/ f

GER MANIUM AND URANIUM

I N COALIFIED WOOD FROM

UPP ER DEVONIAN BLACK SHALE

By Irv:.ng Ao Breger and James Mo Schopf _______ . ____ ........._. _______________________ _

I'

J

I

· Tra ce Element s Investigations Report 496

UNITED STATES DEPARTMENT OF THE INTERIOR

GEOLOGICAL SURVEY t I

Geology and Mineralogy

This document consists of 12 pages Series A o

·UNITED STATES DEPARTMENT OF THE INTERIOR

GEOLOGICAL SURVEY

GERMANIUM AND URANIUM I N - COALIFI~D WOOD

FROM UPPER DEVONIAN BLACK SID}-LE"*

By

I . Irving A. Breger and James Mo Schopf

December 1954 .

Trace Elements Investig~t}ons Report 496

This preliminar y report is distributed . without editorial ~nd t~chnical review

fO;t" conformity ·with. official standards and nomenclature o It is ·. not for _publi c inspection or · quotationo, -- ·

*This report concernr;J work d.one on beha l f of t he Division of Raw Mat -erials of the Ua. S o ~to.mic Energy Commission ..

2

USGS TEI-496

GEOLOGY AND MI NERALOGY

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A . E~ Weissenborn, Spoka11e oo ··• • o•o •••· "· ···••'·""'"""o•···••o. o. o••o· -··· • l TEPCO:. Denv er· o o o o o o •• ._ ·I· .. o o o • o .. o o 0 o . .. ... o • .• o. o o o " ._ •• " •.•• o o •••. o • 2 TEPCO ~ RPS , Wa shington , (Including mas t er) •• o • • o •• o o o o o o o o o. o o 2

69

3

GERMANIUM AN:O ·uRANIUM IN COALIFIED WOOD

FROM UPPER DEVONIAN BLACK SHALE

By Irving A., Breger and J ame s M.. Schopf

ABSTRACT

Microscopic study of black 1 vi tr·eous, carbonaceous material occurring in the Chattanooga shale in Tennessee and. in the Cleveland member of the Ohio shale in Ohio has revealed coalified woody plant t is sueo Some samples have shown sufficient detail to be identified wit h the genus Callixylon~ Similar material has been reported in the l iterature as ubituminous" or "asphaltic'' stringers o

Spectrographic analyses of the ash from ·the coalified wood have shown unusually high percentages of germanium, uraniwn? vanadium, and nickel " The inverse relationship between uraniwn and germanium in t he ash andthe ash content of various samples shows an association of thes e elements with the organic constituents of the coalo

On the basis of geo.chemical consider·ations 1 it seems most probable that the wood .or coalified wood was germanium-bearing at the time logs or woody fragments were floated int o the basins of deposition of the Chatt anooga shale and the Cleveland member of the Ohio shale, Once within the marine environment~ the material probably absorbed uraniwn with the formation of organo-uranium compounds · such as have been found to exis t in coalso

·It is suggested that ·a more systemat i c search for germaniferous coals in t he vicinity of the Chattanooga shale and the Cleveland member of t he OhJ.o sha le might be r ewardingo

Black~ vitreous bands of carbonaceous material (l/8 to 5/8 inch

thick and as much as several f 'eet long) occur in the Chatt anooga shale

in Tennessee and in the Cleveland member of. tbhe , ;Ohio1shale in Ohio .o·

In des criptions of' these Upper Devonian black shales, these bands have

been sporadically reported as "bituminousn or "asphaltic" lenses or

stringers ~ Stauffer C!:) des cribed similar O C(~urrences up to 3 inches

thick in the Huron member of the Ohio shale in northern Ohio as

4

11gilsonite seamsa" Microscopic study o:f the material has invflriably

revealed co&:.lified woody plant tissue identical with that observed in

vi train"' Some of this material shows sufficient detail of vascular

pitting to be identified with the genus Callixylona

Nearly fresh vitrain (g) collected from the top black interval of

the Chattanooga shale in Davidson County, Tennp ~ and weathered vitrain

obtained from the Cleveland member in the Bedford Reservation in Cuyahoga

County ·southeast of' Cleveland, Ohio, were available in sufficient

quanti ties to 'Obtain the standard coal analyses (2) shown in tables l

·and 2 o The vitrain from the Chattanooga shale corresponds in rank to

high=volatile A bituminous coal; the rank o.f that from the Cleveland

member is probably similar, but the properties that are critical for

determination of rank in this specimen have been altered by weathering.,

The vitrain :from the Chattanooga shale is from one of the thickest

bands recently observed (about half an inch)<> Other bands a quarter

of an inch or thinner have been reported to be sparsely scattered in

the shale which . contains on t he average three to five thin bands

in a 30-foot core in central Tennessee (~)o Other streaks have been

observed in the black Dunkirk shale member o:f the Perrysburg formation

i.n wee tern New York and in the black Ohio shale near Chillicothe 9 Ohio o

Tabular pieces of coal from the Chattanooga shale and Cleveland

member of' the Ohio shale were cleaned with particular care to remove

extraneous mineral matter before initiating geochemical studieso

Spectrographic analysis (2) of the ash from each sample showed unusually

high percentages of germanium~ uranium.? vanadium, and nickel (table 3)o

An ·analysis of a sh :from a sample of Chattanooga shale is also shown

in table 3 for com];)arison o

5

Table l o ~"~.Ana,lys:is o:f vi:train from the Chattanooga shale pl/

Pro:z:imate analysis Moisture Volatil e matter Fixe d carbon Ash

Ulti.m.ate analysis Hydrogen Ca!"b on Nitrogen ·oxygen Sulfur Ash

Briti.sh thermal units

As rece:i.v ed. (per cent)

2ol 4o,6 55 a1 2Q~~

5A) 77 .r1 lo ·r 9J3 3o6 2·6; ~?

Moi.s ture free (percent)

4l g.4 56:oJ '2 ii 3

5'!5 78~ 7

l o.7 8 ~2 )o6 2 .Q3

14640

Moisture and ash free (percent)

42o.4 57u6

'5o6 80 .. 5

lo7 845 3 .. 7

14990

!:.:,/ Analyses by U"' S .. Bureau of Mines , Lab .. No., E-<52291, Feb" 2, 1954 p

Table 2 a'"""'Analysis of vtt:r.ain from the Cleveland member of the Ohio shaleoJ../

Proxirria. te aw,l ys i .s Moisture Volatile matter Fixed carbon Ash

Ultimate analys is Hydrogen Car·bon Nitrogen O,xygen Sul:fur Ash

Bri.t ish thermal units

As recelved (percent)

12o7 3Jo5 50 ,2.

3a6

5a0 62o5

1 .,5 26a4

l ,Q 3o6

10620

Moisture free (percent)

;8 014 57<>5

4 p. l

4 <l l 7l o.6 1"7

1794 la l 4 g.l

12170

Moisture and ash free (percent)

4o~o 6QQO

l~ 0 3 74o6 lll7

18;,2 1d2

12700

l/ Analyses .by U o S a Bureau ·of Mines j) Lab o No Q E:..:32292 Feb, 2 9 1954p.

'fl hlP ":2; - -C: c mo-i .,, ....,~+ ··ta·t..: "'' .-,t 0 't'a" 'h·" '. l ~··o 1/ ~a ~.~ ~ ,/ o .._.. \A U.k q U<:..!..Ll U } . ,.i, ve cpe l_, ,;r g , P.- .. l. f2: ana . y s .l,:'J o . .:....:

Percent

Over 10

5 ~ 10

l - 5

Oo5 - 1

0.1 ~ Oo5

Oo05 - Q.1

OoOl - Oo05

Oo005 - OoOl

0.001 - Oo005

Oo0005-0a00l

Oo00Ql-Oo0005

Ash of :n0l from Chattanooga shale g/

Element.

Fe

Si

Ge Al ca .,_v.

Ni TJ Mg

Cu Ti Cr Mo Na Sr B

Y Pb Ba

Co Sn Zr Mn Z:a

Yb

Ga Sc Be

Ash of coal from Cleve land member 2../

Element

Fe

Al Ca Si

V Ge

Co Mg Zn

Cu Cr Ni Ti U

Ba B Na Mn Sr Y

Mo Sn Ph Zr

~0

La Ga Sc

Be

1/ Analyses by Mona Frank~ U o So Geological Survey., 2/ Ash of coal= 1.27 percent. 3/ Ash of coal = l. 7 percent. ~/ Ash of shale = 77 .32 percent.

Ash f :rom t 1ha-t+anong·a -·hale 11 / 'i,_.J,_ . .I"...) u ... ..,.., : t; ,_, . _. 2

Element

Al Si

Fe

K

Mg

Ca Na Ti. Ba

Co B Cu Sr Cr Mo Ni Mn

V Ga I.a Zr

Y Pb Sc Ge

Yb Be Ag

0\

7

Semiquantitative analyses were supplemented and confirmed by the

quantitative data shown in table 4o Analytical t e chniques that have

already been described (g) were employed to obtain percentages of

moisture, ash, and uranium in the sampleso Germanium was determined

·quantitatively using a sodium carbonate dilution technique and appro­

priate standards; vanadium and nickel wer e det ermined using the pegmatite-

base dilution technique described by Gordon and Murat a (~) o

A small sample of Chattanooga shale from Davidson County~ Tenn .. ,

containing several thin coal bands was investigated in detail to

determine the relationships of germanium and uranium in the coalified

wood and in the shale o The specimen was dissected to remove four coal

bands ranging from 2 to 5 mrn in thicknesso Five shale layers (2 to 10 mm)

between the coal bands were also isola ted for analysiso Four of the

shale samples were highly weatheredo The fift h shale sample was thicker

· than the ot hersy very compact, and unweather~do Surfaces of the coal

samples were cleaned of adhering mineral matter 9 and t he individual

samples were than pulverized in an agate morta;r and analyzed. Analyses

are shown in table 5o

The data of table 5 show that all the coal samples contain unusually

high percentages ?f germanium and uranium a The ash content of each coal

band is low and approximates that to be expected for vitrain (])o

Determinations of percentages of ash and uran:i.urn in the shale matrix

adjacent to these coal samples indicate a de crease in ash and uranium

probably as a .result of weathering o The germanium content of the shale

samples may be somewhat high because of the presence of very thin hair­

line streaks of coal, which could not be entirely removed and which

probably contribute a small amount of germanium to the shale samples.

8

Table 4~·-Analysis of coals from the Chattanooga shale and the Cleveland ~embe~ of the Ohio shale ..

Moisture Ash Uranium in asP. . Germanium in -ash 2/ Vanadium in ash 37 Nickel in ash 3r Uranium in dry-coal Ger manium in dry coal Vanadium in dry coa+ Nickel in dry coal

Coal from Chattano.oga sha~e (weight percent)

2 e.:3 l v..27 -2.58

4 ~ o, 4 .. 5 2~90 0 .. 36 o ~o33

0.051, 0 .. 057 0!>-037 o.oo46

Coal from Cleveland member 1/ (weight percent) -

1~7 0 .. 50 2 ..

o .. oo85 0.034

1/ Analysis on ·dry basis by Audrey Smith, U. S .. Geological Survey:• 2/ Analyses by Katherine Valentine and Mona Frtank, u. S" .

Geological Sl1rvey ... ·)./ A;rialysis oy A .. -T .. . Myers 1 u. S .. Geological Survey ..

Table 5 .. --Artalyses of e®le and coal bands from the Chattanooga shale .-'

Sample

Coal 'Coal coal Coal Shale ,

(unweathered) Shale Shale Shale Shale

.Ash (percent)

4.23 3 .. 80 2 ~45 11'69

77-32 56.17 55 .. 46 54 .. 19 43 .. 83

Uranium

In 'ash (p~rc·ent)

0 .:42 Oo55 0.457 1.;32

o.oo68 0 .. 0038 o .. oo49 Oo0083 0 .. 0099

In sample (percent)

0.0178 0 .. 0209 0.0140 0.0223

0 .. 0053 0~~0021

0<>0027 o .. oo45 o.oo43

Germanium]:}

In ash In sam:ple (percent) (percent)

0 .. 6 2 •. 0 1o5 3 .. 0

0 .. 001

o •. oo4

0.025 Oo076 Oo037 01'051

o ~oooB

o ~oo:L8

. ]:./ Analyses by Mona Frank, U ... S. ·Geolqgtcal Survey-o..

9

The inverse re~tionship (table 5) between uranium in the ash

and the ash content of the coa), samples shows an association of uranium

with the organic constituents of the coal. The same relationship is

true for germanium.

·The association of uranium with coalified logs or coal.ified

woody debris has long been known (~), and the o·ccurrenc·e of germanium

in such materials h~s been well establ-ished (2_, 10, _g). An association

of both uranium and germanium in the same specimen, such as has .been

described in this paper, has not previously been reported.

Stadnichenko (11), in reporti1;1g on o<;currences of germanium in

American coals, states, '''l'he highest concentrations oX germanium b,ave

been found in ·coalified logs and pieqes of 'woody co~l occurring isolated

in sediments." Germanium in the coalified wood from the Chattanooga

s",hale represents ·a:p.other occurrence similar to those which Stadnichenko

·and her coworkers have described •.

The germanium content of coal ash has been, reported to range from

less than 0.001 to 9 percent (2_, 10, ~). Because germanium is

frequently concentrated at the top and bottom of coal seams, it has

been suggested that the element has entered the coal through the medium

of ground water. Unusually high percentages of germanium may also have

been introduced into ancient buried tree stum.ps by the movement of

ground waters .~ Aubrey and otners (10, ~) have suggested that germanium

is retained in coals in intimate association w;ith the organic constit-

uents rather than with the mineral matter.

The concentration of germanium in sea vater has been reported to

be less than 10-8 percent (1:;). Shales have been reported by Preuss (14) ,.4

to contain, on tbe average, appro~imately 7 x 10 perc·ent of germaniU+n.

10

From these data it would appear t hat sedimentation in a marine environ­

ment may concent rate germanium t o an appreciable extent from sea water,

but the content of t he element in marine sediments is considerably

lower than has been found in many coals or coalified logs from fresh­

water environments ., The highly anomalous concentration of germanium

in coalified wood from th~ Chattanooga shale and the Cleveland member

of t he Ohio shale is several orders of magnit ude greater than any con­

cent ration yet noted in marine sediments and can hardly be explained

on t he basis of absorption from a marine environment.

As has been noted by McKelvey and Nelson (15) and others, fine­

grained shales deposited from marine environments may be uranium bearing.

Two examples of such shales are the S-wedish alum shale (16) and the

Chattanooga shale ( 15) ... Sea water contains about 2 :x 10- 7 percent of

uranium (17) , mari.ne formations normally contain approximately 10-4

percent of uranium (18), and certain strata in marine formations such as

the Chattanooga and Swedish alum shales are known to contain from

several t housandths to severa l tenths of l percent of uranium indicating

even greater concentration of the element from sea water .0

Several explanations are possible to account for this asso:ciation

of germanium and uranium, but it seems most probable that the ·wood or .

coalified wood was germanium-bearing at the time logs or woody fragments

were floated into the basins of deposition of the Chattanooga shale

and the Cleveland member of the Ohio shale.. Once within the marine

environment ~ the material probably absorbed uranium vith the formation

of orgCl.no-uraniu.m compounds such as have been found to exist in coals

11

The presence of germanium in the coalified wood from these shales .

~uggests that a more systematic search for gertrianiferous coals in

the 'Vicinity of the Chattanooga .shale and the Cleveland member of ·the

OhiO shale might be rewa:rdingp, I

The authOrs a;cknowietE~ the as~istance of Lo. C •. Conant and T .• M,

Kehn. in providing samples 10f the Chattanooga shaleo ·This work is

·part ·Of a program undertak\en by the U .. S ... Geological S~rvey on behalf

of the Divi:sion o-f Raw Materials of the U ~ So. Ato:mic Ene:rgy Commission.

REFERENCES AND NOTES

lo ·c., Ro Stauffer j Am, Jd Sci, ·242, 251 (1944) ...

2.. I .. Ali Breger 1 R. Meyro-w:Ltz~ and Mp Deul, Scienc·e 120, 310 (1954} ..

3 o A. Co · Fieldner and W ~ A. Selvig, Uo S • . Bur. Mines Bull~- 492 ( 1951).

4, ·Tp' M .. Kehn9 Personal .cQl'nmunieation ..

5.. C."' L,.,-·waring and Co S <> Annell~ Analo Chemo ·25, 1174 (1953) ..

6" MD G.ord.on 9 Jr o , and K .o ~ ~r o- Murata, Econ" Qeol'"' 4 7, 169 ( 1952) "

7 ~~' G.. C -" Sprunk and H .. · J <> 0 'Donne 11, U.. S o Bur~~ Mines Tech.. Paper 648, 3 (1942) d

8 !>' ·a" P lt. FiE?cher, Econ... Geol o 45, 1 ( 1950) .ill

9o Ao J!l W~. Headlee and R ... Gs;, Hunter, West Virginia Geo.1 .. Survey Rept.. Invest .. §., 1 ( 1951) ..

10.. K .. v~. Aubrey, Fuel~' J+29 (1952) ~-

11 .. Ttr Stl3.dnichenko, K .. J~. Murata~ Po Zubovic~ and E .. L~~ Hufschmidt~ U '"· So Geol., Survey Circ P' 272 ( 1953) ..

12., 'Eo: Afi ·Rudge and S" E p: As: Moon, Chemistry ~nd Industry, 40 (1946} .,

13 o. I .. N.oddack and W .. Nod~ck $ A;rk g Zool~~, (Swed..c) 32A, no o • 4, :55 ( 1939) ..

14. ·E .. Preuss, Z, Angewo _ Min!. - .2~ 8 (1940) o

12

V. E. McKelvey and J, M. Nelson, Econ. Geol. 45, 35 11950) o

J" Eo Eklund, Quart., Rev " Skand., Banken 28 , 5 (1947)

17 .. D" C, Stewart and Wfi Go Bentley, Science 120, 50 (19 ~ 4)"

18 o I"' A." Breger, Manuscript in preparation ..

19 , Io Ao Bregerj Mo Deu1 j and So Rubinstein, Abstracts f Papers, Amo Cherne Soc"~ l26th Meeting, New York, 6K (Se ' t" 12, 1954).,