carefully siphoned off. After the salt brine was

removed, the residue was washed with approximately 250 m illilite rs

of deionized water. The samples were run three times through a Frantz

L -l magnetic separator which was set at 1.5 amperes with the track set

horizontal. The non-magnetic residue was collected in a beaker at

the end of the system (Figure 5). The magnetic particles were

magnetically held on the inside of the plastic tubing in the

apparatus. The tubing was then removed from the separator and

washed thoroughly to collect the particles. Both the non-magnetic

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 33

PLASTIC TUBING

BEAKER

FRANTZ SEPARATOR

Figure 5. Frantz magnetic separator set-up.

SAMPLE

■LITHIUM TETRABORATE BACKING

Figure 6. Typical PIXE pellet used for analysis of the non-magnetic fraction (approximately 1 centimeter in diameter).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 34

and magnetic fractions were dessicated in an oven at 120 degrees

Fahrenheit until a ll moisture was removed. The duration of

dessication was from 1 to 14 days. The beakers (which had been

weighed previously) were allowed to cool before they were reweighed.

The weight data are presented in Appendix B.

Non-Magnetic Fraction

A sample of each non-magnetic fraction was pressed into a pellet

for Particle Induced X-ray Emission (PIXE) analysis. The pellets

consisted of two layers: a top layer of the sample its e lf, and a

bottom layer of lithium tetraborate (Figure 6). The lithium tetra

borate was used as backing because the elemental weights of this

substance are too light to be detected by PIXE analysis. To

ascertain that no contaminants in the lithium tetraborate were

considered as actual data a pellet composed of pure lithium te tra

borate was run as a blank. The blank contained some iron, but this

is considered to be insignificant relative to the large amount of

iron contained in the samples.

Magnetic Fraction

The magnetic fraction was too small to press into pellets. A

technique developed by P. Simms and F. Rickey at Purdue University

for amounts less than five milligrams was used to prepare these

materials for PIXE analyses (Figure 7). The sample along with

five millimeters of deionized water is put into columns (Figure 8)

which s it on a manifold which in turn is connected to a vacuum pump.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 35

COOLING APPARATUS

COLUMNS

.WATER TRAP

MANIFOLD VACUUM PUMP

Figure 7. Apparatus used to made PIXE targets for the magnetic fraction.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. « COLUMN

CELLOPHANE

MANIFOLD

Figure 8. Individual column used in making PIXE targets for the magnetic fraction.

MAGNETIC SAMPLE J PLASTIC RING (SECTIONED) t CELLOPHANE

Figure 9. Cross-section of PIXE target for magnetic fraction (approximately 2 centimeters in diameter).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 37

A clean piece of cellophane is inserted between the manifold and the

column. When the vacuum pump is turned on, the water is drawn

through the cellophane as water vapor and the sample is le ft

attached to i t . The water which has vaporized to pass through the

cellophane is then frozen out of the system in an alcohol bath set

at minus 50 degrees Fahrenheit. This prevents moisture from entering

the vacuum pump and destroying i t . When a ll the water has been

pumped through the cellophane, the cellophane is then removed and

mounted on a small plastic ring (Figure 9) and stored in an a ir-tig h t

v ia l. These plastic rings can be mounted on the tandem Van de Graaff

generator (as could the previously described pellets) for the PIXE

analysis.

X-Ra.y Diffraction Analysis

X-ray diffraction analysis was performed on a ll non-magnetic

samples, but only on the two largest samples of the magnetic fraction

samples. The other magnetic samples were too small to be analyzed.

The X-ray machine used for diffraction analysis is a Norelco Philips

and is in the Department o f Geology at Western Michigan Univeristy.

The non-magnetic samples were large enough to put in aluminum

holders for analysis. The largest magnetic sample run was le ft

on the cellophane mount used in the PIXE analysis.

Microprobe Analysis

The microprobe analysis was performed by Vivian Schull of

Michigan State University. The machine used is an Applied Research

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Laboratories model EMX-SM and is located in the Horticulture Depart

ment at Michigan State University. The magnetic samples used in

the PIXE were carefully brushed o ff the cellophane targets into a

small disposable container. The container then had epoxy carefully

poured into i t . A magnet was placed under the container to keep the

magnetic fraction on a single plane. After the epoxy had hardened,

the container was carefully removed. The epoxy mount was then

polished with six micron and one micron diamond paste prior to

analysis.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. RESULTS

PIXE Results

The PIXE results are summarized in Figures 10 through 13. The

total analysis is given in Appendix C. Potassium is found only in

the A-l Evaporite samples. The potassium is most lik e ly associated

either with clays or with sylvite (KC1). It appears that the

potassium must be assoicated with clays because any sylvite present

should have been washed away during the dissolving and centrifuging

process. Whole rock analysis-was run on sample 8159. A portion of

the potassium in this sample can be considered to be from sylvite,

but the amount is not known.

The PIXE results of the magnetic fraction are given in Table 1.

Comparison of the PIXE results to total meteorite compositions

iS' given in Appendix D. The iron/nickel ratio stands out in the magnetic samples. I f they represented only extraterrestrial material

the ratio should be equal to approximately 10. The actual ratio ,

considering all magnetic samples is 453. I f just the ones that

report nickel are considered the ratio is 725. This shows that a

considerable amount of the iron in the sample is from terrestrial

sources.

I t is interesting to note that no nickel was found in the

samples reporting less than 50 parts per million (ppm) iron in the

total rock analysis, or 5 ppm iron in the magnetic fraction. If

one assumes the iron/nickel ratio in the samples was approximately

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 40

Iron Variation 1n 10,000 th* Saaplia (■agnatic frictio n)

,000 -

g 6,000

4,000

2,000

Cor* Otpth

Figure 10. Iron variation in the samples.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. without prohibited reproduction Further owner. copyright the of permission with Reproduced iue 1 Nce vrain n h samples. the in variation Nickel 11. Figure

(■Urogram/gras of residue) Cora Otpth tkl aUln 1n VarUtlon Ntckol ngol fraction) (nognotlc h Singles tho Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. without prohibited reproduction Further owner. copyright the of permission with Reproduced Figure

(alcrograas/graa of residue) 2 Cpe vrain n h samples. the in Copper variation 12. 100 30 50 70 8 I Is I I I .8 i l l l l Core Oepth J a a Copper Variation In In Copper Variation agol fraction) (aagnotle h Seaplot tho Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. without prohibited reproduction Further owner. copyright the of permission with Reproduced Fi gure

3 Zn vrain n h samples. the in variation Zinc 13. (•Icrogrns/graa of residue) 400 § § i i § S * 8 * GO * 8 »*. i 1 I Cora Dtptft ugntl fraction) ttlc n g (u Zinc Vorlttlon In In Vorlttlon Zinc I tho Suplts Suplts tho 43 Table 1. PIXE results of the magnetic fraction.

Sample Formation Element Weight Percent Depth (micrograms/gram) Uncertainty

7529 B-Salt Ca 63,216 • 99% Ti 57 27% Fe 1,229 25% Ni 8 26% Cu 15 25% Zn 118 25% Sr 4 56% Pb 12 28%

7708 A-2 Evaporite Ca 288,055 99% Ti 106 26% Cr 45 8% Mn 64 25% Fe 5,558 25% Ni 20 25% Cu 95 25% Zn- 46 25% As 9 27% Br 4 54% Sr 46 50% Zr 24 51% Pb 38 27%

8082 A-2 Evaporite Ca 58,692 99% Mn 12 28% Fe 837 . 25% Ni no data Cu 15 25% Zn 10 25% Sr 36 50% Pb 6 32%

8084 A-2 Evaporite Ca 47,171 99% Fe 1,979 25% Ni 6 28% Cu 26 25% Zn 64 25% Sr 70 50% Pb 62 25%

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table 1. (continued)

Sample Formation Element Weight Percent (micrograms/gram) Uncertainty

8150 A -l Evaporite Ca 15,275 99% Fe 10,287 25% Ni 11 27% Cu 8 28% Zn 22 25% Sr 59 50% La 422 26% Pb 59 27%

8151 A -l Evaporite Cl 5,119 66% Ca 3,283 99% Fe 364 25% Ni no data Cu 13 26% Zn 9 26% Sr 9 52% Pb 26 26%

8161 A -l Evaporite Ca 76,991 99% Cr 96 5% Mn 69 25% Fe 9,878 25% Ni 17 26% Cu 42 25% Zn 321 25% Sr 26 51% Pb 40 26%

8394 A -l Evaporite Cl 38,853 50% K 16,345 99% Ca 8,250 99% Fe 446 25% Ni no data Cu 18 26% Zn 56 25% Sr 22 51% Pb 27 26%

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table 1. (continued)

Sample Formation Element Weight Percent (micrograms/gram) Uncertainty

8568 A -l Evaporite Ca 97,154 99% Ti 426 25% Mn 155 25% Fe 18,075 25% Ni 12 26% Cu 62 25% Zn 306 25% Br 8 52% Sr 132 50% Zr 115 50% Pb 122 25%

8577 A -l Evaporite Cl 36,598 50% K 8,834 99% Ca 7,626 99% Mn 11 31% Fe 186 25% Ni no data Cu 11 26% Zn 36 25% Sr 805 50%

8579 A -l Evaporite Cl 110,824 50% K 30,102 99% Ca 156,216 99% Mn 36 27% Fe 1,944 25% Ni 7 22% Cu 55 25% Zn 158 25% Pb 71 26%

8593 A -l Evaporite Cl 96,386 50% K 17,061 99% Ca 17,037 99% Fe 1,470 25% Ni 5 34% Cu 45 25% Zn 196 25% Cd 83 34% Pb 110 25%

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 725 to I , i t can be assumed that there was not enough nickel in

these samples to be detected by the PIXE due to background levels. Where nickel was not detected this is considered to be the case.

The analysis of nickel in the core samples w ill, unless otherwise

noted, take into account a ll o f the samples whenever an average is

used.

Cobalt was not shown on the PIXE results because the iron-beta

line obscures the cobalt-alpha line which is the one most easily

detected.

The PIXE analysis shows that noncosmically abundant materials

are depleted in the magnetic fraction. This supports an extra

terrestrial origin. The iron content is much higher than one would

predict for an extraterrestrial origin alone, and apparently 98

percent of the iron is te rre s tria lly derived, or associated with

type S spheres. The iron associated with type S spheres can be

explained by the fact that magnetite forms from ablation of olivine

and iron-rich silicates (Brownlee et a l., 1975).

X-Ray Results

The non-magnetic samples all showed the presence of halite,

anhydrite, and possibly some gypsum. Strontium carbonate was also

very common. The largest magnetic sample run did show several

distinct peaks. I t was determined optically that this sample

(7708) contained the greatest number of black, magnetic spheres.

It also showed distinct wustite (Fe]_x0) peaks. The presence

of wustite supports an extraterrestrial origin for these spheres

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. (personal communication, D.E. Brownlee, 1982).

Microprobe Results

No type I spheres were seen on the polished pellet used for

microprobe analysis. Type S spheres were detected and analyzed.

Most of the particles were spheroidal, but not truly spherical.

These appear to be the ablation debris from stony meteors. The

iron in most of the particles was segregated in the shell of the

particles. Most of the shells appeared to be composed entirely

of iron.

The nickel was concentrated throughout the particles in much

smaller amounts. Nickel, iron, and silica were detected in the

particles. The nickel was highly depleted as would be expected

in stony spheres. The presence of nickel and the concentration

of iron in the shell of the particles (as would be expected if

the particle melted while moving) suggest ex traterrestriality.

Several particles were checked for the presence of iridium,

but because the results were so close to the boundary between

being significant and nonsignificant (due to background) they

were dismissed.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. SUMMARY

The work of Finkelman (1972) and Blanchard and Davis (1978)

established certain c rite ria that must exist i f micrometeorites are

to be assigned to a nickel-iron parent meteoroid origin. The

criteria they developed for individual particles is as follows:

iron, nickel, and cobalt ratios compatible with meteorites; presence

of metallic nickel and iron; presence of wustite, and low abundances

of manganese, titanium, and chromium (noncosmically abundant

elements).

With the photographic proof of spheres being present, the

number of spheres located by optical means, the presence of metallic

iron and nickel suggested by the microbrobe and PIXE, and the pres

ence of wustite demonstrated by X-ray diffraction; the presence of

extraterrestrial iron-nickel spheres in the A-l Evaporite is

considered to have been established.

Discussion

L ittle is known about the physical-chemical conditions on the

deep-sea floor, and even less is known about the conditions required

for the deposition of thick salt deposits (such as the A-l Evaporite).

The possibility remains that some of the nickel could have been

biochemically precipitated directly from seawater, but this cannot

be assumed to have been a factor controlling nickel concentrations

in the sediments. Matthews and Egleson (1974) investigated the

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. concentration of bromine as a function of salt brine deposition. I f

one assumes that nickel would be concentrated in a similar manner,

then there would be an insufficient concentration of nickel to

precipitate.

The pH of the basin is assumed to have been alkaline, greater

than 7.5, during the precipitation of carbonates and evaporites.

Such an environment would have preserved wustite and any metallic

nickel, and chemical alteration of the sphere during lith ific a tio n

or shortly thereafter is unlikely. Chemical alteration of these

materials would have required an extremely acidic environment. It

is unlikely such conditions existed in these rocks at any time

after the sediments were deposited because there is no trace of

dissolution by acids. I t is doubtful that the pH ever dropped to

that of rainwater (pH of approximately 5.6).

The iron/nickel ratio for the iron-nickel spheres is assumed

to be 10. This is derived, from several sources. Two possible

sources are: the average composition of nickel-iron meteorites; the

composition of individual nickel-iron micrometeorites. Millard and

Finkelman (1970) gave the iron/nickel ratio for individual

meteoritic spheres as ranging from 2.5 to 25 with an average ratio

of approximately 10. The ratios of iron/nickel determined in this

study are much higher than 25, but this is due to the fact that

bulk analysis of the samples were run rather than a particle by

particle analysis.

Pettersson (1960) used a value of 2.5 percent nickel content

for all extraterrestrial material. As a check on the accuracy of

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. using an iron/nickel ratio of 10, the nickel content was multiplied

by 40 to obtain the total extraterrestrial influx (assuming the

nickel content represents 2.5 percent of a ll the extraterrestrial

in flux). I t should be noted that Pettersson (1960) is the only

investigator to have used this method and that i t is only being used

here to check other calculations.

In addition to assuming an iron/nickel ratio of 10, it it also

assumed that approximately 30 percent of the nickel is actually

te rre s tria lly derived. This is in accord with Chester and Messiha-

Hanna's (1970) work on nickel associated with deep-sea sediments.

We will assume that the remaining nickel is extraterrestrially

derived from the ablation of iron and stony iron meteorites. The

30 percent that we consider to be te rre s tria lly derived may come

from the weathering of pre-existing rocks, or i t may represent

the direct precipitation of nickel from seawater. This assumption

w ill lead to a slower sedimentation rate than i f all of the nickel

is considered to be ex trate rrestria l. Unless otherwise noted

each calculation involving nickel w ill have 30 percent substracted

from the nickel value.

In f1ux

The amount of extraterrestrial material falling to earth has

been calculated by several investigators. Parkin and Til 1es (1968)

arrived at an influx rate that ranged from 3.6 x 102 to 3.6 x 103

tons per year for a wide range of sources. They then analyzed for

nickel found in sea sediments and Antarctic ice and arrived at a

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. slightly higher influx rate. From nickel in sea sediments they got

a rate that was less than 3.6 x 104 to 1.1 x 105 tons per year.

Fireman and Kistner (1961) reported an influx of 3 x 104 tons per

year and Brocas and Picciotto (1967) reported values of 3 x 106 to

1 x 10^ tons per year. Mi liman (1975) calculated the rate for

particles weighing less than one kilogram and got an influx rate

1 x 104 tons per year. I t was noted in Brownlee (1979) that

Millman's figure represents only a fraction of the supposed total

influx. This figure w ill be used for calculations in this study

primarily because it distinguishes between small and large extra

terrestrial particles.

Differential Transport

Differential transport by water currents could locally enrich

or impoverish micrometeorites in sediment (Parr, 1966). The amount

of variation in the number of spheres per kilogram of sediment

reported in the literature also leads one to believe that the spheres

may be preferentially transported and redeposited. More work needs

to be done in this area. For the purpose of this study i t is

assumed that this phenomenon did not play an important role in the

rocks investigated since deposition appears to- have been relatively

constant except for storms (and subsequent dilutions) which are

postulated to have formed the laminae.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 53

Calculations

The following tables show the constants used for the deter

mination of the sedimentation rates and the amount of extrater

restrial material in the samples.

Table 2. Constants used for sedimentation rate determinations.

lO O Area of the earth: 5.1 x 10 cm

Meteoritic material influx: 1 x 10^ tons/year (Millman, 1975) 2 Influx/area/year: .0019605 micrograms/cm /year 2 Specific gravity of the samples (halite): 2.165 g/cm

Cross-sectional areas of the samples were determined by dividing

the volume of the sample by the sample's length.

Iron meteorites represent 6.6 percent of a ll meteoritic material,

and stony-iron meteorites represent 1.9 percent (Prior and Hey,

1953).

Published salt sedimentation rates: 5 cm/yr (Mutch, 1964a),

12 to 18 cm/yr (Ivanov and Florenskiy, 1968), .4 to 8 cm/yr

(implied Dellwig, 1955), and 6 to 10 cm/yr (Borchert and Muir,

1964).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission 54

Table 3, Amount of extraterrestrial material in the samples.

Sample Extraterrestrial Extraterrestrial Extraterrestrial content using content using content using iron-nickel content iron-nickel content 40 times the less 30 percent nickel content (micrograms) (micrograms) (micrograms)

7529 17.5 12.2 5.4

7708 71.8 50.3 22.2

8082 no data no data no data

8084 9.7 6.8 3.0

8150 18.1 12.7 5.6

8151 no data no data no data

8161 27.8 19.5 8.6

8394 no data no data no data

8568 20.7 14.5 6.4

8577 no data no data no data

8579 7.8 5.4 2.4

8593 5.8 4.1 1.8

Sedimentation rates derived from these figures are shown in

Figure 14.

Deposition Rite (centlwters/yeir) .1 4 Sdmnain ae o te samples. the of rates Sedimentation L4. * * 1 3 3 3 3 s S 8 o* Depth Cor* il1 SedleenUtlon Ritei Ritei SedleenUtlon Ulculeted) (U 55 CONCLUSIONS

1. I f one assumes that most of the nickel present in the samples

from the A-l Evaporite is from extraterrestrial material, and that

the influx at the time of deposition was approximately the same as

today, then one can conclude that salt sedimentation rates of 10 to

400 centimeters per thousand years for the A -l Evaporite are lik e ly .

This is a much slower rate than suggested by previous authors.

2. Many evaporite deposits are laminated, but these laminations

should not be considered varves. Gypsum and anhydrite show thin

laminations, and halite displays somewhat thicker banding, but no

evidence exists to indicate that these are the result of annual

phenomena. In many cases "extra layers" are present, some lamina

tions are extremely thick, and some laminations bifurcate. These

factors suggest an origin that was not influenced by annual variations.

Diagenetic changes may play a larger role in the formation of lamina

tions than has generally been assumed. Until information is available

regarding their mode of origin, these layers should not be considered

varves.

3. The association of organic matter and salt indicates that

the salt was deposited under reducing conditions. This fact combined

with a relatively slow sedimentation rate (10 to 400 centimeters per

thousand years) suggests that the original hydrocarbon content of

the salt is likely much greater than previously believed.

Consequently, salt may be a good source rock for hydrocarbons as

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. well as acting as an impermeable seal for traps. Basins in which

salts are assoicated with accumulations of hydrocarbons should be

re-evaluated with regard to hydrocarbon generation, movement, and

entrapment.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. APPENDIX A

Petrographic Descriptions and Photographs of Core Samples

(Petrographic Descriptions From Dow Chemical Company and Personal Observation)

Sample Depth Formation Petrographic Descriptions

7529 B-Salt Clear, recrystallized salt.

7708 A-2 Evaporite White, pure, coarsely crystalline salt.

8082 A-2 Evaporite White, pure, coarsely crystalline salt.

8084 A-2 Evaporite White, pure, coarsely crystalline salt.

8150 A-l Evaporite Dark brown, coarsely crystalline salt.

8151 A-l Evaporite Dark brown, coarsely crystalline salt.

8159 A-l Evaporite Dark brown, coarsely crystalline salt.

8161 A-l Evaporite Dark brown, coarsely crystalline salt.

8394 A-l Evaporite White, pure, coarsely crystalline salt.

8568 A-l Evaporite White, pure, coarsely crystalline salt.

8577 A-l Evaporite White, impure salt associated with black carbonaceous shaly streaks with a sulfur odor.

8579 A-l Evaporite White, impure salt associated with black carbonaceous shaly streaks with a sulfur odor.

8593 A-l Evaporite White, impure salt associated with black carbonaceous shaly streaks with a sulfur odor.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 59

U l WELL DEPTH t o < LITHOSTRATIGRAPHIC UNIT (feet) GROUP 7,123

h” ►-H Z B-SALT

/jUUH

A-2 CARBONATE

/ j U y H

Z I— M Z

< c CM HH 1 CO < A-2 EVAPORITE c c c CO Q. = 3

O 9 U O J A-l CARBONATE O jlH - O

H- HH Z 3 A-l EVAPORITE 1—l < '

------0 C O /I

Strati graphic column showing depths of units.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 60

CENTIMETRE Sample 7529 B-Salt

CENTIMETRE

Sample 7708 A-2 Evaporite

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 03

Sample 8082 A-2 Evaporite

CENTIMETRE

Sample 8084 A-2 Evaporite

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CENTIMETRE Sample 8150 A-l Evaporite

< r. t

i„- '«r ^Mrm p^HTITTpBaiTnpn^B " 11

CENTIMETRE

Sample 8151 A-l Evaporite

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CENTIMETRE

Sample 8161 A-l Evaporite

CENTIMETRE

Sample 8394 A-l Evaporite

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 64

i P i l S i P

m s ^ s m s m

CENTIMETRE Sample 8568 E-l Evaporite

CENTIMETRE

Sample 8577 A-l Evaporite

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 65

CENTIMETRE Sample 8579 A-l Evaporite

CENTIMETRE Sample 8593 A-l Evaporite Niagaran contact at the extreme le ft edge.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. APPENDIX B

Weights of Samples

Sample Formation Weight of Weight of Weight of Depth Sample Magentic Non-Magnet' Fraction Fraction (feet) (grams) (grams) (grams)

7529 B-Salt 527.9 .0175 5.8

7708 A-2 Evaporite 520.0 .0283 1.8

8082 A-2 Evaporite 889.0 .0189 2.2

8084 A-2 Evaporite 483.8 .0128 22.3

8150 A -l Evaporite 561.4 .0125 2.8

8151 A-l Evaporite 617.8 .0127 4.2

8159 A -l Evaporite 762.7 no data no data

8161 A -l Evaporite 415.7 .0127 2.8

8394 A-l Evaporite 561.9 .0111 1.9

8568 A -l Evaporite 1,184.2 .0139 14.9

8577 A -l Evaporite 765.2 .0168 10.8

8579 A -l Evaporite 710.6 .0082 4.5

8593 A -l Evaporite 797.9 .0088 5.9

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. APPENDIX C

Total PIXE Results

Non-magnetic fraction

Sample Element Counts Percent Actual Weight Uncertainty Wei ght Percent (micrograms)

7529 Cl 734,120.9 50% 4,257,901 73.14 Ca 6,278.6 25% 36,416 .63 Fe 2,653.0 15% 15,387 .27 Cu 53.8 12% 312 .01 Zn 21.5 17% 125 .00 Br 71.8 31% 416 .01 Sr 267.7 15% 1,553 .03

8082 Cl 79,656.3 50% 175,244 7.97 Ca 231,852.8 25% 510,076 23.19 Fe 1,419.6 15% 3,123 .14 Sr 448.4 15% 986 .04

8084 Cl 723,630.8 50% 16,136,967 72.36 Ca 45,871.4 25% 1,022,932 4.59 Fe 739.2 15% 16,484 .07 Ni 28.6 23% 638 .00 Br 32.2 32% 718 .00 Sr 523.9 15% 11,683 .05

8150 Cl 80,922.0 50% 226,582 8.09 K 3,257.3 25% 9,120 .33 Ca 15,413.2 25% 43,157 1.54 Ti 1,321.0 25% 3,699 .13 Mn 58.5 33% 164 .01 Fe 10,064.1 15% 28,179 1.01 Ni 20.0 25% 56 .00 Zn 36.8 14% 103 .00 Br 43.9 31% 123 .00 Rb 21.4 22% 60 .00 Sr 834.6 15% 2,337 .08 Pb 29.6 41% 83 .00

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 68

Sample Element Counts Percent Actual Weight Uncertainty Weight Percent (micrograms)

8151 Cl 532,582.4 50% 2,236,846 53.25 Ca 5,223.8 25% 21,940 .52 Fe 1,004.2 15% 4,218 .10 Br 111.0 30% 466 .01 Sr 28.8 22% 121 .00

8161 Cl 256,106.4 50% 717,098 25.61 K 3,596.4 25% 10,070 .36 Ca 168,958.9 25% 473,085 16.90 Ti 2,303.1 25% 6,449 .23 Mn 210.3 26% 589 .02 Fe 21,438.4 15% 60,028 2.14 Cu 52.7 12% 148 .01 Zn 128.5 12% 360 .01 As 38.0 51% 106 .00 Br 93.1 30% 261 .01 Rb 32.8 18% 92 .00 Sr 545.8 15% 1,528 .05

8394 S 43,660.2 50% 82,954 4.37 Cl 107,498.3 50% 204,247 10.75 Ca 90,188.7 25% 171,359 9.02 Fe 534.7 15% 1,016 .05 Br 59.3 31% 113 .01 Sr 1,007.2 15% 1,914 .10

8568 Cl 727,034.1 50% 10,832,807 72.70 Ca 15,870.2 25% 236,466 1.59 Fe 582.7 15% 8,682 .06 Br 72.5 31% 1,080 .01 Sr 110.1 16% 1,640 .01

8577 S 106,427.5 50% 1,149,417 10.64 Cl 34,180.5 50% 369,149 3.42 Ca 291,412.1 25% 3,147,251 29.14 Fe 484.4 15% 5,232 .05 Sr 12,121.3 15% * 130,910 1.21

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 69

Sample Element Counts Percent Actual Weight Uncertainty Weight Percent (micrograins)

8579 Cl 151,794.5 50% 683,075 15.18 Ca 432,322.7 25% 1,945,452 43.23 Fe 1,009.2 15% 4,541 .10 Sr 3,846.9 15% 17,311 .38

8593 S 89,499.8 50% 528,049 8.95 Ca 339,623.1 25% 2,003,776 33.96 Fe 1,346.0 15% 7,941 .13 Zn 195.3 12% 1,152 .02 Sr 2,847.1 15% 16,798 .28 Pb 73.3 30% 432 ,01

Sample Element Counts Percent National Bureau Uncertainty of Standards numbers

Orchard leaves K 14,596.2 25% 14,700 + 300 (standard) Ca 21,043.9 25% 20,900 + 300 Mn 98.1 26% 91 + 4 Fe 277.5 15% 300 + 20 Cu 10.6 21% 12 + 1 Zn 24.9 17% 25 + 3 As 12.7 53% 10 + 2 Br 10.0 35% 10 + ? Rb 11.8 26% 12 + 1 Sr 30.3 18% 37 + ? Pb 61.7 28% 45 + 3

Magnetic fraction

Sample Element Counts Percent Actual Uncertainty Weight (micrograms)

7529 Ca 22,125.6 99% 1,106.280 Ti 20.0 27% 1.000 Fe 430.3 25% 21.515 Ni 2.7 26% .135 Cu 5.4 25% .270 Zn 41.4 25% 2.070 Pb 4.3 28% .215 Sr 1.5 56% .075

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Sample Element Counts Percent Actual Uncertainty Weight (micrograms)

7708 Ca 163,039.0 99% 8,151.950 Ti 60.3 26% 3.015 Cr 25.6 8% 1.280 Mn 36.1 25% 1.805 Fe 3,145.9 25% 157.295 Ni 11.1 25% .555 Cu 53.9 25% 2.695 Zn 25.8 25% 1.290 Pb 21.7 27% 1.085 As 5.1 27% .255 Br 2.4 54% .120 Sr 26.0 50% 1.311 Zr 13.6 51% .682

8082 Ca 22,185.7 99% 1,109.285 Mn 4.7 28% .235 Fe 316.4 25% 15.820 Cu 5.6 25% .280 Zn 3.8 25% .194 Pb 2.4 32% .123 Sr 13.6 50% .680

8084 Ca 12,075.9 99% 603.795 Fe 506.6 25% 25.333 Ni 1.5 28% .075 Cu 6.8 25% .340 Zn 16.5 25% .825 Pb 15.9 25% .795 Sr 18.0 50% .900

8150 Ca 3,818.8 99% 190.940 Fe 2,571.8 25% 128.590 La 105.4 26% 5.270 Ni 2.8 27% .140 Cu 2.1 28% .105 Zn 5.6 25% .280 Pb 7.0 27% .350 Sr 14.7 50% .735

8151 Cl 1,300.2 66% 65.010 Ca 834.0 99% 41.700 Fe 92.4 25% 4.622 Cu 3.3 26% .165 Zn 2.4 26% .121 Pb 6.5 26% .325 Sr 2.4 52% .121

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Sample Element Counts Percent Actual Uncertainty Weight (micrograms)

8161 Ca 19,555.7 99% 977.785 Cr 24.3 5% 1.215 Mn 17.6 25% .887 Fe 2,509.0 25% 125.455 Ni 4.3 26% .215 Cu 10.6 25% .534 Zn 81.6 25% 4.080 Pb 10.1 26% .505 Sr 6.5 51% .325

8394 Ca 1,831.6 99% 91.580 Cl 8,625.4 50% 431.270 K 3,628.7 99% 181.435 Fe 99.0 25% 4.950 Cu 3.9 26% .195 Zn 12.4 25% .620 Pb 6.1 26% .305 Sr 4.9 59% .245

8568 Ca 27,008.9 99% 1,350.445 Ti 118.4 25% 5.920 Mn 43.1 25% 2.155 Fe 5,024.9 25% 251.245 Ni 3.2 26% .160 Cu 17.3 25% .865 Zn 85.2 25% 4.260 Pb 33.9 25%. 1.695 Br 2.2 52% .111 Sr 36.6 50% 1.830 Zr 32.1 50% 1.605

8577 Cl 12,297.1 50% 614.855 K 2,968.4 99% 148.420 Ca 2,562.4 99% 128.120 Mn 3.7 31% .185 Fe 62.6 25% 3.130 Cu 3.6 26% .181 Zn 12.0 25% .602 Sr 270.6 50% 13.530

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Sample Element Counts Percent Actual Uncertainty Weight (micrograms)

8579 Cl 18,175.2 50% 908.760 K 4,936.8 99% 1,280.970 Mn 6.0 27% .333 Fe 318.9 25% • 15.945 Ni 1.2 32% .064 Cu 9.0 25% .453 Zn 26.0 25% 1.297 Pb 11.7 26% .585 Br 2.6 51% .131 Sr 878.2 50% 43.910

8593 Cl 16,964.0 50% 848.211 K 3,002.8 99% 150.140 Ca 2,998.5 99% 149.925 Fe 258.7 25% 12.935 Ni .9 34% .045 Cu 8.0 25% .389 Zn 34.5 25% 1.725 Pb 19.4 25% .972 Cd 14.6 34% .734

Whole rock analysis

Sample Pellet Iron Weight Bromine Weight (micrograms/gram) (micrograms/gram)

8159 1 135 157 2 309 164 3 54 168 4 437 172 5 239 151 6 32 133 7 494 164 8 37 161 9 386 170 10 36 135 11 245 162 12 402 175

Average 208 160

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. APPENDIX D

PIXE Results Versus Meteorite Composition

Sample Formation Element Weight Percent

7529 B-Salt Ti .0057 Fe .1229 Ni .0008

7708 A-2 Evaporite Ti .0107 Cr .0045 Mn .0064 Fe .5558 Ni .0020

8082 A-2 Evaporite Mn .0012 Fe .0837

8084 A-2 Evaporite Fe .1979 Ni .0006

8150 A-l Evaporite Fe 1.0287 Ni .0011

8151 A-l Evaporite Fe .0364

8161 A-l Evaporite Cr .0096 Mn .0069 Fe .9878 Ni .0017

8394 A-l Evaporite Fe .0446

8568 A-l Evaporite Ti .0426 Mn .0155 Fe 1.8075 Ni .0012

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. APPENDIX D

PIXE Results Versus M eteorite Composition

Sample Formation Element Weight Percent

7529 B-Salt Ti .0057 Fe .1229 Ni .0008

7708 A-2 Evaporite Ti .0107 Cr .0045 Mn .0064 Fe .5558 Ni .0020

8082 A-2 Evaporite Mn .0012 Fe .0837

8084 A-2 Evaporite Fe . 1979 Ni .0006

8150 A-l Evaporite Fe 1.0287 Ni .0011

8151 A-l Evaporite Fe .0364

8161 A-l Evaporite Cr .0096 Mn .0069 Fe .9878 Ni .0017

8394 A-l Evaporite Fe .0446

8568 A-l Evaporite Ti .0426 Mn .0155 Fe 1.8075 Ni .0012

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 74

Sample Formation Element Weight Percent

8577 A-l Evaporite Mn .0011 Fe .0186

8579 A -l Evaporite Mn .0037 Fe .1945 Ni .0007

8593 A -l Evaporite Fe .1470 Ni .0005

Average composition of iron meteorites Mg .03 Si .01 Ca .02 . Cr .01 Mn .05 Fe 90.85 Co .60 Ni 8.50

Average composition of stonym'ron meteorites Mg 12.33 Si 8.06 Fe 55.33 Co .30 Ni 5.43

Average composition of stony meteorites Mg 14.30 A1 1.56 Si 21.00 Ca 1.80 Ti .12 Cr .40 Mn . 16 Fe 15.50 Co .08 Ni 1.10

Average composition of meteorites from Krinov (1960).

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