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~ Pergamon Org. Geochem. Vo l. 29, No. 1 3, pp. 315-323 , 1998(~i) 1998 Elsevie rScience Ltd . All rights reservedPrinted in G reat BritainPII S0 14 6-6 38 0(9 8)0 00 72 -2 0146-6380/98/ - see f ront matter

I sotope s tudy on organi c n i trogen of Westphal i an anthrac i te s from theW e s t er n M i d d l e f ie ld o f P e n n s y l v a n i a U . S . A . ) a n d f r o m th e B r a m s c h eM a s s i f G e r m a n y )

M A G A L I A D E R ~*, J E A N - P A U L B O U D O U 2 t , M A R C J A V O Y ' ,B R U N O G O F F I ~ 3 : ~ E R I C D A N I E L S 4

'Labo ratoire de GO ochimie des Isotopes Stables , CN RS U RA 1762, Unive rs i t6 Par is VII , 4 PlaceJussieu, 75251 Par is Cedex 05, France, 2Laboratoire de G6ochimie et M6tal log+nie, CN RS U RA 1762,Physicochimie des Fluid es G6ologiques, Case 124 , Universit6 Paris VI, 4 Place Jussieu, 752 52 ParisCedex 05, France, 3Laboratoire de G6ologie, Ecole N orm ale Sup6rieure, 24, rue L hom ond , 75005 Par is ,F rance and 4Chevron Pe t ro leum Technology Compan y , P . O. Box 446 , La H abra , CA , U. S . A. 90633-0446Abstract The object ive of this s tudy was to examine an aspect of the thermal cycl ing of organic ni t ro-gen in s ed iment s and metas ed iment s . The cyc ling of o rgan ic n i t rogen i s impor t an t because s ed imentaryorgan ic mat t e r i s a s hu t t l e o f n i t rogen f rom the a tmos phere to the lower c rus t and thermal decompo-s i t ion of organic matter is a cr i t ical s tep in the recycl ing of ni t rogen between the dif ferent ni t rogenpools . Abun dance and i s o top ic compos i t ion of o rgan ic n i t rogen were de te rmined in the par t i cu la r cas eof two low sulfur Westph al ian anthraci tes ser ies f rom Penn sylvan ia and Bramsche Mass if . They rep-resent go od examples o f Euram erica coals span ning the whole rang e of anth raci t iza t ion in single f ields .Gold ce ll exper imenta l s imula t ion of the den i t rogena t ion proces s was conducted a t m odera te p res sureto show that both sui tes make ideal metamorphic prof i les without any shif t due to change of facies orto h ydro thermal d i s tu rbance . Dur ing an thrac i t i za t ion , o rgan ic n i t rogen c on ten t decreas es r ap id ly whi leorgan ic n i t rogen i s o top ic comp os i t ion does no t change w i th r ank increas e . T he pres erva t ion of the i s o-topic s ignature implies that org anic ni t rog en isotopes could be used as indica tors for the paleoecologicaland pa leodepos i t iona l h i s to ry r econs t ruc t ion of the bas ins . The s t r ik ing con t r as t be tween the r ap id an ds harp decrease o f n i t rogen organ ic con ten t an d the invar i ance o f i t s i s o top ic compos i t ion dur ing thewhole an thrac i t i za t ion sugges ts tha t a mm onia i s an impo r tan t p roduct o f the d en i t rogenat ion process .@) 199 8 Elsevier Science L td. All righ ts reservedKey words--nitrogen i so tope , an thrac i t e , Penns y lvan ia , Nor th Germ any , me tamorphi s m, coa l, kerogen ,gold cell

INTRODUCTIONT h e r m a l n i t r o g e n c y c l i n g i n s e d i m e n t s a n d m e t a s e -d i m e n t s h a s r e c e i v e d l i t t l e a t t e n t i o n . V a r i a t i o n s o fo r g a n i c n i t r o g e n c o n t e n t a n d o f i ts i s o to p i c c o m p o -s i t i o n w i t h m a t u r a t i o n r e m a i n l a r g e l y u n k n o w n .H o w e v e r , s i n c e h i g h ly m e t a m o r p h o s e d o r g a n i c m a t -t e r i s s u p p o s e d t o c o n t a i n o n l y t r a c e a m o u n t s o fn i t r o g e n , o n e c a n p r e d i c t t h a t n i t r o g e n i s r e l e a s e db y s e d i m e n t a r y o r g a n i c m a t t e r d u r i n g d i a g e n e si sa n d m e t a m o r p h i s m . I m p r o v e m e n t s o f o u r k n o w l -e d g e a b o u t t h e f a t e o f o r g a n i c n i t r o g e n i n n a t u r a la n d e x p e r i m e n t a l m a t u r a t i o n s e r ie s sh o u l d l e a d t o ab e t t er u n d e r s t a n d i n g o f t h e p r o c e ss o f d e n i t r o g e n a -t i o n a n d m a y h e l p i n u s i n g o r g a n i c n i t r o g e n i s o -t o p e s t o e s t a b l i s h th e d i s t r i b u t i o n o f n i t r o g e na m o n g v a r i o u s r e s e r v o ir s i n e a r t h ( J a v o y et a l .

*To wh om cor r es pondence s hould be addres sed . E -mai l :ade r @ipgp.jussieu. fr.?E-mai l : boudou@ cicrp . jus s i eu . fr:~E-mail: bruno@ euclase.ens.frE-mai l: e jda@ chevron . com

1 9 8 6 ; Z h a n g a n d Z i n d l e r , 1 9 9 3 ; B e b o u t , 1 9 9 5 ;J a v o y , 1 9 9 7 ) .

T h e p r e s e n t s t u d y r e p o r ts o r g a n i c n i t ro g e n a b u n -d a n c e a n d i s o t o p i c c o m p o s i t i o n d u r i n g a n t h r a c i ti z a -t i o n . T h e o b j e c t i v e i s t o i n v e s t i g a t e i d e a lm e t a m o r p h i c p r o f i l e s o f o r g a n i c n i t r o g e n f r o m l o wv a s c u l a r p l a n t s i n t w o W e s t p h a l i a n a n t h r a c i t es u i t es .

MATERIALANDMETHODST h e s a m p l e s a r e l i s t e d i n T a b l e 1 . T h e W e s t e r n

M i d d l e a n t h r a c i t e f ie l d o f P e n n s y l v a n i a ( U . S . A . )a n d t h e B r a m s c h e M a s s i f ( G e r m a n y ) , p a l e o b o t a n i -c a l ly d a t e d a s W e s t p h a l i a n ( M i d d l e P e n n s y l v a n i a n ) ,w e r e c h o s e n b e c a u s e t h e c o a l s r e p r e s e n t a w i d er a n g e o f r a n k f r o m a n t h r a c i te t o m e t a - a n t h ra c i t e .H e n c e , t h e w h o l e a n t h r a c i t i z a t i o n c o u l d b e e a s il yo b s e r v e d i n t h e s a m e f i e l d . A s e c o n d r e a s o n w a st h a t t h e re i s a n a b u n d a n c e o f b a c k g r o u n d m a t e r i a la v a i l a b l e f o r t h e r e g i o n , i n c l u d i n g g e o l o g ic a l , p e t r o -g r a p h i c a l , g e o c h e m i c a l s y n t h e s e s a n d e x p e r i m e n t a ls i m u l a t i o n o f c o a l a n t h r a c i t iz a t i o n a n d g r a p h i ti z a -

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316 M . A d e r et al.Table 1. Samples, rank, organic N abundance and isotopic composition

Sample No Source* F i e ld Stratigraphy Rm~x (%) 100 N/C * 615N (%0) 613C (%0)PennsylvaniaWM -GP-M8-CH JL Mam moth#8 Mid. Penn. 2.68 1.34 4.45 -24.30WM -ED-M9-CH JL Mam moth#9 Mid. Penn. 2.97 1.43 4.65 -23.50WM -SH-M8-GR JL Mam moth#8 Mid. Penn. 3.45 1.29 4.35 -24.30WM -RN-LO-CH JL Little Orch. Mid. Penn. 3.78 1.22 5.05 -25.80WM -CR-LY-CH JL Lykens Mid. Penn. 5.30 0.66 4.05 -24.20

PSOC 1468 PSOC Buck Mtn Mid. Penn. 5.45 0.61 4.95 -24.15PSOC 870 PSOC Primrose Mid. Penn. 5.57 0.62 4.85 -23.9516H ED Mammoth Mid. Penn. 5.66 0.67 4.75 -24.4017A ED Buck Mtn Mid. Penn. 5.74 0.69 5.35 -23.502C ED Buck Mtn Mid. Penn. 6.30 0.66 4.15 -23.50BramscheU150-7723 AVR Ibbenbfiren W est fal . 2.91 1.00 2.80 -24.10U150-7796 AVR lbbenbfiren W es tfa l. 3.51 1.01 3.72 -25.40IB-115229 BGR lbbenb0ren W es tfa l. 4.22 0.92 3.05 -23.70IBW1-13493 AVR lbbenbfiren W es tfa l. 4.27 0.92 2.70 -24.00IBW2-14488 AVR Ibbenbfiren W es tfa l. 4.72 0.98 3.00 -23.30PIES-751 AVR Pi es be rg W es tfa l . 6 .00 0 .50 3 .70 -24 .15PIES-693 BGR Pi es be rg W es tfa l . 7 .00 0 .40 3 .60 -24 .05PIES-6770 AVR Pi es be rg W es tfa l . 7 .14 0 .41 3 .45 -24 .92

*JL: J. Levine, PSOC: Penn State Office of Coal Research, ED: E. D aniels, AVR:BGR: Bundesanstalt f iir Geowissenschaften und Rohstoffe.*Organic N/organic C, atomic ratio x 100.A. V ieth-Redemann (Geologishes Landesamt NRW ),

t i o n ( T e i c h m f i l l e r a n d T e i c h m f i l l e r , 1 9 5 0 ;H r y c k o w i a n e t a l . 1 9 6 7; M u n d r y , 1 9 7 1; S t a d l e r a n dT e i c h m f il l e r, 1 9 71 ; B u n t e r b a r t h a n d T e i c h m i i l le r ,1 9 7 9 ; E d m u n d s e t a l . 1 9 7 9; O l e k s y s h y n , 1 9 82 ;L e v i n e a n d D a v i s , 1 9 8 3, 1 9 8 9; P h i l i p s e t a l . 1 9 8 5 ;D a n i e l s a n d A l t a n e r , 1 9 9 0, 1 9 9 3; L e v i n e a n dE g g l e s t o n , 1 9 9 2 ; W i l k s e t a l . 1 9 9 3 ; D a n i e l s e t a l .1 9 9 4 ; B u s t i n e t a l . 1 9 9 5 ) .

P e n n s y l v a n i a n c o a l s a m p l e s w e r e co l l e ct e d f r o mo u t c r o p s a n d s t r i p m i n e s . B r a m s c h e M a s s i f s a m p l e sw e r e c o l l e ct e d f r o m t h e c o a l m i n e s o f I b b e n b f i r e na n d P i e s b e r g . I n o r d e r t o a v o i d a n y c h a n g e o fp a l e o d e p o s i t i o n a l f a c i e s a l o n g t h e a n t h r a c i t i z a t i o ns e q u e n c e , o n l y s a m p l e s w i t h l o w s u l f u r c o n t e n t( < 1 % ) w e r e s e l e c t e d f o r t h e s t u d y . L o w - s u l f u r c o a li n d i c a t e s p a r t i c u l a r p a l e o g e o g r a p h i c a l - s e d i m e n t o l o -g i c a l o r i g i n a n d n o n - m a r i n e p o s t - d e p o s i t i o n a l g e o -c h e m i s t r y . A c i d c o n d i t i o n s d u r i n g t h e p e a t s t a g e o fc o a l f o r m a t i o n s h o u l d r e s u l t in l e a c h i n g o f a c i d- s o l-u b l e e l e m e n t s , a s w e l l a s i n h i b i t i n g s u l f u r f i x a t i o na n d m i c r o b i a l d e g r a d a t i o n o f o r g a n i c m a t t e r( W e s t g a t e a n d A n d e r s o n , 1 98 4 ; C e c il e t a l . 1 9 8 5 ) .

V i t r i n i t e r e f le c t a n ce m e a s u r e m e n t s a n d e l e m e n t a la n a l y s i s o f c ru d e s a m p l e s w e r e p e r f o r m e d a c c o r d i n gt o S t a c h e t a l . ( 1 9 8 2 ) , L e v i n e a n d D a v i s ( 1 9 8 3 ) ,D a n i e l s a n d A l t a n e r ( 1 99 0 , 1 9 93 ) a n d D a n i e l s( 1 9 9 2 ) . O r g a n i c m a t t e r w a s i s o l a t e d u s i n g H F / H C 1d i g e s t i o n o f t h e m i n e r a l m a t t e r i n a P r o l a b o m i c r o -w a v e d i g e s t o r ( M i c r o d i g e s t 3 0 1 ) . I s o t o p i c a n a l y s e so f t h e o r g a n i c m a t t e r w e r e m a d e u s i n g a F i n n i g a nD e l t a E m a s s s p e c t r o m e t e r a n d w e r e r e p o r t e d i n t h e

d e l t a n o t a t i o n : p e r m i l, re l a t iv e to t h e P e e D e eB e l e m n i t e S t a n d a r d ( ~ 1 3 C) a n d r e l a t i v e t o t h e a t -m o s p h e r i c n i t r o g e n ( 6 1 5 N ) . N i t r o g e n s a m p l e s w e r e

p r e p a r e d u s i n g c o m b u s t i o n i n q u a r t z t u b e s w i t hC u O , C u a n d C a O i n o r d e r to t r a p C O 2 a n d H 2 0( K e n d a l l a n d G r i m , 1 99 0 ; B o y d e t a l . 1 9 9 4 ; B o y de t a l . 1 9 95 ). E v a c u a t i o n o n a v a c u u m l i ne p ro -c e e d e d a s f o ll o w s : C u O , C u a n d C a O w e r e d e g a ss e df o r 4 h a t 6 0 0 C , t h e n p o w d e r e d s a m p l e w a s a d d e da n d c o n d i t i o n e d a t 3 0 0 C f o r 2 h . T h e l o a d e d a n dp r e t r e a t e d t u b e w a s t h e n f l a m e s ea l e d, c o m b u s t e d a t9 5 0 C f o r 4 h , c o o l e d a t 6 0 0 C f o r 3 h t o a l l o w ( i)r e s i d u a l o x y g e n t o r e c o m b i n e w i t h c u p r i c o x i d e , ( ii )n i t r o u s o x i d e t o b e r e d u c e d b y c o p p e r a n d ( ii i) c a r -b o n d i o x i d e t o b e t r a p p e d b y C a O . T h e n t h e tu b e sw e r e s l o w ly c o o l e d to a m b i e n t t e m p e r a t u r e a l l o w i n gw a t e r t o c o m b i n e w i t h C a O . T h e q u a r t z t u b e w a so p e n e d o n a v a c u u m l i ne w i th a t u b e c r ac k e r . T h ec o m b u s t i o n g a s e s w e r e c o o l e d t o l iq u i d n i t r o g e nt e m p e r a t u r e . U s i n g a T o e p l e r p u m p , t h e p u ri f ie dn i t r o g e n w a s c o n c e n t r a t e d i n a c a l i b r a t e d v o l u m ea l l o w i n g q u a n t i f i c a t i o n . P o s s i b l e c o n t a m i n a t i o n w a sc h e c k e d b y s c a n n i n g o f m / z 1 2 , 1 5 , 1 6 , 3 0 , 3 2 a n d4 0 ( A r ) . S a m p l e s f o r 6 1 3 C d e t e r m i n a t i o n w e r e p r e -p a r e d i n a si m i l a r b u t s i m p l e r w a y: n o C a O w a sa d d e d t o t h e c o m b u s t i o n t u b e a n d t h e C O 2 w a ss e p a r a t e d c r y o g e n i c a l l y u s i n g a l i q u i d n i t r o g e n t r a p .P r e c i s i o n f o r 6 1 5 N w a s _ 0 . 1 5 % o a n d f o r6 1 3 C + 0 . 0 5 % o .

R E S U L T S N D DISCUSSIONV a r i a t i o n o f o r g a n i c n i t r o g e n c o n t e n t w i t h m a t u -r a t i o n

I n F i g . 1 , t h e a t o m i c N / C r a t i o o f o r g a n ic m a t t e ri s e x p r e s s e d w i t h r e s p e c t t o v i t r i n i t e r e f l e c ta n c ebetwe en ~ ma x 2 .5 a n d 7 . 5 % . T h e o r g a n i c N / C

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lsotope study on organic nitrogen of Westphalian anthracites 317

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0

o ~ P e n n s y l v a n i a

B r a m s c h e\ \

\\

~ ~ ~0 N

2.5 3.5 4.5 5.5 6.5 7.5R m x , %

Fig. 1. Organic nitrogen abundance vs Rn~ax or Pennsylvania and Bramsche natural samples.

(100) fo r the Pennsy lvan ian coa l s dec reases f rom~ 1 .4 t o 0 .6 ( a t R m a 6 % ) w h e r e a s f o r B r a m s c h ecoa l s N/C (100) the range i s lower and decreasesf rom ~ 1 .0 to 0 .4 (a t Rmax 7%) . The d ec reas ing o r -g a n i c N / C w i t h r a n k f o r t h e I b b e n b i i r e n / P i e s b e r gseries is here reported for the f irs t t ime. Similarr a p i d o r g a n i c N / C d e c r ea s e a b o v e ~ R m a x 4 .5 % w a sa l s o r e p o r t e d , b u t n o t c o m m e n t e d o n , b y V o l k o v aa n d B o g d a n o v a ( 1 9 8 9 ) i n t h e D o n e t z a n t h r a c i t e a n dmeta -an th ra c i t e su i te . A few au thors , who c la imtha t to ta l n i t rogen i s an accep tab le subs t i tu te fo rOrgan ic n i t rogen , a l so repo r ted a dec reas ing t r endin the l a te s t ages o f coa l i f i ca tion : Sugg a te (1959) onN e w - Z e a l a n d c o a l s ( w h o w r o t e t h a t f u r t h e r i n fo r -m a t i o n i s c l e a rl y r e q u i r e d t o p r o v i d e a n a d e q u a t ejus t i f i ca t ion o f the obse rved t r ends ) , Shap i ro a ndG r a y ( 1 9 6 6 ) o n A n t a r c t i c c o a l s , D r e c h s l e r a n dSt ieh l (1977) on German an th rac i t e s , Pax ton (1983)on the Pennsy lvan ian an th rac i t e f i e ld and Burch i l land Welch (1989) on the Br i t i sh coa l s . Morerecen t ly , L i t tke et a l . (1995) show ed a ve ry wea kdecrease o f the to ta l N c on te n t in a se ries o f 3an th rac i t e s an d 2 meta -a n th rac i t e s f rom severa l o r i -g ins . These repea ted obse rva t ions t end to suppor tthe va l id i ty o f a genera l in te rp re ta t ive scheme wheret h e m a i n l o s s o f o r g a n i c n i t r o g e n o c c u r s i n t h e v e r yla te s tage o f coa l i f i ca t ion (Boud ou et a l . 1984;Bo ud ou and Espital i~, 1995).

O rg a n i c n i t ro g e n i so t o p i c c o m p o s i t i o n a s a t ra c e r o forig in

Prev ious works (Pe te r s et a l . 1978; Mar io t t i ,1982; R igby an d Ba t t s , 1986; Scho l ten , 1991) haveassessed the po ten t ia l o f 15N/I4N ra t io as ind ica to ro f s e d i m e n t a ry e n v i r o n m e n t . I n t h e P e n n s y l v a n i aand Bra ms che M ass if suites, c515N as well as 613Cdo no t change sys temat ica l ly wi th rank (Tab le 1 ) ,b u t a n t h r a c i t e s d i s p l a y t w o n a r r o w r a n g e s o f 61 5 Nvalues : Penn sy lvan ian c515N va lues ran ge f rom 4 .1to 5 .4%0 and Bram sche va lues range f rom 2 .7 to3.7%o (Fig. 2) . As exp ected, there is no 6 13C shif tdur ing matura t ion (Ga l imov , 1980 ; Lewan , 1986) .The p resen t paper shows , fo r the f i r s t t ime , tha t int h e p a r t i c u l a r c a s e o f s e d i m e n t a r y o r g a n i c m a t t e rf r o m l o w e r v a s c u l a r p l a n t s , o r g a n i c n i t r o g e n i s o t o -p i c c o m p o s i t i o n d o e s n o t c h a n g e d u r i n g m e t a -m o r p h i s m ( u n t i l ~ R m a x 7 % ) , f r o m a n t h r a c i t e ( P Pfac ies ) to meta -an th rac i t e r ank (g reensch is t f ac ies ,K i s h , 1 9 8 7) . I n t h e ca s e o f N o r t h e r n G e r m a n y ,G e r l i n g et a l . (1997) , s tudy ing the to ta l n i t rogen ,p resen ted s imi la r r e su l t s to ours fo r the an th rac i t es tage (un t i l ~Rma x 4%) , i t me ans fo r the l e ss im-p o r t a n t s t a g e o f c o a l d e n i t r o g e n a t i o n w h e r e i n o r -gan ic n i t rogen con ten t i s s t i l l ve ry low (Danie l s andAl taner , 1990 , 1993) . Our resu l t s add subs tance tot h e a r g u m e n t o f H a e n d e l et a l . (1986) who had

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318 M. Ade r et al.

6

~ 5

~ 42 L-L _ _ _

2 . 5 3 . 5 4 . 5 5 . 5 6 . 5 7 . 5R~ , ,

Fig. 2. ,615N of org anic nitroge n vs Rmax for Pennsylvania and Bramsche natural samples.

a s s u m e d t h a t a l e v el i n g o f t h e n i t r o g e n i s o t o p ec o m p o s i t i o n w o u l d t a k e p l a c e d u r i n g d i a g e n e s i s u pt o t h e b o u n d a r y o f g r e e n s c h i s t f a c ie s .

S l i g h t d if f e r e n c e s o f o r g a n i c N c o n t e n t a n d 6 1 5Ni n b o t h a n t h r a c i t e s ui t es P e n n s y l v a n i a a n dB r a m s c h e ) a r e t h o u g h t t o r e f l e c t t h e s i m i l a r i t i e s a n ds l i g h t d i f f e r e n c e s o f t h e p a l e o p h y t o g e o g r a p h y a n dt h e p a l e o c l i m a t e o f t h e t w o b a s i n s , a t a t i m e o fm a x i m u m a s s em b l y o f P a n g a e a d r i f t in g n o r t h w a r dS c o t e s e et a l . , 1979) . These fac ts wou ld be in con-

f o r m i t y w i t h t h e p a l e o b o t a n i c a l r e s u l ts o f P h i l i p s e tal. 1 9 8 5 ) w h o w r o t e t h a t r e g i o n a l d i f f e r e n c e s i n t e c -t o n i c s e t t i n g , h i s t o r i c a l a s p e c t s o f t h e v e g e t a t i o na n d l o c a l e n v i r o n m e n t a l d i ff e r en c e s m a y m a k e t h ep a t t e r n s o f v e g e t a t i o n a l c h a n g e s o m e w h a t d i f f e r e n ti n e a c h c o a l r e g i o n . T h e d r a s t i c c h a n g e s i n c o a l -s w a m p v e g e t a t i o n a r e t r a n s i t i o n a l a c r o s s t h eM i d d l e - U p p e r P e n n s yl v a n ia n b o u n d a r y a n d a r ev e r y s i m i l a r in e a c h o f t h e m a j o r c o a l r e g i o n s o f t h eU n i t e d S t a t e s a n d E u r o p e . H o w e v e r , a n i m p o r t a n td i f f e r e n c e b e t w e e n t h e v e g e t a t i o n o n e i t h e r s i d e o ft h e A p p a l a c h i a n s i s t h e c o n t i n u e d p r e s e n c e o f s o m eL y c o s p o r a - b e a r i n g L y c o p o d s i n E u r o p e . T h i s isp o s s i b l y th e r e s u l t o f a m o r e a s y m m e t r i c c h a n g e i nt h e d r y i n g o f t h e c l i m a t e t h e r e H e d e m a n n a n dT e i c h m f i l l e r , 1 9 7 1 ) . T h e s l i g h t d i f f e r e n c i a t i o n o f t h eP e n n s y l v a n i a n a n d o f t h e B r a m s c h e a n t h r a c i t es u i te s o n t h e b a s i s o f o r g a n i c n i t r o g e n i s o t o p e s

s h o w s t h a t n i t r o g e n i s o t o p e d a t a m a y b e a s i g n i f i -c a n t i n d i c a t o r o f t h e p r e c u r s o r f l o r a , t h e e n v i r o n -m e n t o f d e p o s i t i o n a n d t h e t y p e a n d d e g r e e o fa l t e r a t i o n o f t h e p l a n t s u b s t a n c e s . T h i s d i f f e r e n -t i a t i o n s h o u l d b e e x p l a i n e d b y f u r t h e r s t u d i e s o nt h e p a l e o e c o l o g y o f b o t h c o a l - b e a r i n g d e p o s i t i o n a ls y s te m s f o l l o w i n g t h e a p p r o a c h o f A l t e N i u m e r1 9 83 ), W n u k 1 9 85 , 1 9 89 ), W n u k a n d P f e f f e r k o r n1987) and Diesse l 1992) .

E x p e r i m e n t a l s i m u l a t i o nS i n c e t h e r e i s n o v a l i d m e t h o d t o e x p e r i m e n t a l l y

s i m u l a t e t h e n a t u r a l m e t a m o r p h i s m s t a r t i n g w i t h a ni m m a t u r e c o a l W i l k s et a l . , 1993) , the s imula t ionw a s d o n e w i t h a n a n t h r a c i t e s a m p l e t a k e n a t t h eo n s e t o f th e d e n i t r o g e n a t i o n w i n d o w a n t h r a c i ti z a -t i o n a n d f u r t h e r g r a p h i t i z a t i o n ) . T h e s i m u l a t i o n w a sc o n d u c t e d u n d e r h y d r o s t a t i c p r e s s u r e b e c a u s e t h er o l e o f t e c to n i c s h e a r i n g o n a n t h r a c i t i z a t io n h a s n o ty e t b e e n p u t i n e v i d e n c e L e v i n e , 1 9 93 ). M o d e r a t eh y d r o s t a t i c p r e s s u re 0 .2 G P a ) w a s c h o s e n b e ca u s eh i g h p r e s s u r e m a y h a v e a s u p p r e s s i n g e f fe c t o nm a t u r a t i o n G o f f 6 a n d V i l l e y , 1 9 84 ; D o m i n 6 , 1 9 87 ;D a l l a T o r r e et a l . , 1 9 9 7 ) . T h e a n t h r a c i t e s a m p l e , t h et e m p e r a t u r e a n d p r e s s u r e c o n d i t i o n s w e r e c h o s e na c c o r d i n g t o o u r p r e v i o u s w o r k o n o p e n s y s t e m p y -r o l y s i s B o u d o u a n d E s p i t a l i 6 , 1 9 95 ), g o l d ce l l e x -p e r i m e n t s p r e v i o u s l y p e r f o r m e d b y H r y c k o w i a n e t

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Isotope study on organic nitrogen of Westphalian anthracites 319Table 2. Analysis of anthracite sample WM-GP-M8-CH

As received Dry Dry ash freeHzO 1.47Volatile matterFixed carbonAshBTU*CHNSO (by difference)

9.9774.8215.2112869 90.93.741.420~982.94

*British Thermal Unit per pound.al . 1 9 67 ) a n d s o m e p r e l i m i n a r y e x p e r im e n t s u s i n gi s o s t a t ic p r e s su r e b y m e a n s o f a n a n v i l p r es sB o u d o u e t a l . 1 9 9 7 ) . B e i n g t h e l e a s t m a t u r e

a n t h r a c i t e o f t h e P e n n s y l v a n i a n s e r i e s , a n t h r a c i t es a m p le W M - G P - M 8 - C H f r om t h e M i d d l eM a m m o t h se a m H r y c k ow i a n et al . 1967 ; Lev inea n d D a v i s , 1 9 83 ) w a s c h o s e n f o r t h e g o l d c e l l e x p e r -i m e n t . I t s m a i n c h a r a c t e r i s t i c s , g i v e n b y L e v i n e a n dD a v i s 1 9 83 ) , a r e p r e s e n te d i n T a b l e 2 . T h e s a m p l ew a s h e a t e d a t 6 0 0 C , 0 . 2 G P a f o r 1 5 d a y s , i n as e a l e d g o l d c e l l D o m i n 6 , 1 9 87 ). H r y c k o w i a n et al .1 9 6 7 ), w h o p e r f o r m e d g o l d c e l l e x p e r i m e n t s w i t h

a n a n t h r a c i t e s a m p l e f r o m t h e s a m e c o a l s e a m a sW M - G P - M 8 - C H , h a d o b s e r v e d t h a t 6 0 0 C is c r i ti -c a l i n r e a c t i o n s p r o d u c i n g a r a p i d i n c r e a s e o f r e f l e c -t a n c e a n d a f u s i o n o f t h e m a t e r i a l t o f o r m a h a r dc o m p a c t m a s s t h a t w e e f f ec t iv e l y o b s e r v e d i n o u re x p e r i m e n t s . T h e g o l d c e ll s i m u l a t io n , p e r f o r m e d i no u r l a b o r a t o r y , s h o w e d t h a t o r g a n i c N c o n t e n td e c r e a s e s w h i l e t~13C a n d ~15N o f t h e o r g a n i c m a t t e rr e m a i n u n c h a n g e d F i g . 3 a n d T a b l e 3 ). T h e s ec h a n g e s a r e s i m i l a r t o t h o s e o b s e r v e d i n t h e n a t u r a ls e r ie s F i g s 1 a n d 2 , T a b l e l ) . T h e c o n s t a n c y o f t h e

Table 3. Effect of the gold cell experimental simulation on the or-ganic atomic N/C ratio, tSN and 613C of the WM-GP-MS-CHanthraciteExperimental conditions N/C 6aSN ( 0) ~13 C 0)Initial sample 1.34 4.45 -24.30Gold cell, 600C, 0.2 GPa, 0.77 4.40 -24.35360 h

6 1 5 N s u g g e s t s t h a t d e n i t r o g e n a t i o n , i n c o n f i n e d s y s -t e m , a s w e l l a s i n n a t u r e , i n v o l v e s o t h e r r e a c t i o n st h a n i n o p e n s y s t em p y r o l y s i s , w h e r e ~ l S N i n c r ea s e s

D r e c h s l e r a n d S t i e h l , 1 97 7 ). T h e e x p e r i m e n t a lw o r k o f K a t r i t z k y et al . 1 9 9 5 ), E v e r l i e n 1 9 9 7 ) a n dG e r l i n g et al . 1 9 9 7 ) s u g g e s t s t h a t p r e s s u r e d w a t e r ,w h i c h , i n o u r s t u d y , m a y r e s u l t f r o m a n t h r a c i t ed e g r a d a t i o n a s w e l l a s f r o m c l a y p a r a g e n e s is , m i g h tp l a y a d e n i t r o g e n a t i n g r o l e . W a t e r , i n a s e a l e d c a p -s u l e , a s w e l l a s i n h y d r o u s p y r o l y s i s e x p e r i m e n t s ,w o u l d h a v e a n h y d r o g e n a t i n g r o le H u a n g , 1 99 6;Ever l ien , 1997 ; Lewan , 1997) . Win tsch et al . 1981)p r o p o s e c o a l h y d r o g e n a t i o n b y p r e s s u r e d n e o -f o r m e d m o l e c u l a r h y d r o g e n a s a n i m p o r t a n t s t e p i nt h e m e c h a n i s m o f g r a p h i t i z a t io n , c o n s e q u e n t l y o fd e n i t r o g e n a t i o n .O r g a n i c n i t r o g e n i s o t o p e s a s t r a c e r s o f t h e m e c h a n -i s m o f d e n i t r o g e n a t io n

B e c a u s e i t t a k e s l e s s e n e r g y t o b r e a k 14N-12Cb o n d s t h a n I S N - t 2 c b o n d s , t h e r m o c r a c k i n g o f N -C b o n d s s h o u l d p r o d u c e a p r e f e r e n t i a l r e l e as e o f14N B i g e l e i s e n , 1 9 6 5 ; M e l a n d e r a n d S a u n d e r s ,1 9 80 ). A s a r e s u l t , i f d e n i t r o g e n a t i o n i n v o l v e d t h e r -m a l b r e a k i n g o f a h i g h e n e r g y b o n d , i t s h o u l d l e a dt o a s t r o n g e n r i c h m e n t o f t h e h e a v i e r n i t r o g e n i s o -t o p e D r e c h s l e r a n d S t i e h l , 1 9 77 ; H a e n d e l et al .1 9 8 6 ; B e b o u t a n d F o g e l , 1 9 9 2 ) . T h e p r e s e n t s t u d y

6

4

O 2

natural trend- ~ - / -~5 O T ~.d 6 0 0 C 0 . 2 GPa, 15 days O

treated sample Initial sampleWM-GP-M8-C H

T I ~ J I

0.5 0.7 0.9 1.1 1.3 1.5o r g a n i c N / C a t o m i c r a t i o x 1 0 0

Fig. 3. Results of gold cell experimental simulation with the Pennsylvania WM-GP-M8-CH sample at600C and 0.2 GPa during 15 days (average of 2 runs). O: natur al Penns ylvania samples (Table 1).

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320 M. Ad er et al .s h o w s t h a t 6 15 N o f o r g a n i c n i t r o g e n d o e s n o tc h a n g e w i t h r a n k d e s p i t e t h e N / C r a t i o f a l l in g t oh a l f o f i ts o r i g i n a l v a l u e . A s s u m i n g t h a t a m m o n i ah a s b e e n p r o d u c e d b y i r r e v e rs i b l e r e a c t i o n s w i t h o u ta n y i s o t o p i c f r a c t i o n a t i o n ( W i l l i a m s e t a l . 1995;S h e a r e r a n d K o h l , 1 99 3) a n d t h a t m o l e c u l a r n i tr o -g e n d e r i v e d f r o m o r g a n i c m a t t e r h a s a l o w 6 1 5 N( B o i g k e t a l . 1 9 7 6 ; P r a s a l o v e t a l . 1990) , i t comest h a t m o l e c u l a r n i t r o g e n w o u l d n o t b e a n i m p o r t a n tp r i m a r y p r o d u c t o f t h e a n t h r a c i t e d e n i t r o g e n a t i o n .A f t e r S o h n s e t a l . ( 1 9 9 4 ) , t h e B o i g k e t a l . (1976)d a t a s h o w s y s t e m a t i c d e v i a t i o n f r o m t h e t r u ev a l u es , a s a r e s u lt o f a i r c o n t a m i n a t i o n f o r a s a m p l ew i t h v e r y l o w n i t r o g e n c o n c e n t r a t i o n , o f i n c o m p l e t ec o m b u s t i o n o f h y d r o c a r b o n s , o f f l u c tu a t i o na m o u n t s o f o x y g e n in t h e i o n s o u r c e d u e t o c o n -t a m i n a t i o n w i t h a i r , e tc . H o w e v e r , n e w s t a b l e n it r o -g e n is o t o p e r a t io b y G C / I R M S ( S o h ns e t a l . 1994;G e r l i n g e t a l . 1 99 7 ) s t i ll s h o w t h a t l i g h t n i t r o g e np r e d o m i n a t e s ( 6 1 5 N r a n g i n g f r o m - 9 t o + 3 % 0 ) i nt h e a r e a a d j a c e n t t o t h e i n t r u s i v e s o f t h e B r a m s c h em a s s i f , w h e r e t h e r o c k s r e a c h m a t u r i t y a b o v e R m a x4 % . T h e r e f o r e , a m m o n i a w i t h h i g h e r 6 J S N s h o u l db e a n i m p o r t a n t p r i m a r y p r o d u c t o f th e d e n i t r o -g e n a t i o n p r o c e s s . T h i s i n t e r p r e t a t i o n d o e s n o t p r e -c l u d e a d i r e c t c o - g e n e si s o f m o l e c u l a r n i t r o g e n f r o mc o a l ( K r o o s s e t a l . 1 99 5 ), a g e n e r a t i o n o f m o l e c u l a rn i t r o g e n f ro m a s e c o n d a r y d e c o m p o s i t i o n o f a m m o -n i a ( R o h r b a c k e t a l . 1 9 83 ) o r a m i x i n g o f N 2 f r o ms e v e r a l s o u r c e s ( M i i l l e r e t a l . 1 9 7 3 ; G e r l i n g e t a l .1 9 9 7 ) . I n d e e p s e d i m e n t a r y b a s i n s , w h e r e t h e r e d o xp o t e n t i a l i s l o w , N H ~ - , w h i c h w o u l d f i n d i t s w a y i nt h e i l l i t e / m u s c o v i t e i n t e r l a y e r s , is t h e m o s t s t a b l ef o r m o f a q u e o u s n i t r o g en , u n l e s s a n o x i d i z in g c a t a-l y t ic ag e n t i s e n c o u n t e r e d a l o n g t h e p a t h t h a t p r o -d u c e s N 2 ( G e t z , 1 9 7 6 , 1 9 8 1 ; H a l l a m a n d E u g s t e r ,1 9 7 6 ; E v e r l i e n a n d H o f f m a n n , 1 9 9 1 ) . I n f a c t ,D a n i e l s a n d A l t a n e r (1 9 90 , 1 9 93 ), s h o w e d , i n t h ec a s e o f t h e P e n n s y l v a n i a n a n t h r a c i t e f i e l d , t h a t t h eo r g a n i c m a t t e r d i s p e r s e d i n t h e s h a l e a n d c o n c e n -t r a t e d i n n e a r b y c o a l s e a m s r e l e a s e s n i t r o g e n i n c o n -n a t e b r i n e i n t h e f o r m o f a q u e o u s a m m o n i u m .A u t h i g e n i c N H 4 - r i c h i l li t e f o r m s b y h i g h t e m p e r a -t u r e r e a c t io n o f a m m o n i a , d e r i v e d f r o m m a t u r a t i o no f l o c a ll y a b u n d a n t o r g a n i c m a t t e r , w i t h k a o l i n i t e( J u s t e r e t a l . 1 9 8 7 ) . T h e p o s t u l a t e d h y d r o t h e r m a lf l u i d s t h a t f l o w e d t h r o u g h s o m e j o i n t s i n th ea n t h r a c i t e a p p e a r t o h a v e b e e n e n r i c h e d i n M g , F ea n d o t h e r t r a n s i t i o n e l e m e n t s . T h e y a r e r e s p o n s i b l ef o r f o r m i n g s o m e u n u s u a l o r d e r e d m i x e d - l a y e r c l a ym i n e r a l s , s u c h a s t o s u d i t e , s u d o i t e a n d r e c t o r i t e .T h e s e b r i n e s d o n o t a p p e a r t o h a v e c a r r i e d a m -m o n i u m i n t o a u t h i g e n i c m i n e r a l s , s u c h a s N H 4 - i l -l i te a n d p y r o p h y l l i t e . R a t h e r , t h e s e m i n e r a l s o c c u ri n c l o s ed , l o w p e r m e a b i l i t y e n v i ro n m e n t s i n t h es h a l e a n d c o a l m a t r i x a n d s p o r a d i c a l l y in s o m ej o i n t s s e t s. A l l e l e m e n t s in N H 4 - i l l i t e a n d p y r o p h y l -l i t e a r e e a s i l y d e r i v e d f r o m t h e r o c k m a t r i x i t s e l f .

CONCLUSIONST h e s t u d y o f o r g a n i c n i t r o g e n a b u n d a n c e a n d i s o -

t o p i c c o m p o s i t i o n i n U p p e r C a r b o n i f e r o u s a n t h r a -c i te s u i te s o f P e n n s y l v a n i a ( U . S . A . ) a n d o f t h eB r a m s c h e M a s s i f ( G e r m a n y ) b r i n g s t h e f o l l o w i n gresu l t s :

( 1 ) T h e d a t a p r e s e n t e d c o n f i r m e a r l i e r re p o r t st h a t t h e o r g a n i c n i t r o g e n c o n t e n t d e c r e a s e s r a p i d l yf r o m a n t h r a c i t e t o h i g h e r r a n k .

( 2 ) C o n t r a r i l y t o n i t r o g e n c o n t e n t , t h e o r g a n i cn i t r o g e n i s o t o p i c c o m p o s i t i o n d o e s n o t c h a n g e w i t hr a n k a n d h e n c e c o u l d n o t b e u s e d a s i n d i c a t o r o fm e t a m o r p h i s m .

( 3 ) S l i g h t d i f f e r e n c e s o f 6 1 5 N i n b o t h a n t h r a c i t es u i t e s m a y r e v e a l d i f f e r e n c e s o f t h e p a l e o p h y t o g e o -g r a p h y a n d t h e p a l e o c l i m a t e o f t h e t w o b a s i ns .

( 4 ) S e a l e d g o l d c e l l e x p e r i m e n t a t i o n r e p r o d u c e st h e b e h a v i o r o f o r g a n i c n i t r o g e n w i t h r a n k i n c r e a s e:r a p i d d e c r e a s e o f N c o n t e n t a n d p e r s is t e n ce o fn i t r o g e n i s o t o p e c o m p o s i t i o n a s w e l l a s c a r b o n i s o -t o p e c o m p o s i t i o n .( 5 ) T h e r a p i d d e n i t r o g e n a t i o n a n d t h e i n v a r i a n c eo f N i s o t o p e c o m p o s i t i o n i n b o t h a n t h r a c i t e s u it e ss u g g e s t t h a t a m m o n i a m i g h t b e a n i m p o r t a n t p r o -d u c t o f t h e d e n i t r o g e n a t i o n p r o c e s s i n t h e l a t es t a g e s o f c o a l i f i c a t i o n .A c k n o w l e d g e m e n t s - - T h e authors w ish to thank Dr JeffreyLevine, Consulting geologist, Tuscaloora, Alabama, forproviding some Pennsylvannian anthracites and for helpfuldiscussion and encouragement on our efforts to furtherunderstand the processes of deep gas formation. AngelikaVieth-Redemann from Geologisches Landesamt, Krefeldand Bundesanstalt ftir Geowissenschaften und Rohstoffe,Hannover are gratefully acknowledged for supplying thesamples from the Bramsche Massif . The authors thankProfessor A . M ariott i (La boratoire de Biog6ochimie desIsotopes Stables, U niversit+ Paris VI) for the replication o fsome isotopic analyses presented in the paper and E. Petit(Laboratoire de G6ochimie des Isotopes Stables,Universit+ Paris VII) for his assistance with the t~ 3 C de-termination. Many thanks also to PROLABO (France) forthe Microdigest 301 apparatus used in this work. The criti-cal review s of the manuscript by D r B. H. Horsfield (edi-torial) , Dr B. M. K rooss and D r E. F aber were greatlyappreciated.

R E F E R E N E S

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