Hydrocarbon inclusions in vein quartz (the "Marmarosh diamonds") from the Krosno and Dukla zones of the Ukrainian Carpathians

Geological Quarterly, 2000,44 (4): 41 5-423

Hydrocarbon inclusions in vein quartz (the "Marmarosh diamonds") from the Krosme, and Dralda zones of the Ukrainian Carpathians

Ihor DUDOK and ICatanyna JARMOLOWICZ-SZULC

Dudok I. and Jnrmolowicz-Szulc K. (2000) -Hydrocarbon incIusions in vcin quartz (thc 'TuIarmarosR diamonds'? from thc Krosno and Duklazoncs of thc Ukrainian Carpathians. GcoI. Quart., 44 (4): 415-423. Wanzawa.

Fluid inclusion studics wcrc conducted in the vein quartz known as ihe "Marmamh diamonds" of thc Kmno and DukIa zoncs of thc Ukraininn Carpathians, which arc potcniiaIly oil- and gas-bcaring. Thc "Marmarosh diamonds" contain diffcrcnt typcs of fluid inclu- sions which rccord thc evolution of thc quark formation. Thc ~nclusions wcrc studicd by mcans o f gas climrnatograpl~y, microthcrmornchy and flutlrcsccncc. Thc follow~ng scquencc llas bccn obscnrcd: rnethanc inclusions displaying characteristic fcaturcs duc to crystallography, lighl hydrocarbons, cornplcx inclusions with a mricty of bitumcns, and gas-liquid inclusions with two diffcrcnt hydrocarbon phascs. Thc rcgions ~vl~crc thc light l~ydrocarbon inclusions occur sccm to bc tho most promising as rcgards oil andgaspros- pccts.

Ihor Dudok, Ukr.ai~iiait Natioi~al Rcadcrny of Scierrces, Naukovu 3a, 290053 Lviv. Ubair~c; Katalzy~m Jartnolmin-Szirlc. Polish Geo- logical brsfitute, Rakowiecka 4, PL-00-975 Warszawa, Poieird (I-eceived: Mnwh 24, 20D0; accepted: April 17, ZOOO).

Kcy words: Ukrainian Carpathians, "Marmamsh diamonds", quartz, hydrocarbon inclusions, mcthanc, bitumcns, light hydrocflrbons.

INTRODUCTION

The Krosno and Dukla zona OCCLU in the central part of the strucbre of the Carpathians in the territory of Ukt-aine (Fig. 1). They _{are built of} Cretaceo~ls-Paleogene sedimentary rocks and display a nappe structure. Numerous h c t u r e zones occur, which are important as regards h e migration of hydro- carbons and the formation of hydrocarbon accumulations of commercial significance (Kudriavcev, 1963 ; Kopystianskij, 1978; Dole&, 1986).

The Kromo and D ~ d a zones may contain oil and gas.

Along strike in Poland, the same structures, known as the Silesia and Dulcla zones, contain recognised oil and gas fields (Karnkewski, 1993).

The first description of the "Mmarosh diamonds" in the Ukrainian Cnrpathians was by Matkovskij (1 961). Subse- quently, inass spectrometTic analyses and cryometric studies identified methane and heavier hydrocarbons (up to pentane), in the inclusions as well as carbon dioxide and nitrogen (Zacycha, 1975; Brahts ^d al., 1 98 1 ; Dudolc, 19961, Some de- tenninations of the concentrations of the hydrocarbons were made (ICaliumyj and Lomov, 1490,1992; Bratus eta]., 1991;

Vityk eb a[., 11995). The possibility of using the fluid inclusion

data to interpret the tectonic history of the Ukrainian Carpathiam was suggested by Vityk eb at. (1 996). Aspects of the phase com- position and the problems of classifying the hydrocarbon h c l ~ l - sions were described by Dudok et nl. (1997), and prehinary fluorescence studies were reported by Dudok and Jarmolowicz-Smlc (1 999).

This paper gives the latest data on the hydrocarbon inclu- sions in the quartz of the "'Mmarosh diamonds" and recon-

s.hucts fluid evolutiion in the Ukrainian part of the Carpathians.

GEOLOGICAL AND MINERALOGICAL SETTING

Tectonic fractures within the Krosno and Dukla zones show various orientations. The ^most pronounced systems have NE (4040') and NW (4&60°) trends. These are ore present throughol~t. Their orientation i s parallel to the main regional tec- tonic trends. There occur also tluee other fracture directions, as:

two near N-S (34b350 and 10-20') and one approximately transverse to these (255-275O). These Fractures are best ^seen in tlie Middle and Upper Paleogene deposits.

These ii.acttres are filled with various vein minerals. Calcite and quartz are predominant, together with bitumens such as e.g.

416 Ihor Dudok and Katarzyna Jarmdowicz-Swlc

UKRAINIAN CARPATH! ANS

Fig. 1. Schematic tectonic map o f tl~c Ukrainian Carpathians (aftcr Kruglova and Cypko cds., 1988)

1 - SW margin of thc East European Craton, la - Boryslav-Pokutsk zonc, II - ^{Sk~ba zonc,} III --Krosno zonc, IV - Tschcrnogorsk zone, V

- Ouklazone, VI-Porkulensk wnc, VII-Rahvzonc, VIII-Magum zonc, IX- Marrnarosh Klippcn Bclt, X- Mamarosh clyslallinc massif, XI - Pieniny Klippm zone, XI1 - Carpathian Intradeprcssion; p i n t s show ssmplc locations of thc "Marmamsh diamonds" in thc Kmsno and Dukla zones

anthraxolite, ekerite and asphaltite. The thickness of veins ranges from some nillimeires to 10-20 cm, averaging some centimetres.

ColourI ess quartz is the most informative mineral in this as- sociation, Quartz crystals display two pyramids and have a prismatic, rhombohedra1 as well as pseudocuknc habit (Fig. 2).

Such characteristic crystals were frst found in the Marmarosh Massif in the Carpathians and were called "Marmarosh dia- mends". Q u m of this type has been described from many re- gons of the Alpine province, and characteristically conrains hydrmafbon inclusions (Vomidc et al., 1973).

The c M ~ a r o s h diamonds" £ram the Krosno and Dukla zones range in size from millimebes to 3-3.5 cm. Generally they are 2-8 mm.

FLUID INCLUSIONS: EVOLUTION OF MORPHOLOGY, COMPOSITION

AND P-T PAMMETERS

Fluid inclusions of various size were studied in quartz crys- tals from regions where "Marmarosh diamonds" commonly

occur in the Wainian part of the K.rosno and Dulda zones (Fig. I),

In the Krosno zone, such quartz occurs in the Czemaja Tisa river basin (close to Jasinia), along the and Ripinka rivers and their tributaries (around Miezgorije, Sojma, Riphnoje, Riechkq Majdan, Goliath and Bielasmica) and along the Latorica river (the region of Volovec, Nimi Vorota, Oporec,

Abramka and Jabliunica).

In the Dukla zone

-

the "Mannarosh diamonds" occur in the basin of the Uz river (near Stavne) and Pinia (near PIoskoje).

The nomenclature of Dudok et al. (1997) is used in this pa- per:

G

- gas phase containing d ymethane; L - liquid, water-like phase with a low concentration of saIts; L1 -liquid, hydrocarbon-like phase; (G2) - condensed methane-butane mixture, gaseous in n dconditions; I3 - solid phase repre- sented by bitumens of diment composition.

The hydrocarbon incIusions con~spond to four groups:

methane, oil-methane, methane-oil, and ail.

Represenbtive image of the inclusions are shown in Fig- ures 3-5. Sample numbers correspond to the site (e.g. 723) and the individual crystal studied (e.g. 72312 ).

Methane inclusions (G2) are those earliest ones in

the

"Mannarosh diamonds'' from the Ukrainian part of the Carpathians. They eitha dispIay a negative crystal form (Fig.

3a, b) or ate characteristically elongated (Fig. 3c, d). Methane is at the s~lpercritical stage and contains a Iittle water (3-5%). RS homogenisation temperatures fall into the intervaI of -145 to

-90°C (into the liquid phase) and -1 10 to -85OC (into the Iiquid phase) in the Kmsno and Dukla zones, repectively. The inclu- sions display a white-blue to blue fluorescence in the ultraviolet light.

The walls of the vacuoles of some inclusions are covered with a yellow-brown film of hard parafin. This film formed in

Fig. 2. Morphology of tRc crystals of thc "Marmnrosh diamonds"

rn - prism; p, z - rhombohcdrons (right, Icft); s - trigonal bipyramid

a, b - rrmfticomponextt inclusion in the34ramo zone, wnple 70912 (se-t Ripinnaje)

-

^{m d m s inclusion with} hard phuc ofof type 4L

+

^B (Lz -

methane Zq critical a t e , 3 -Ma& anthrmotib]: a- in the polarised light, b - in ultreviolet; c, d - diEorwt multiogmpo~cnl inclusion in tho Dukta zono, sample 76U41 (settlement Stavne)- hydraarbom incIusionwithafgaaic mined in hard phase, Thc57"C (into @I: ^G-in polariscd light, d -in dtmviolet; e, f - w q I e T13P2 (ssttiemwrt P I o ~ ) - light bmwh paraffin showing orange f i u o m w in the hard mclusion p b c , T h = W C (Into liquid): c - in potdtiad light, f- la dtraviolct

1

^{O,OS rnm}

FIE. 5. Primary h y h d o n inchsions with oiI dmplets of brown colour

a, b-sampIo 799110 (Krosno zone): a-in poIarisd light, b- inuItr&violst: c, d-ample ?OW7 ( b m o zone): c-in polaris& light, d- in ultmviotot;

e, f - Iwo different hydrocarbonphasss m the inclusions, large primary methane Inclusion with crystalline wganic matter in the walls ofthrr vacuulc: c- in ultraviolet; f

-

^socodaq gas-liquid h~lusious with hydmarbons of "light ail"type, m ulbaviolct

420 mar Dudok md Katai zyna Jarmotowicz-Szulc

the inclusion vacuole after n decrease in p T conditions. The film looks to have a complex crystalhe siructure, indicating

"stn~cttualisation" of the organic matter into ~Raracteristic

shapes.

The inclusions of

L

(G2) type which are paranel to the "c"

axis are swoundcd by aureoles of da~lghter gas-liquid inch- sions (Fig. 3a, b). They display a light yellow colour and their chemical composition corresponds to that of primary ones (Gar. When heated to 1 10°C, their gas bubbles diminish nearly by half, expldng at about I 1

5°C.

The palaeotemperature decrease to 170-1 80°C resulted in formation of the following types of the inclusions in the

"Marmarosh diamonds": light hydrocarbon inclusions

(L,),

difhent bitlunens and complex inclusions as - I_z (G2)

+

B,

L

-I-

L1

t- G, L, ^-I- G, Ll -t- G +B, LI + B (Figs. 3e, f and 4% b). The solid phase developed as block anthraxolite is most characteris- tic of the methane inclusions (Fig. 3e). LocalIy, the a n h o l i t e foms the base for the (G?) inclusion (Fig. 3e, f). The solid phase can be also represented by asphdtite (Fig. 4% b) and oc- casionally - by organic matter (Fig. 4c, d). No cbanga have b m observed on heating to 250°C. The solid phase has no flu- orescence.

Inclusions with liquid hydrocarbons are characteristic of the quartz sampled in the basins of the Uz and Pinia rivers (the Dukln zone) and Lacorica (the Krosno zone). Hydrocarbons display blnish-white fl~~orescence (Fig, 4e, f). When heated to 45-50°C they change their phase relations, generally ha- mogenising either into a liquid or gas phase. The tramition m- perature ofthe hydrocarbon fluid into the critical state l i a in a wide interval of -43 to 80.8"C (Xh~dok et al., 1997). In the in- clusion of LI

+

G type the separated oil phase is often observed in the form of individual drops (Fig. 5a, b) which may even ar- range themselves into some bigger forms perpendicular to the

"c" axis of the i n c l ~ ~ i o n pig. 5c, d).

The gas-liquid inclusions with two different hydrocarbon phases me the latest ones in the qr- from the DlIWa zone.

The majority of the vacuole's volunle (60-70%) is filled with the lighter hydrocarbon phase @ILI~ fluorescence in UV) being s~u-rounded by heavier hydrocarbons of yellow fluorescence;

tlie gas phase (20%) corresponds to the lighter hydrocarbon phase. S L I C ~ heavier hydrocarbons fill the gas or gas-fluid in- clusions which correspond to the healed fissures in the quartz crystals (Fig. 5e, f). In ultraviolet light these inclusions display yellow or yellow-orange fluorescence.

In the central zones of the crystals, xenogenic inclusions of calcite and small idiornorphic quartz crystals together with anthraxolite may be observed. Their formation took place at a temperature of about 50°C and at pressures of some tens of bars.

AnthmxoIite fragments also form zones parallel to the crys-

tal margn, occurring at the crystal stnface or filling the cmml part of the veins.

According to the pT data for the gas-fluid aqueous iaclu- sions (type L -k G), crystallisation of quartz occurred in the tem- pemture interval of 190-230°C and pressures of 2.7 kbar in the Krosno zone and 1.9 kbas in the. Dukla zone (Fig. 6).

Gas composition in inclusions in the 'CMsrmarosh dlomonds"

-

^Ukraininn Carpathians

Sampling localisation and thc ago: 704 - Sojma, 708 - Miczgorijc.

722-721 - Veca, 725 - Lay, 796 - Ripinnojc, 799 - Bcskid dcpres- sion, 7 1 1,712,741,742 (in Tab. 2) - Svalava-YoIovcc, 7 13 - Ploskojc, 762.163 - Stavnc

GAS COMPOSITION OF THE INCLUSIONS

IN

THE "MARMAROSH DIAMONDS"

Analytical studies on the gas composition in the inclusions were performed using the chromatograph 'Thorn 5". It was possible to detect N, C02 and hydrocarbons until octane. This is the first application of this method to the vein minerals of the Carpathian oil-bearing province.

The ~ s d $ of the chromatographic analysis are shown in Table 1. The accuracy of the determinations is as foIlows: C&

- 2 x 1 o - ~ ~ ; GH4

-

^{7 x 1 o-'gf}

^&HB

^C3Hs

-

^{5 x 10-~g; CzWs}

- 4 x 1 0 ~ ~ ; C~HIO, i - C ~ H ~ O - 3 x 11)-log; C5HI2-4x 10-log;

C6HL2 - 2 x 10-lag; CsH14, C7HI6, CsHla -2 x f

o - " ~ .

H y d m c a h n inclusions in vein quarlz (thc "Mmamsh diamonds") from thc Kmsno and Dukla zoncs of thc Ukrainian Carpathians 42 1

T a b l c 2 Hydrocarbon composition (%) of fluid inclusions in the "Marrnarosh diamonds" in the Krosno and DukIn zones

As it is seen f m n the table the methane and carbon dioxide tion and precipitation of the ore components. In the region of contents are between 76-1 00 and 5-22%, respectively. Only in Sojma (sample 796) polyrnetallic ores occur (Laanenko et a]., samples 708/2,713,723 and 796 does the CH4 content decrease 1963). Nitrogen is characteristic only for the samples taken to 33-54% together with an increase in COT to 46-67%. Ths fiom the boundary befween the Dukla zone and the Krosno one, last increase is associated with inclusions of kg f. G type, where as welI as that between the Krosno zone and the Skiba one.

L3

corresponds to liquid COz, These inclusions indicate mipa- Table 2 gves the hydrocarbon composition ofthe samples tion of methane - c m h n dioxide fluids, enabling transporia- studied, from methane to octane.

422 rhor Dudok and Karamyna JarmofowiczSzulc

Fig. 6. Rcsults of microthcrmometric analyses of fluid incIusions in thc "Marmamsh diamonds"

Rcsuits arc shown as a plot of mcthanc isochorcs (in glcm3); thc critical isochorc of mcthanc lics bchilccn 0.1 35 and 0.185

In general, hydrocarbons from methane to octane occur.

Methane predominates with very similar levels in both zones 175.77, 75.0 1 %, respectively). This is a lugher percentage of ethylene. and propylme in the Krosno zone than in the Dukla one. And, there is a higher percentage of ethane and alkanes in the DtMa zone than in the h s n o zone.

There is a correlation behveen the composition determined by gas chromatography md the gas composition ofthe individ- ual fluid incltlsions as determined by fluorescence (tftraviolet) and cryometric studies. Liquid hydrocarbons fm the inclu- sions in fhe Dukla zone (samples: 741 and 762) and

in

the Krosno zone (samples: 722, 796, 799) displaying a fltiores-

cence in yellow and yellow-mange colours. The hydrocarbon composition of the inclusions is chmcterised by heavy homo-

The '%farmarosh diamonds" from the Krosno and Dukla zones in the Ukrainian part of the Carpatlliaas: display a wide variety of fluid inclusion types.

They include pure methane inclusions, light hydrocarbon inclusions and complex inclusions with bittunens or organic matter. The regions where the light hydrocmhn inclusions oc- cur seem to be the most promising as regards the search for oil and gas.

These studies were partly supported by The Committee of Scientific Research (KBN) grant no 6 P04D 046 16 (PGI no.

5.45.0000.99.2).

logu& of methane (from 25.89 to 86.06%).

-

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