~ Pergamon

Org. Geochem. Vol. 29, No. 1 3, pp. 315-323, 1998

(~i) 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0146-6380(98)00072-2 0146-6380/98/$ - see front matter
Isotope study on organic nitrogen of Westphalian anthracites from the
Western Middle field of Pennsylvania (U. S. A. ) and from the Bramsche
Massi f (Germany)
MAGAL I ADE R ~*, J EAN- P AUL BOUDOU2t , MARC J AVOY' ,
BRUNO GOFFI~3:~ ERI C DANIELS4
' Laboratoire de GOochimie des Isotopes Stables, CNRS URA 1762, Universit6 Paris VII, 4 Place
Jussieu, 75251 Paris Cedex 05, France, 2Laboratoire de G6ochimie et M6tallog+nie, CNRS URA 1762,
Physicochimie des Fluides G6ologiques, Case 124, Universit6 Paris VI, 4 Place Jussieu, 75252 Paris
Cedex 05, France, 3Laboratoire de G6ologie, Ecole Normale Sup6rieure, 24, rue Lhomond, 75005 Paris,
France and 4Chevron Petroleum Technology Company, P.O. Box 446, La Habra, CA, U.S.A. 90633-
0446
Abstract The objective of this study was to examine an aspect of the thermal cycling of organic nitro-
gen in sediments and metasediments. The cycling of organic nitrogen is important because sedimentary
organic matter is a shuttle of nitrogen from the atmosphere to the lower crust and thermal decompo-
sition of organic matter is a critical step in the recycling of nitrogen between the different nitrogen
pools. Abundance and isotopic composition of organic nitrogen were determined in the particular case
of two low sulfur Westphalian anthracites series from Pennsylvania and Bramsche Massif. They rep-
resent good examples of Euramerica coals spanning the whole range of anthracitization in single fields.
Gold cell experimental simulation of the denitrogenation process was conducted at moderate pressure
to show that both suites make ideal metamorphic profiles without any shift due to change of facies or
to hydrothermal disturbance. During anthracitization, organic nitrogen content decreases rapidly while
organic nitrogen isotopic composition does not change with rank increase. The preservation of the iso-
topic signature implies that organic nitrogen isotopes could be used as indicators for the paleoecological
and paleodepositional history reconstruction of the basins. The striking contrast between the rapid and
sharp decrease of nitrogen organic content and the invariance of its isotopic composition during the
whole anthracitization suggests that ammonia is an important product of the denitrogenation process.
@) 1998 Elsevier Science Ltd. All rights reserved
Key words--nitrogen, isotope, anthracite, Pennsylvania, North Germany, metamorphism, coal, kerogen,
gold cell
INTRODUCTION
The r ma l ni t r ogen cycl i ng i n sedi ment s a nd met ase-
di ment s has recei ved little at t ent i on. Var i at i ons of
or gani c ni t r ogen cont ent and of its i sot opi c compo-
si t i on wi t h ma t ur a t i on r emai n l argel y unknown.
However , since hi ghl y me t a mor phos e d or gani c mat -
t er is supposed to cont ai n onl y t race a mount s of
ni t r ogen, one can predi ct t hat ni t r ogen is rel eased
by sedi ment ar y or gani c mat t er dur i ng di agenesi s
a nd met amor phi s m. I mpr ovement s of our knowl -
edge a bout t he fate of or gani c ni t r ogen i n na t ur a l
and exper i ment al ma t ur a t i on series shoul d l ead to a
bet t er unde r s t a ndi ng of t he process of deni t r ogena-
t i on and may hel p i n usi ng or gani c ni t r ogen iso-
t opes t o est abl i sh t he di s t r i but i on of ni t r ogen
a mong var i ous reservoirs i n ear t h (Javoy et al.,
*To whom correspondence should be addressed. E-mail:
ader @ipgp.jussieu. fr.
?E-mail: boudou@cicrp.jussieu.fr
:~E-mail: bruno@ euclase.ens.fr
E-mail: ejda@chevron.com
1986; Zha ng a nd Zi ndl er , 1993; Bebout , 1995;
Javoy, 1997).
The pr esent st udy report s or gani c ni t r ogen a bun-
dance a nd i sot opi c compos i t i on dur i ng ant hr aci t i za-
t i on. The obj ect i ve is to i nvest i gat e ideal
met amor phi c profiles of or gani c ni t r ogen f r om l ow
vascul ar pl ant s i n t wo Wes t phal i an ant hr aci t e
suites.
MATERIAL AND METHODS
The sampl es are listed i n Tabl e 1. The Wes t er n
Mi ddl e ant hr aci t e field of Penns yl vani a ( U. S. A. )
and t he Br amsche Mas s i f ( Ger many) , pal eobot ani -
cal l y dat ed as Wes t phal i an ( Mi ddl e Penns yl vani an) ,
were chosen because t he coal s r epr esent a wide
r ange of r a nk f r om ant hr aci t e to met a- ant hr aci t e.
Hence, t he whol e ant hr aci t i zat i on coul d be easily
obser ved i n t he same field. A second r eason was
t hat t here is a n a bunda nc e of ba c kgr ound mat er i al
avai l abl e for t he regi on, i ncl udi ng geological, pet r o-
graphi cal , geochemi cal synt heses and exper i ment al
s i mul at i on of coal ant hr aci t i zat i on a nd gr aphi t i za-
315
316 M. Ader et al.
Table 1. Samples, rank, organic N abundance and isotopic composition
Sample No Source* F i e l d Stratigraphy Rm~x (%) 100 N/C * 615N (%0) 613C (%0)
Pennsylvania
WM-GP-M8-CH JL Mammoth#8 Mid. Penn. 2.68 1.34 4.45 -24.30
WM-ED-M9-CH JL Mammoth#9 Mid. Penn. 2.97 1.43 4.65 -23.50
WM-SH-M8-GR JL Mammoth#8 Mid. Penn. 3.45 1.29 4.35 -24.30
WM-RN-LO-CH JL Little Orch. Mid. Penn. 3.78 1.22 5.05 -25.80
WM-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 -24.15
PSOC 870 PSOC Primrose Mid. Penn. 5.57 0.62 4.85 -23.95
16H ED Mammoth Mid. Penn. 5.66 0.67 4.75 -24.40
17A ED Buck Mtn Mid. Penn. 5.74 0.69 5.35 -23.50
2C ED Buck Mtn Mid. Penn. 6.30 0.66 4.15 -23.50
Bramsche
U150-7723 AVR Ibbenbfiren Westfal. C 2.91 1.00 2.80 -24.10
U150-7796 AVR lbbenbfiren West fal . B 3.51 1.01 3.72 -25.40
IB-115229 BGR lbbenb0ren West fal . B 4.22 0.92 3.05 -23.70
IBW1-13493 AVR lbbenbfiren West fal . B 4.27 0.92 2.70 -24.00
IBW2-14488 AVR Ibbenbfiren West fal . B 4.72 0.98 3.00 -23.30
PIES-751 AVR Pi esber g West f al . D 6.00 0.50 3.70 -24.15
PIES-693 BGR Pi esber g West f al . D 7.00 0.40 3.60 -24.05
PIES-6770 AVR Pi esber g West f al . D 7.14 0.41 3.45 -24.92
*JL: J. Levine, PSOC: Penn State Office of Coal Research, ED: E. Daniels, AVR:
BGR: Bundesanstalt fiir Geowissenschaften und Rohstoffe.
*Organic N/organic C, atomic ratio x 100.
A. Vieth-Redemann (Geologishes Landesamt NRW),
t i on ( Tei chmf i l l er a n d Tei chmf i l l er , 1950;
Hr y c k o wi a n e t al . , 1967; Mu n d r y , 1971; St adl er a n d
Tei chmf i l l er , 1971; Bu n t e r b a r t h a n d Tei chmi i l l er ,
1979; Ed mu n d s e t al . , 1979; Ol e ks ys hyn, 1982;
Levi ne a n d Davi s , 1983, 1989; Phi l i ps e t al . , 1985;
Da ni e l s a n d Al t a ne r , 1990, 1993; Levi ne a nd
Eggl es t on, 1992; Wi l ks e t al . , 1993; Da ni e l s e t al . ,
1994; Bus t i n e t al . , 1995).
Pe n n s y l v a n i a n coal s ampl es wer e col l ect ed f r om
o u t c r o p s a n d s t r i p mi nes. Br a ms c he Ma s s i f s ampl es
wer e col l ect ed f r o m t he coal mi ne s o f I b b e n b f i r e n
a n d Pi esber g. I n or de r t o a voi d a ny c ha nge o f
pa l e ode pos i t i ona l faci es a l ong t he a n t h r a c i t i z a t i o n
s equence, onl y s ampl es wi t h l ow s ul f ur c o n t e n t
( < 1%) wer e sel ect ed f or t he st udy. Low- s ul f ur coal
i ndi cat es pa r t i c ul a r p a l e o g e o g r a p h i c a l - s e d i me n t o l o -
gi cal or i gi n a n d n o n - ma r i n e pos t - de pos i t i ona l geo-
chemi s t r y. Aci d c ondi t i ons d u r i n g t he pe a t st age of
coal f o r ma t i o n s houl d r es ul t i n l eachi ng o f aci d- sol -
ubl e el ement s , as wel l as i nhi bi t i ng s ul f ur f i xat i on
a n d mi c r obi a l d e g r a d a t i o n o f or ga ni c ma t t e r
( We s t ga t e a n d An d e r s o n , 1984; Ceci l e t al . , 1985).
Vi t r i ni t e r ef l ect ance me a s u r e me n t s a n d e l e me nt a l
anal ys i s o f c r ude s ampl es wer e p e r f o r me d a c c or di ng
t o St a c h e t al . (1982), Levi ne a n d Da vi s (1983),
Da ni e l s a n d Al t a n e r (1990, 1993) a n d Dani el s
(1992). Or ga ni c ma t t e r was i s ol at ed us i ng HF/ HC1
di ges t i on of t he mi n e r a l ma t t e r i n a P r o l a b o mi cr o-
wave di ge s t or ( Mi c r odi ge s t 301). I s ot opi c anal ys es
of t he or ga ni c ma t t e r wer e ma d e us i ng a Fi n n i g a n
De l t a E ma s s s pe c t r ome t e r a n d wer e r e p o r t e d i n t he
" d e l t a " n o t a t i o n : pe r mi l , r el at i ve t o t he Pee Dee
Be l e mni t e S t a n d a r d (~13C) a n d r el at i ve t o t he at -
mo s p h e r i c ni t r oge n (615N). Ni t r o g e n s ampl es wer e
p r e p a r e d us i ng c o mb u s t i o n i n q u a r t z t ubes wi t h
Cu O, Cu a nd Ca O i n or de r t o t r a p CO2 a nd H2 0
( Ke nda l l a n d Gr i m, 1990; Boyd e t al . , 1994; Boyd
e t al . , 1995). Ev a c u a t i o n on a v a c u u m l i ne pr o-
ceeded as fol l ows: Cu O, Cu a n d Ca O wer e degas s ed
f or 4 h at 600C, t he n powde r e d s ampl e was a dde d
a n d c o n d i t i o n e d at 300C f or 2 h. Th e l oaded a n d
pr e t r e a t e d t ube was t h e n f l ame seal ed, c o mb u s t e d at
950C f or 4 h, cool ed at 600C f or 3 h t o al l ow (i)
r es i dual oxygen t o r e c ombi ne wi t h cupr i c oxi de, (ii)
ni t r ous oxi de t o be r e duc e d by c o p p e r a nd (iii) car -
b o n di oxi de t o be t r a p p e d by Ca O. Th e n t he t ube s
wer e sl owl y cool ed t o a mb i e n t t e mp e r a t u r e al l owi ng
wa t e r t o c o mb i n e wi t h CaO. The q u a r t z t ube was
o p e n e d on a v a c u u m l i ne wi t h a t ube cr acker . The
c o mb u s t i o n gases wer e cool ed t o l i qui d ni t r oge n
t e mpe r a t ur e . Us i ng a Toe pl e r p u mp , t he pur i f i ed
ni t r oge n was c o n c e n t r a t e d i n a c a l i br a t e d vol ume
al l owi ng qua nt i f i c a t i on. Pos s i bl e c o n t a mi n a t i o n was
c he c ke d by s c a nni ng of m / z 12, 15, 16, 30, 32 a n d
40 ( Ar ) . Sampl es f or 613C d e t e r mi n a t i o n wer e pr e-
pa r e d i n a s i mi l ar but s i mpl er way: no Ca O was
a dde d t o t he c o mb u s t i o n t ube a n d t he CO2 was
s e pa r a t e d cr yogeni cal l y us i ng a l i qui d ni t r oge n t r ap.
Pr eci s i on f or 615N was _0. 15%o a n d f or
613C+0.05%o.
RESULTS AND DISCUSSION
V 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 wi t h m a t u -
r a t i o n
I n Fi g. 1, t he a t o mi c N/ C r a t i o o f or gani c ma t t e r
is expr es s ed wi t h r es pect t o vi t r i ni t e r ef l ect ance
bet ween ~Rma x 2.5 a n d 7. 5%. The or gani c N/ C
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 ~ Pennsyl vani a
o
\
Bramsche
\
- \
\
\
\
o ~ ~ o ~ o
0 N %
1
2.5 3.5 4.5 5.5 6.5 7.5
Rmx , %
Fig. 1. Organic nitrogen abundance vs Rn~ax for Pennsylvania and Bramsche natural samples.
(100) for the Pennsylvanian coals decreases from
~1. 4 to 0.6 (at Rma 6%) whereas for Bramsche
coals N/ C (100) the range is lower and decreases
from ~1. 0 to 0.4 (at Rmax 7%). The decreasing or-
ganic N/ C with rank for the Ibbenbiiren/Piesberg
series is here reported for the first time. Similar
rapid organic N/ C decrease above ~Rma x 4.5% was
also reported, but not comment ed on, by Vol kova
and Bogdanova (1989) in the Donet z anthracite and
meta-anthracite suite. A few authors, who claim
t hat total nitrogen is an acceptable substitute for
Organic nitrogen, also reported a decreasing trend
in the late stages of coalification: Suggate (1959) on
New-Zealand coals (who wrote t hat "furt her infor-
mat i on is clearly required" t o provide an adequate
justification of the observed trends), Shapiro and
Gr ay (1966) on Antarctic coals, Drechsler and
Stiehl (1977) on German anthracites, Paxt on (1983)
on the Pennsylvanian anthracite field and Burchill
and Welch (1989) on the British coals. More
recently, Littke et al. (1995) showed a very weak
decrease of the total N cont ent in a series of 3
anthracites and 2 meta-anthracites from several ori-
gins. These repeated observations tend to support
the validity of a general interpretative scheme where
the main loss of organic nitrogen occurs in the very
late stage of coalification (Boudou et al., 1984;
Boudou and Espitali~, 1995).
Organic nitrogen isotopic composi t i on as a tracer o f
origin
Previous works (Peters et al., 1978; Mariotti,
1982; Rigby and Batts, 1986; Scholten, 1991) have
assessed the potential of 15N/I4N ratio as indicator
of sedimentary environment. I n the Pennsylvania
and Bramsche Massif suites, c515N as well as 613C
do not change systematically with rank (Table 1),
but anthracites display two narrow ranges of 615N
values: Pennsylvanian c515N values range from 4.1
t o 5.4%0 and Bramsche values range from 2.7 t o
3.7%o (Fig. 2). As expected, there is no 613C shift
during mat urat i on (Galimov, 1980; Lewan, 1986).
The present paper shows, for the first time, t hat in
the particular case of sedimentary organic matter
from lower vascular plants, organic nitrogen isoto-
pic composi t i on does not change during meta-
morphi sm (until ~Rmax 7%), from anthracite (PP
facies) t o meta-anthracite rank (greenschist facies,
Kish, 1987). In the case of Nor t her n Germany,
Gerling et al. (1997), studying the total nitrogen,
presented similar results t o ours for the anthracite
stage (until ~Rma x 4%), it means for the less im-
port ant stage of coal denitrogenation where inor-
ganic nitrogen content is still very low (Daniels and
Altaner, 1990, 1993). Our results add substance to
the argument of Haendel et al. (1986) who had
318 M. Ader et al.
6
~" 5
~ 4
o
2"L-L _ _ _
o
2. 5 3. 5 4. 5 5. 5 6. 5 7. 5
R~, , %
Fig. 2. ,615N of organic nitrogen vs Rma x for Pennsylvania and Bramsche natural samples.
assumed t hat a leveling of the ni t rogen i sot ope
composi t i on woul d t ake place duri ng diagenesis up
to the boundar y of greenschist facies.
Slight differences of organi c N cont ent and 615N
in bot h ant hraci t e suites (Pennsyl vani a and
Bramsche) are t hought to reflect the similarities and
slight differences of the pal eophyt ogeogr aphy and
the pal eocl i mat e of the two basins, at a t i me of
maxi mum assembl y of Pangaea dri ft i ng nor t hwar d
(Scotese et al., 1979). These facts woul d be in con-
formi t y wi t h the pal eobot ani cal results of Philips et
al. (1985) who wrot e t hat regi onal differences in tec-
t oni c setting, hi st ori cal aspects of the veget at i on
and l ocal envi ronment al differences may make the
pat t erns of veget at i onal change somewhat different
in each coal region. The drast i c changes in coal -
swamp veget at i on are t ransi t i onal across the
Mi ddl e- Upper Pennsyl vani an boundar y and are
very si mi l ar in each of the maj or coal regions of the
Uni t ed States and Europe. However, an i mpor t ant
difference between the veget at i on on either side of
the Appal achi ans is the cont i nued presence of some
Lycospor a- bear i ng Lycopods in Europe. Thi s is
possi bl y t he result of a mor e asymmet ri c change in
the dr yi ng of the cl i mat e t here ( Hedemann and
Teichmfiller, 1971). The slight differenciation of the
Pennsyl vani an and of t he Bramsche ant hr aci t e
suites on the basis of organi c ni t rogen i sot opes
shows t hat ni t rogen i sot ope dat a may be a signifi-
cant i ndi cat or of the pr ecur sor flora, the envi ron-
ment of deposi t i on and the t ype and degree of
al t er at i on of the pl ant substances. This differen-
t i at i on shoul d be expl ai ned by furt her studies on
the pal eoecol ogy of bot h coal -beari ng deposi t i onal
systems following the appr oach of Al t eNi umer
(1983), Wnuk (1985, 1989), Wnuk and Pfefferkorn
(1987) and Diessel (1992).
Experi ment al simulation
Since t here is no val i d met hod to experi ment al l y
simulate t he nat ur al met amor phi sm starting with an
i mmat ure coal (Wilks et al., 1993), the si mul at i on
was done with an ant hr aci t e sample t aken at the
onset of t he deni t r ogenat i on wi ndow (ant hraci t i za-
tion and furt her graphi t i zat i on). The si mul at i on was
conduct ed under hydr ost at i c pressure because the
role of t ect oni c sheari ng on ant hraci t i zat i on has not
yet been put in evidence (Levine, 1993). Moder at e
hydr ost at i c pressure (0.2 GPa) was chosen because
high pressure may have a suppressing effect on
mat ur at i on (Goff6 and Villey, 1984; Domin6, 1987;
Dal l a Tor r e et al., 1997). The ant hraci t e sample, the
t emper at ur e and pressure condi t i ons were chosen
accordi ng t o our previ ous wor k on open system py-
rolysis ( Boudou and Espitali6, 1995), gold cell ex-
peri ment s previ ousl y per f or med by Hr yckowi an et
Isotope study on organic nitrogen of Westphalian anthracites 319
Table 2. Analysis of anthracite sample WM-GP-M8-CH
% As received % Dry % Dry ash free
HzO 1.47
Volatile matter
Fixed carbon
Ash
BTU*
C
H
N
S
O (by difference)
9.97
74.82
15.21
12869
90.9
3.74
1.42
0~98
2.94
*British Thermal Unit per pound.
al. (1967) and some pr el i mi nar y experi ment s using
i sost at i c pressure by means of an anvil press
( Boudou et al., 1997). Being the least mat ur e
ant hr aci t e of t he Pennsyl vani an series, ant hr aci t e
sampl e WM- GP- M8- CH from t he Mi ddl e
Ma mmot h seam ( Hr yckowi an et al., 1967; Levine
and Davis, 1983) was chosen for the gol d cell exper-
iment. It s mai n characteristics, given by Levine and
Davi s (1983), are present ed in Tabl e 2. The sampl e
was heat ed at 600C, 0 . 2 GPa for 15days, in a
sealed gol d cell (Domin6, 1987). Hr yckowi an et al.
(1967), who per f or med gol d cell experi ment s with
an ant hr aci t e sampl e from the same coal seam as
WM- GP- M8- CH, had observed t hat 600C is criti-
cal in react i ons pr oduci ng a r api d increase of reflec-
t ance and a fusion of t he mat er i al t o f or m a har d
compact mass t hat we effectively observed in our
experi ment s. The gol d cell si mul at i on, per f or med in
our l abor at or y, showed t hat organi c N cont ent
decreases while t~13C and ~15N of the organi c mat t er
r emai n unchanged (Fig. 3 and Tabl e 3). These
changes are similar t o t hose observed in t he nat ur al
series (Fi gs 1 and 2, Tabl e l ). The const ancy of the
Table 3. Effect of the gold cell experimental simulation on the or-
ganic atomic N/C ratio, 6tSN and 613C of the WM-GP-MS-CH
anthracite
Experimental conditions N/C 6aSN (%0) ~13C (%0)
Initial sample 1.34 4.45 -24.30
Gold cell, 600C, 0.2 GPa, 0.77 4.40 -24.35
360 h
615N suggests t hat deni t r ogenat i on, in confined sys-
tem, as well as in nat ure, involves ot her react i ons
t han in open system pyrol ysi s, where ~lSN increases
(Drechsl er and Stiehl, 1977). The experi ment al
wor k of Kat r i t zky et al. (1995), Everlien (1997) and
Ger l i ng et al. (1997) suggests t hat pressured wat er,
which, in our study, may result f r om ant hr aci t e
degr adat i on as well as f r om cl ay paragenesi s, mi ght
pl ay a deni t rogenat i ng role. Wat er , in a sealed cap-
sule, as well as in hydr ous pyrol ysi s experi ment s,
woul d have an hydr ogenat i ng rol e (Huang, 1996;
Everlien, 1997; Lewan, 1997). Wi nt sch et al. (1981)
pr opose coal hydr ogenat i on by pressured neo-
f or med mol ecul ar hydr ogen as an i mpor t ant step in
the mechani sm of graphi t i zat i on, consequent l y of
deni t rogenat i on.
Organic nitrogen isotopes as tracers o f the mechan-
ism of denitrogenation
Because it t akes less energy t o br eak 14N-12C
bonds t han I SN- t 2c bonds, t her mocr acki ng of N-
C bonds shoul d pr oduce a preferent i al release of
14N (Bigeleisen, 1965; Mel ander and Saunders,
1980). As a result, i f deni t r ogenat i on i nvol ved t her-
mal br eaki ng of a hi gh energy bond, it shoul d l ead
to a st rong enri chment of t he heavi er ni t rogen iso-
t ope (Drechsl er and Stiehl, 1977; Haendel et al.,
1986; Bebout and Fogel , 1992). The present st udy
6
4
O
2
natural trend
-~ - / -
~5
O T ~.d 600C, 0.2 GPa, 15 days O
treated sample Initial sample
WM-GP-M8-CH
0 T I ~ J I
0.5 0.7 0.9 1.1 1.3 1.5
o r g a ni c N/ C, a t o mi c r a t i o x 100
Fig. 3. Results of gold cell experimental simulation with the Pennsylvania WM-GP-M8-CH sample at
600C and 0.2 GPa during 15 days (average of 2 runs). O: natural Pennsylvania samples (Table 1).
320 M. Ader e t al.
shows t hat 615N of organi c ni t rogen does not
change wi t h r ank despi t e the N/ C r at i o falling t o
hal f of its ori gi nal value. Assumi ng t hat ammoni a
has been pr oduced by irreversible react i ons wi t hout
any i sot opi c f r act i onat i on (Wi l l i ams e t al . , 1995;
Shearer and Kohl , 1993) and t hat mol ecul ar ni t ro-
gen deri ved from organi c mat t er has a low 615N
(Boigk e t a l . , 1976; Prasal ov e t a l . , 1990), it comes
t hat mol ecul ar ni t rogen woul d not be an i mpor t ant
pr i mar y pr oduct of the ant hr aci t e deni t rogenat i on.
Af t er Sohns e t al . (1994), t he Boi gk e t al . (1976)
dat a show syst emat i c devi at i on from the true
values, as a result of ai r cont ami nat i on for a sampl e
with very low ni t rogen concent rat i on, of i ncompl et e
combust i on of hydr ocar bons, of fl uct uat i on
amount s of oxygen in the i on source due to con-
t ami nat i on with air, etc. However, new stable ni t ro-
gen i sot ope r at i o by GC/ I RMS (Sohns e t a l . , 1994;
Gerl i ng e t a l . , 1997) still show t hat light ni t rogen
pr edomi nat es (615N rangi ng from - 9 to +3%0) in
the ar ea adj acent t o the intrusives of the Bramsche
massif, where the rocks reach mat ur i t y above Rmax
4%. Therefore, ammoni a with hi gher 6JSN should
be an i mpor t ant pr i mar y pr oduct of the deni t ro-
genat i on process. This i nt er pr et at i on does not pre-
clude a di rect co-genesis of mol ecul ar ni t rogen from
coal (Krooss e t a l . , 1995), a generat i on of mol ecul ar
ni t rogen from a secondary decomposi t i on of ammo-
ni a ( Rohr back e t a l . , 1983) or a mixing of N2 from
several sources (Mi i l l er e t a l . , 1973; Gerl i ng e t a l . ,
1997). In deep sedi ment ary basins, where the redox
pot ent i al is low, NH~-, which woul d find its way in
the i l l i t e/ muscovi t e i nt erl ayers, is the most stable
form of aqueous nitrogen, unless an oxidizing cat a-
lytic agent is encount ered al ong t he pat h t hat pr o-
duces N2 (Get z, 1976, 1981; Hal l am and Eugster,
1976; Everlien and Hoffmann, 1991). In fact,
Dani el s and Al t aner (1990, 1993), showed, in the
case of the Pennsyl vani an ant hraci t e field, t hat the
organi c mat t er di spersed in the shale and concen-
t r at ed in near by coal seams releases ni t rogen in con-
nat e brine in the form of aqueous ammoni um.
Aut hi geni c NH4-rich illite forms by high t empera-
ture react i on of ammoni a, deri ved from mat ur at i on
of locally abundant organi c mat t er, with kaol i ni t e
(Juster e t a l . , 1987). The post ul at ed hydr ot her mal
fluids t hat flowed t hr ough some j oi nt s in the
ant hraci t e appear to have been enriched in Mg, Fe
and ot her t r ansi t i on elements. They are responsi bl e
for formi ng some unusual or der ed mi xed-l ayer cl ay
minerals, such as t osudi t e, sudoi t e and rectorite.
These brines do not appear to have carri ed am-
moni um i nt o aut hi geni c mi neral s, such as NH4- i l -
lite and pyrophyl l i t e. Rat her, these mi neral s occur
in closed, low permeabi l i t y envi ronment s in the
shale and coal mat r i x and spor adi cal l y in some
j oi nt s sets. Al l elements in NH4- i l l i t e and pyr ophyl -
lite are easily deri ved from the r ock mat r i x itself.
CONCLUSIONS
The st udy of organi c ni t rogen abundance and iso-
t opi c composi t i on in Upper Car boni f er ous ant hr a-
cite suites of Pennsyl vani a (U. S. A. ) and of the
Bramsche Massi f ( Ger many) bri ngs the following
results:
(1) The dat a present ed confi rm earlier report s
t hat the organi c ni t rogen cont ent decreases r api dl y
from ant hraci t e t o higher rank.
(2) Cont r ar i l y t o ni t rogen cont ent , the organi c
ni t rogen i sot opi c composi t i on does not change wi t h
r ank and hence coul d not be used as i ndi cat or of
met amor phi sm.
(3) Slight differences of 615N in bot h ant hr aci t e
suites may reveal differences of the pal eophyt ogeo-
gr aphy and t he pal eocl i mat e of the two basins.
(4) Sealed gol d cell experi ment at i on reproduces
the behavi or of organi c ni t rogen wi t h rank increase:
rapi d decrease of N cont ent and persistence of
ni t rogen i sot ope composi t i on as well as car bon iso-
t ope composi t i on.
(5) The r api d deni t rogenat i on and the i nvari ance
of N i sot ope composi t i on in bot h ant hraci t e suites
suggest t hat ammoni a mi ght be an i mpor t ant pr o-
duct of the deni t r ogenat i on process in the l at e
stages of coal i fi cat i on.
A c k n o w l e d g e m e n t s - - T h e authors wish to thank Dr Jeffrey
Levine, Consulting geologist, Tuscaloora, Alabama, for
providing some Pennsylvannian anthracites and for helpful
discussion and encouragement on our efforts to further
understand the processes of deep gas formation. Angelika
Vieth-Redemann from Geologisches Landesamt, Krefeld
and Bundesanstalt ftir Geowissenschaften und Rohstoffe,
Hannover are gratefully acknowledged for supplying the
samples from the Bramsche Massif. The authors thank
Professor A. Mariotti (Laboratoire de Biog6ochimie des
Isotopes Stables, Universit+ Paris VI) for the replication of
some isotopic analyses presented in the paper and E. Petit
(Laboratoire de G6ochimie des Isotopes Stables,
Universit+ Paris VII) for his assistance with the t~13C de-
termination. Many thanks also to PROLABO (France) for
the Microdigest 301 apparatus used in this work. The criti-
cal reviews of the manuscript by Dr B. H. Horsfield (edi-
torial), Dr B. M. Krooss and Dr E. Faber were greatly
appreciated.
REFERENCES
Altebfiumer, A. M. (1983) Geochemische Untersuchungen
zur Klfirung der Fazies sowie der primfiren Migration
auf Menge und Zusammensetzung des organischen
Materials im Fl6z Katharina (Westfal A) und in den
hangenden Schiefertonen (Westfal B) im Ruhrgebiet.
Dissertation, Technische Hochschule Aachen.
Bebout, G. E. and Fogel, M. (1992) Nitrogen-isotope
composition of metasedimentary rocks in the Catalina
Schist, California: Implications for metamorphic devola-
tilization history. Geochi mi ca e t Cos moc hi mi c a A c t a 56,
2839-2849.
Bebout, G. E. (1995) The impact of subduction-zone meta-
morphism on mantle-ocean chemical cycling. Ch e mi c a l
Ge ol ogy 126, 191 2849.
Bigeleisen, J. (1965) Chemistry of isotopes. Sci ence 14"/,
463-471.
Isotope study on organic nitrogen of Westphalian anthracites 321
Boigk, H., Hagemann, H. W., Stahl, W. and Wollanke,
G. (1976) Isotopenphysikalische Untersuchungen zur
Herkunft und Migration des Stickstoffs nordwest-
deutscher Erdgase aus Oberkarbon und Rotliegend.
Erd6l und Kohle, Erdgas, Petrochemie vereignit mit
Brennstoff und Chemie 29, 103-112.
Boudou, J. P., Mariotti, A. and Oudin, J. L. (1984)
Unexpected enrichment of nitrogen during the diage-
netic evolution of sedimentary organic matter. Fuel 60,
430-431.
Boudou, J. P. and Espitali~, J. (1995) Molecular nitrogen
from coal pyrolysis. Kinetic modeling. Chemical
Geology 126, 319-333.
Boudou, J. P., Ader, M., Javoy, M., Besson, 21. M. and
Syfosse, G. (1997) Etude exp6rimentale du comporte-
merit sous haute pression de l' azote organique s~dimen-
taire, l er Forum de Technologie des Hautes Pressions. La
Londe les Maures, France.
Boyd, S. R., Rejou-Michel, A. and Javoy, M. (1994)
Noncryogenic purification of subnanomole quantities of
nitrogen gas for isotopic analysis. Analytical Chemistry
66, 1396-1402.
Boyd, S. R., Rejou-Michel, A. and Javoy, M. (1995)
Improved techniques for the extraction, purification and
quantification of nanomole quantities of nitrogen gas:
the nitrogen content of diamond. Measurement Science
Technology 6, 297-305.
Bunterbarth, G. and Teichmiiller, R. ( 1979) Zur
Ermittlung des Pal~totemperatur im Dach des Bramscher
Intrusivs aufgrund yon Inkohlungsdaten. Fortschritte in
der Geologie yon Rheinland und Westfalen 27, 171-182.
Burchill, P. and Welch, L. S. (1989) Variation of nitrogen
content and functionality with rank for some U.K. bitu-
minous coals. Fuel 68, 100-104.
Bustin, R. M., Ross, J. V. and Rouzaud, J. N. (1995)
Mechanisms of graphite formation from kerogen: exper-
imental evidence. International Journal of Coal Geology
2 8 , 1 36.
Cecil, C. B., Stanton, R. W., Neuzil, S. G. N., Dulong, F.
T., Ruppert, L. F. and Pierce, B. S. (1985) Paleoclimate
controls on Late Paleozoic sedimentation and peat for-
mation in the central Appalachian basin (U.S.A.).
International Journal of Coal Geology 5, 195-230.
Dalla Torre, M., Mfihlmann, R. F. and Ernst, W.
G. (1997) Experimental study on the pressure depen-
dence of vitrinite maturation. Geochimica et
Cosmochimica Act a 61, 2921-2928.
Daniels, E. L (1992) Nature and origin of minerals in
anthracite from Eastern Pennsylvania. P h . D. disser-
tation, Illinois University.
Daniels, E. J. and Altaner, P. (1990) Clay mineral authi-
genesis in coal and shale from the Anthracite region,
Pennsylvania. American Mineralogist 75, 825-839.
Daniels, E. J. and Altaner, S. P. (1993) Inorganic nitrogen
in anthracite from Eastern Pennsylvania, U.S.A..
International Journal of Coal Geology 22, 21-35.
Daniels, E. J., Aronson, J. L., Altaner, S. P. and Clauer,
N. A. F. (1994) Late Permian age of NH4-bearing iUite
in anthracite from Eastern Pennsylvania, temporal limits
on coalification in the Central Appalachians. Geological
Society of America Bulletin 106, 760-766.
Diessel, C. F. K. (1992) Coal-bearing Depositional
Systems. Springer Verlag, 721 p.
DominG, F. (1987) Influence de la pression et de la tem-
p6rature sur la cin+tique de pyrolyse d' hydrocarbures
purs. Etude exp6rimentale et simulation num6rique.
Implications g6ochimiques. Ph. D. dissertation,
Universit+ Pierre et Marie Curie.
Drechsler, V. M. and Stiehl, G. (1977)
Stickstoffisotopenvariationen in organischen
Sedimenten. Chemie der Erde 36, 126-138.
Edmunds, W. E., Berg, T. M., Sevon, W. D., Piotrowski,
R. C. Heyman, L. and Rickard, L. Y., (1979) The
Mississippian and Pennsylvanian (Carboniferous)
Systems in the United States: Pennsylvania and New
York (Carboniferous). U.S. Geological Survey,
Professional Papers 1110-B, 33 p.
Everlien, G. and Hoffmann, U. (1991) Nitrogen in natural
gas. Erddl und Kohle, Erdgas, Petrochemie/Hydrocarbon
Technology 44, 166 172.
Everlien, G. (1997) Hydrous pyrolysis of high-maturity
Paleozoic coals and black shales from Central Europe
and Adjacent areas: Thermodynamic considerations.
Geologisches Jahrbuch DI03, 43-64.
Galimov, E. M. (1980) CI3/CI2 in kerogen. In Kerogen,
ed. B. Durand, pp. 271-300. Editions Technip, Paris.
Gerling, P., Idiz, E., Everlien, G. and Sohns, E. (1997)
New aspects on the origin of nitrogen in natural gas in
Northern Germany. Geologisches Jahrbuch D103, 65-85.
Getz, F. A. (1976) Molecular nitrogen: clue in coal-de-
rived-methane hunt. The Oil and Gas Journal 25~ 220-
221.
Getz, F. A. (1981) CH4/N2-ratio in Northwest German
Basin. Erdd'l und Kohle, Erdgas, Petrochemie veriegnit
mi t Brennstoff und Chemie 34, 508.
Goff6, B. and Villey, M. (1984) Texture d' un materiel car-
bon~ impliqu~ darts un m~tamorphisme haute pression-
basse temp6rature (Alpes fran~aises). Les hautes press-
ion influencent-elles la carbonification? Bulletin de
Min~ralogie 107, 81 91.
Hallam, M. and Eugster, H. P. (1976) Ammonium silicate
stability relations. Contributions to Mineralogy and
Petrology 57, 227-244.
Haendel, D., Mfihle, K., Nitzsche, H. M., Stiehl, G. and
Wand, U. (1986) Isotopic variations of the fixed nitro-
gen in metamorphic rocks. Geochimica et Cosmochimica
Act a 50, 749-758.
Hedemann, H. A. and Teichmfiller, R. (197l) Le d6velop-
pement pal6og6ographique du Carboniffire sup6rieur.
Fortschritte in der Geolog& yon Rheinland und Westfalen
19, 134-147.
Hryckowian, E., Dutcher, R. R. and Dachille, F. (1967)
Experimental studies of anthracite coals at high press-
ures and temperatures. Economic Geology Series 62,
517 539.
Huang, W. L. (1996) Experimental study ot" vitrinite matu-
ration: effects of temperature, time, pressure, water and
hydrogenindex. Organic Geochemistry 24, 233-241.
Javoy, M. (1997) The major volatile elements of the earth:
their origin, behavior and fate. Geophysical Research
Letters 24, 177-180.
Javoy, M., Pineau, F. and Delorme, H. (1986) Carbon
and nitrogen isotopes in the mantle. Chemical Geology
57, 41-62.
Juster, T. C., Brown, P. E. and Bailey, S. W. (1987) NHa-
bearing illite in very low-grade metamorphic rocks as-
sociated with coal, northeastern Pennsylvania. American
Mineralogist 72, 555--565.
Kendall, C. and Grim, E. (1990) Combustion tube method
for measurement of nitrogen isotope ratio using calcium
oxide for total removal of carbon dioxide and water.
Analytical Chem&try 62, 526-529.
Kish, H. J. (1987) Correlation between indicators of very
low-grade metamorphism. In Low Temperature
Metamorphism, ed. M. Frey, pp. 227-300. Blackie,
Glasgow, London.
Katritzky, A. R., Shipkova, P. A., Allin, S. M., Barcock,
R. A., Siskin, M. and Olmstead, N. (1995) Aqueous
high-temperature chemistry. 22. Nitrogen-containing
heterocycles in supercritical water at 460C. Energy and
Fuels 9, 580-589.
Krooss, B. M., Littke, R., Miiller, B., Friefingsdorf, J.,
Schowochau, K. and Idiz, E. F. (1995) Generation of
322 M. Ader et al.
nitrogen and met hane from sedimentary organic matter:
implications on the dynamics of nat ural gas accumu-
lations. Chemical Geology 126, 291-318.
Levine, J. R. and Davis, A. (1983) Tectonic" history of
coal-bearing sediments in Eastern Pennsylvania using coal
reflectance anisotropy. Special Research Report SR-118,
Coal Research Section, The Pennsylvania State
University, University Park, Pennsylvania 16802, 323 p.
Levine, J. R. and Davis, A. (1989) Reflectance anisotropy
of Upper Carboni ferous coals in t he Appal achi an fore-
land basin, Pennsylvania, U.S.A.. International Journal
of Coal Geology 13, 341-373.
Levine, J. R. and Eggleston, J. R. (1992) The ant hraci t e
basins of East ern Pennsylvania. 1992 Joint Meeting of
the International Committee /'or Coal and Organic
Petrology and The Society .for Organic Petrology, 72 p.
The Pennsylvania State University, University Park,
Pennsylvania 16802.
Levine, J. R. (1993) Coalification: the evolution of coal as
source rock and reservoir rock for oil and gas. In
Hydrocarbons .from Coal, eds. B. E. Law and D. D.
Rice. Studies in Geology Series 38, 39 77. Ameri can
Association of Petroleum Geologists.
Lewan, M. D. (1986) Stable car bon isotope of amorphous
kerogens from Phanerozoic sedimentary rocks.
Geochimica et Cosmochimica Acta 50, 1583 1591.
Lewan, M. D. (1997) Experiments on the role of water in
petroleum formation. Geochimica et Cosmochimica Acta
61, 3691-3723.
Littke, R., Krooss, B. M., Idiz, E. F. and Frielingsdorf,
J. (1995) Molecular nitrogen in nat ural gas accumu-
lations: generation from sedimentary organic mat t er at
high temperatures. American Association of Petroleum
Geologists Bulletin 79, 410 430.
Mfiller, E., Goldbecher, K., Botnewa, G. and Botnewa, T.
A. (1973) Zur Geochemie und Genese stickstoffreicher.
Erdgase Zeitschr(ft Ji'ir Angewandte Geologic 19, 494
499.
Mariotti, A. (1982) Apport s de la g6ochimie isotopique ~i
la connaissance du cycle de l' azote Ph.D. dissertation,
Universit6 Pierre et Marie Curie.
Melander, L. and Saunders, W. H. (1980) Reaction Rates
of Isotopic Molecules. John Wiley and Sons, p. 333.
Mundry, E. (1971) Der Temperat urverl auf im Dach des
Bramscher Massives nach der W~rmeleitungs-Theorie.
Fortschritte in der Geologic yon Rheinland und Westfiden
18, 539-546.
Oleksyshyn, J. (1982) Fossil plants from the Ant hraci t e
coal fields of Eastern Pennsylvania. Pennsylvania
Geological Survey (4th Series). General Geological
Report 72, 157 p.
Paxton, S. T. 0983) Relationships between Pennsylvanian-
age lithic sandst one and mudrock diagenesis and coal
r ank in the Central Appalachians. Ph.D. dissertation,
The Pennsylvania State University.
Peters, K. E., Sweeney, R. E. and Kapl an, 1. R. (1978)
Correlation of carbon and nitrogen stable isotope ratios
in sedimentary organic matter. Limnology and
Oceanography 23, 598-604.
Philips, T. L., Peppers, R. A. and DiMichele, W. A. (1985)
Stratigraphic and interregional changes in
Pennsylvanian coal-swamp vegetation: Envi ronment al
inferences. International Journal of Coal Geology 5, 43
110.
Prasalov, E. M., Subbotin, Y. S. and Tikhomirov, V.
V. (1990) Isotope composition of molecular-nitrogen in
USSR nat ural gases. Geochemistry International 28, 11
22.
Rigby, D. and Batts, B. D. (1986) The isotopic compo-
sition of ni t rogen in Aust ral i an coals and oil shales.
Chemical Geology 58, 273-282.
Rohrback, B. G., Peters, K. E., Sweeney, R. E. and
Kaplan, I. R. (1983) Ammoni a format i on in l aborat ory
simulated t hermal mat urat i on: implications related to
the origin of nitrogen in nat ural gas. In Advances in
Organic Geochemistry 1981, eds. M. Bjoroy et al., pp.
819-823. J ohn Wiley and Sons.
Shapiro, N. and Gray, R. J. (1966) Physical variations in
highly met amorphosed Ant arct i c coals. In Advances in
Chemistry Series, ed. R. F. Gould, pp. 196 211.
American Chemical Society Publication, Washi ngt on
D.C.
Scholten, S. O. (1991) The di st ri but i on of nitrogen iso-
topes in sediments. Ph. D. dissertation, Ut recht
University.
Scotese, C. R., Bambach, R. K., Barton, C., Van Der
Voo, R. and Ziegler, A. M. (1979) Paleozoic base maps.
Journal of Geology 87, 217-277.
Shearer, G. and Kohl, D. H. (1993) Nat ural abundance of
tSN: Fract i onal cont ri but i on of two sources to a com-
mon sink and use of isotope discrimination. In Nitrogen
lsoto#e Techniques, eds. R. Knowles and T. H.
Blackburn, pp. 89-124. Academic Press.
Sohns, E., Gerling, P. and Faber, E. (1994) Improvements
in stable isotope determinations on nat ural gases.
Analytical Chemistry 66, 2614-2620.
Stach, E., Mackowsky, M. Th., Teichmiiller, M., Taylor,
G. H., Chandra, D. and Teichmiiller, R. (1982)
Textbook of Coal Petrology. Borntraeger, Stuttgart,
p. 482.
Stadler, G. and Teichmfiller, R. (1971) Zusammen-
fassender Uberblick fiber die Entwicklung des
Bramscher Massives und des Nieders/ichsischen
Tektogens. Fortschritte in der Geologic yon Rheinland
und WestJalen 18, 547-564.
Suggate, R. P. (1959) New Zeal and coals, their geological
setting and its influence on their properties. Bulletin of
New Zealand Department of Sciences Industry
Ressources 13, 113 p.
Teichmtiller, M. and Teichmfiller, R. (1950) Das
Inkohlungsbild des Nieders/ichsischen Wealdenbeckens.
Zeitsehr![~ der deutschen geologischen GesellschqJt 100,
498-517.
Volkova, I. B. and Bogdanova, M. V. (1989) Properties of
hi gh-rank coals and dispersed organic matter of associ-
ated rocks in the Donets Basin (USSR). International
Journal of Coal Geology 11, 315-339.
Westgate, L. M. and Anderson, T. F. (1984) Isotopic evi-
dence for the origin of sulfur in the Herrin (No. 6) coal
member of Illinois. International Journal of Coal
Geology 4, 1-20.
Wilks, K. R., Mastalerz, M., Bustin, R. M. and Ross,
J. V. (1993) The role of st rai n in the graphitization of
high volatile bi t umi nous and anthracitic coals.
International Journal qf Coal Geology 22, 247--277.
Williams, L. B., Ferrell, R. E. Jr., Hutcheon, I., Bakel, A.
J., Walsh, M. M. and Krouse, H. R. (1995) Nitrogen
isotope geochemistry of organic mat t er and minerals
during diagenesis and hydrocarbon migration.
Geochimica et Cosmochimica Acta 59, 765 779.
Wintsch, R. P., O' Connell, A. F., Ranson, B. L. and
Wiechmann, M. J. (1981) Evidence for the influence of
fcn4 on the crystallinity of disseminated car bon in
greenschist facies rocks, Rhode Island, U.S.A..
Contribution to Mineralogy and Petrology 77, 207-213.
Wnuk, C. (1985) The ontogeny and paleoecology of
Lepidodendron rimosum and Lepidodendron bretonense
trees from the Middle Pennsyl vani an of the Bernice
basin (Sullivan County, Pennsylvania).
Palaeontolographia 195B, 153-181.
Wnuk, C. (1989) Ont ogeny and palaeoecology of the
Middle Pennsylvanian arborescent lycopod
Bothrodendron punctatum, Bot hrodendraceae (Western
Isotope study on organic nitrogen of West phal i an anthracites 323
Middle Ant hraci t e field, Shamoki n Quadrangle,
Pennsylvania). American Journal of Botany 76, 966-980.
Wnuk, C. and Pfefferkorn, H. W. (1987) A Pennsylvanian
age terrestrial st orm deposit: Using pl ant fossil to
characterize the history and process of sediment ac-
cumulation. Journal of Sedimentary Petrology 57, 212-
221.
Zhang, Y. and Zindler, A. (1993) Di st ri but i on and evol-
ut i on of car bon and nitrogen in earth. Earth and
Planetary Science Letters 117, 331-345.