Discovery of high-abundance diamondoids and thiadiamondoids and

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Discovery of high-abundance diamondoids and thiadiamondoids and severe TSR alteration of Well ZS1C condensate, Tarim Basin, China Guangyou Zhu, Ying Zhang, Meng Wang, and Zhiyao Zhang Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.8b00908 • Publication Date (Web): 21 May 2018 Downloaded from http://pubs.acs.org on May 21, 2018

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Energy & Fuels

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Discovery of high-abundance diamondoids and thiadiamondoids

3

and severe TSR alteration of Well ZS1C condensate, Tarim Basin,

4

China

5 6

Guangyou Zhu a, *, Ying Zhang a, Meng Wang a, Zhiyao Zhang a,

7 8 9

a

Research Institute of Petroleum Exploration and Development, PetroChina, Beijing 100083, China

10 11

*Corresponding author. Tel.: +86 10 8359 2318; +86 18601309981.

12

E-mail address: [email protected] (G. Y. Zhu)

13

1

ACS Paragon Plus Environment

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Abstract: Diamondoid and thiadiamondoid compounds in crude oils are

15

generally related with thermal cracking and TSR (thermochemical sulfate

16

reduction). Diamondoids occur in almost all petroleum, but usually with low

17

concentration (2 µg/g or less). The abundance of thiadiamondoid reflects the

18

extent of TSR, which is rarely detected > 20 µg/g. Recently, a commercial

19

oil-gas production has been discovered in the deep Cambrian strata of the Tarim

20

Basin, China. The condensate sample conducted with GC×GC-TOFMS

21

(two-dimensional

22

analysis revealed that diamondoids series contains 281 components with total

23

concentration of 187 mg/g, and the thiadiamondoids series contains 267

24

components with total concentration of 28 mg/g, respectively. In this study, we

25

reported the identification of 14 compounds, including 11 dithiatriamantanes

26

and 3 tetrathiadiamantanes for the first time in natural oils. According to the

27

comprehensive analysis of sulfur and carbon isotopes and hydrocarbon

28

composition of the condensate, these compounds are considered to be residual

29

products of thermal cracking at high temperature and severed TSR alteration.

30

The extremely heavy sulfur isotope of the thiadiamondoid compounds from TSR

31

alteration illustrates that hydrogen sulfide enriched gas reservoirs exist in the

32

deep Cambrian strata of the Tarim Basin.

33

Key words: Diamondoid; Thiadiamondoid; Thermochemical Sulfate Reduction;

34

H2S; Deep Strata; Tarim Basin

gas

chromatography/time-of-flight

35 2


mass

spectrometry)

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1. Introduction:

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Oil and gas in deep strata is a recent hot topic in scientific studies and

38

exploration activities. Thermal cracking at high temperatures and TSR are two

39

of the significant secondary alteration processes in oil and gas from deep

40

carbonate strata, thus, diamondoid and thiadiamondoid compounds are often

41

detected in deep oil and gas, which are used to indicate thermal cracking1-3 and

42

TSR4-7.

43

Adamantane was first isolated by Landa and Machacek8 from Hodonin crude

44

oil. The structure of adamantane was confirmed by Prelog and Serwerth 9.

45

Further homologues of adamantane were isolated from petroleum fractions.

46

Birch et al.10 reported thiaadamantanes isolated from South Iran crude oil.

47

Thiadiamondoids have the same skeleton structure with diamondoids, with

48

carbon atom(s) replaced by sulfur atom(s) at the bridgehead position(s)

49

Diamantane was chosen as the official emblem of a 1963 IUPAC conference.

50

Triamantane was isolated and characterized in 1966. Diamondoid hydrocarbons

51

had aroused the interest of many scientists11-19. Chen et al.20 mainly applied

52

diamondoid compounds as maturity parameters. Dahl et al.21 demonstrated that

53

the relative abundance of diamondoid compounds can be used as indicators for

54

natural oil cracking to identify the occurrence and estimate the extent of oil

55

destruction and the oil deadline in a particular basin. Alkylated diamondoids

56

have been identified in crude oils and source rocks 22-24. On further study, 3 3


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tetramantanes, 6 isomeric pentamantanes, and as many as 17 possible

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hexamantane isomers have been isolated from petroleum1,25. Bridgehead

59

alkylated 2-thiaadamantanes were identified in the sulfurization process affected

60

petroleum which has undergone high thermal stress and indicated the occurrence

61

and extent of TSR26. More thiadiamondoids were found in oils and reservoirs

62

from the Smackover Formation4,27-28, and oils from the Tarim Basin6,29-33.

63

The concentration of diamondoids and thiadiamondoids in crude oil is

64

usually low2,21-22. They were often difficult to be isolated in GC-MS analysis.

65

Recently,

66

chromatography/time-of-flight mass spectrometry) has widely been used in

67

analysis of oil and condensate6,31-34. In GC×GC-TOFMS data, diamondoid and

68

thiadiamondoid compounds can be well separated from other alkanes and

69

aromatic hydrocarbons, and much more substitutions of these compounds can be

70

identified.

GC×GC-TOFMS

(comprehensive

two-dimensional

gas

71

Recently, we conducted GC×GC-TOFMS analysis on the condensate

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sampled from the first discovery well (ZS1C) that penetrated oil-gas in deep

73

Cambrian strata of the Tarim Basin. A series of diamondoid and thiadiamondoid

74

compounds were detected with extremely high abundance. We have detected

75

281 components of adamantane, diamantane, triamantane, tetramantane and

76

pentamantane;

77

thiatriamantane,

267

components

dithiaadamantane,

of

thiaadamantane,

dithiadiamantane, 4


thiadiamantane, dithiatriamantane,

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trithiaadamantane, trithiadiamantane, tetrathiaadamantane, tetrathiadiamantane

79

in ZS1C condensate, much more than previous studies32,38. Dithiatriamantane,

80

tetrathiadiamantane were detected in oil for the first time. The identification of

81

these diamondoids and thiadiamondoids were based on the comparison with

82

literature

83

tetrathiadiamondoids were detected in GC×GC-TOFMS for the first time.

data2,4,27,30.

Dithiadiamondoids,

trithiadiamondoids,

84

The discovery of the commercial oil-gas production in the well ZS1C has

85

opened a new exploration area and will lead to an extensive hydrocarbon

86

exploration in deep Cambrian reservoirs of the Tarim Basin.

87 88

2. Methods

89

2.1 GC×GC-TOFMS

90

The comprehensive GC×GC system for the GC×GC-TOFMS is from Leco

91

Corporation. Studies reporting GC×GC analysis of condensate samples are

92

rare43. The GC×GC system was composed of an Agilent 7890 GC coupled to a

93

hydrogen flame ionization detector (FID) and a liquid-nitrogen-cooled pulse jet

94

modulator. The TOF mass spectrometer is a Pegasus 4D (Leco Corporation). All

95

the data were processed with ChromaTOF software.

96

The one-dimensional chromatographic column was a DB-petro (50 m × 0.2

97

mm × 0.5 mm). The temperature program used was 0.2 min at 35 °C; increased

98

to 210 °C at a rate of 1.5 °C/min and held for 0.2 min; and increased to 300 °C 5


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99

at the rate of 2 °C/min and held for 20 min. The two-dimensional

100

chromatographic column was a DB-17ht (3 m × 0.1 mm × 0.1 μm). The

101

temperature program applied was the same as that for the one-dimensional gas

102

chromatography, but the temperatures were 5 °C higher. The modulator

103

temperature was 45 °C higher than for the one-dimensional gas chromatography.

104

The inlet temperature was 300 °C, the inlet mode was split injection, the split

105

ratio was 700:1, and the sample volume was 0.5μL. Helium was used as the

106

carrier gas, with a flow rate of 1.5 mL/min. The modulation time was 10s, 2.5s

107

of which was the hot pulse time. For the mass spectrometry, the temperatures of

108

the transfer line and the ion source were 300 °C and 240 °C, respectively, the

109

detector voltage was 1600 V, the scan range was 40-520 amu, the acquisition

110

rate was 100 spectra/s, and the delay time of the solvent was 9 min.

111

The group components of the compounds were quantified by peak area

112

normalization. D16-adamantane (using CH2Cl2 as a solvent) was added in the

113

condensate sample, and the quantitative results of conventional diamondoids in

114

the condensate were obtained using the internal standard method.

115

2.2 Carbon isotope analysis

116

The carbon isotope analysis of the hydrocarbon constituents of the natural

117

gas samples, collected in steel bottles at the production well site, was measured

118

using a GC interfaced to a Thermo Scientific Delta V Advantage isotope ratio

119

mass spectrometer. All δ13C values are given in per mil (‰, VPDB) according to 6


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delta notation with standard deviation accuracy of 0.10‰.

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2.3 Sulfur isotope analysis

122

The δ34S analysis of the aromatic fraction of ZS1C condensate (isolated by

123

liquid chromatography) were achieved using an Agilent 6890 GC coupled to a

124

Thermo Neptune Plus multi-collector inductively coupled plasma mass

125

spectrometer (ICP-MS)44. The OSCs were separated on the GC with a DB-5 MS

126

column (30 m × 0.25 mm i.d. × 0.1 µm film thickness). The GC oven was

127

heated from 100 °C (held for 0.5 min) to an end temperature of 300 °C (held for

128

15 min) at a rate of 8 °C/min. The argon gas for the plasma torch was pre-heated

129

and introduced co-axially with the analytes from the GC. An SF6 gas standard of

130

known

131

pulses were included at both the start and end of all sample analyses to internally

132

calibrate

133

relative to the international sulfur isotope standard Vienna Canyon Diablo

134

Troilite (VCDT) and represent the average of duplicate analyses and their

135

variance expressed as standard variation (SV ±).

136

34

S value was used for tuning and calibration of the ICP-MS. Two SF6

34

S measurements.

34

S results were reported as per mil (‰)

The aromatic fraction of ZS1C condensate contained large series of 34

137

alkylated benzothiophene and dibenzothiophene products, however,

138

measurement was only possible for those of highest abundance. The OSCs were

139

identified based on correlation of their GC elution position with published data

140

(e.g., Garcia et al.,45; Asif et al.,46). Methyl DBT isomers were identified from 7


S

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previously reported GC elution data (order of elution is 4-, 3+2- and 1-mDBT;

142

Garcia et al.,45). Isomeric assignment of higher molecular-weight alkyl DBTs

143

(and alkyl BTs) was not attempted and these analytes are simply referred to as

144

isomers i to iv (i.e., 34S data was measured for up to 4 different isomers of

145

some OSCs).

146

3. Results

147

3.1 Physical characteristics of the condensate oil

148

A condensate sample was obtained from 6861-6944 m interval of well ZS1C

149

which penetrated the lower Cambrian strata. The density of this condensate was

150

0.79 g/cm3 (20°C), the viscosity was 1.2-1.4 mPa·s (50°C) and the sulfur

151

content was less than 0.2%.

152

The bulk oil composition in well ZS1C condensate is dominated by saturated

153

and aromatic hydrocarbons which are 36.0%and 50.5%, respectively. This oil

154

contains unusually large amount of aromatic hydrocarbons. With increasing

155

maturity level, oils are generally enriched in saturated hydrocarbons. ZS1C

156

condensate enriched in aromatic hydrocarbons is caused by TSR alteration. So,

157

the organosulfur compounds are generated, and the density of oils becomes

158

heavy with highly aromatic hydrocarbons5,35.

159

3.2 Chemical composition of the condensate oil

160

The composition of the condensate samples was analyzed using

161

GC×GC-TOFMS to obtain a comprehensive two-dimensional color contour 8


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chromatogram (Fig. 1). The quantitative analysis of group components based on

163

the GC×GC-FID of oil samples indicates that the content of saturated

164

hydrocarbons, aromatic hydrocarbons, and resins was 42.2%, 54.9%, and 2.9%,

165

respectively. This result is rarely seen in ordinary condensates. According to the

166

GC×GC-FID analysis, the hydrocarbon distribution in the condensate ranges

167

from C6 to C30 with the main peak carbon of C11. Hydrocarbons greater than C30

168

are insignificant6.

169

The dominant aromatic hydrocarbons were multi-substituted series of

170

benzene, naphthalene, and phenanthrene. The content of alkylbenzene series and

171

polycyclic aromatic hydrocarbons was low. No sterane or terpane compounds

172

can be detected.

173 174

Fig. 1. GC×GC-TOFMS 2D contour chromatogram of ZS1C condensate.

175 176

3.3 Distribution of diamondoids

177

There are abundant diamondoids in ZS1C condensate, where adamantanes,

178

diamantanes, triamantanes, tetramantanes and pentamantanes can be detected

179

(See Fig. S1 for the family of diamondoids). The total content of diamondoids is

180

up to 187.8 mg/g. Fig. 2a shows the GC×GC-TOFMS color contour

181

chromatogram of the diamondoids. The lightness of each peak represents the

182

content of the compound. The closer the peak color to the red, the greater the 9


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183

peak area is. The quantitative results of all diamondoids were listed in Table S1.

184

In GC×GC-TOFMS data all diamondoids are well separated from each other,

185

different substitutions of diamondoids distribute regularly in their own cages in

186

distinctive regions. Different compound isomers show a distinctive linear

187

GCGC-TOFMS profile.

188 189 190

Fig. 2. Diamondoid hydrocarbons GC×GC-MS analysis of ZS1C condensate.

191 192

Adamantanes: at least 144 alkyl-adamantanes have been identified in the

193

selected m/z 135,136, 149, 163, 177, 191 or 205 chromatograms from ZS1C

194

condensate (Fig. 2b). The concentration of summed alkyl-adamantanes in this

195

condensate is up to 125.7 mg/g. The C0-, C1-, C2-, C3-, C4-, C5-, C6-, C7-, C8- and

196

C9-adamantane groups comprised 1, 2, 8, 23, 29, 30, 26, 13, 9 and 3 isomers,

197

respectively.

198

Diamantanes: a total of 74 alkyl-diamantanes have been detected (Fig. 2c).

199

The concentration of summed alky-diamantines is 56.0 mg/g. The C0-, C1-, C2-,

200

C3-, C4- and C5-diamantane groups comprised 1, 3, 21, 33, 13 and 3 isomers,

201

respectively.

202

Triamantanes: 50 alkyl-triamantanes exist with s/n ratios of over 100 (Fig.

203

2d). The concentration of alkyl-triamantanes is 6.0 mg/g. The C0-, C1-, C2- and 10


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Energy & Fuels

C3-triamantane groups comprised 1, 6, 21, 22 isomers, respectively.

205

Tetramantanes: 9 alkyl-tetramantanes have been detected (Fig. 2e). The C0-,

206

C1- and C2-tetramantane groups comprised 3, 4, 2 isomers, respectively. The

207

structure of three isomers of tetramantane has already been confirmed.

208

According to the distribution of these tetramantanes and 3 corresponding

209

C1-tetramantanes, it is inferred that the substituents of these three

210

C1-tetramantane are the same.

211

Pentamantanes: 3 alkyl-pentamantanes were detected (Fig. 2f). The

212

concentration of alkyl-pentamantanes is only 0.005 mg/g. There are six isomers

213

of alkyl-pentamantanes. Two isomers of pentamantane (cannot confirm their

214

structure) and one C1-pentamantane have been found in this condensate.

215

The identification of alkyl-tetramantanes and alkyl-pentamantanes is based

216

on their distribution in GC×GC-TOFMS chromatogram and the prominent

217

fragmental ions of 77, 91 and 105 in the mass spectra of all 12 compounds (see

218

Fig. S2 for the mass spectra of alkyl-tetramantanes and alkyl-pentamantanes).

219

3.4 Distribution of organic sulfur compounds

220

Extensive distributions of abundant OSCs (organic sulfur compounds) were

221

detected in ZS1C condensate (Fig. 3). The different OSCs’ resolved by

222

GCGC-TOFMS

223

benzylmercaptane,

224

phenanthrothiophene and thiadiamondoid compounds. Among the OSCs,

analysis

included

tetrahydrothiophene,

alkylbenzothiophene,

11


alkylthiophene,

dibenzothiophene,

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225

dibenzothiophenes have the highest concentration of 163.7 mg/g (Table S2). The

226

total content of thiadiamondoids is up to 28 mg/g (See Table S3 for

227

concentration and identification of all the thiadiamondoids). Such a high

228

abundance of OSCs in crude oil is very rare, indicating unique formation

229

mechanism of ZS1C condensate. The formation of ZS1C oil and gas represents

230

the complexity of geology and geochemistry progress.

231 232 233

Fig. 3. OSCs detected in ZS1C condensate collectively highlighted in the 2D GC×GC contour chromatograms.

234 235

3.5 Distribution of thiadiamondoid compounds

236

Diamondoids have the prominent fragmental ions of 79, 93,107 (77, 91 and

237

105) in the mass spectra. Thiadiamondoids have the same structure as

238

diamondoids, therefore, they have the similar prominent fragment ions.

239

Different compound isomers showed a distinctive linear distribution pattern,

240

which formed several lines in each cage separately. The identification of

241

thiadiamondoids was based on the comparison with mass spectra data reported

242

by Wei et al.2,4 Cai et al.30 respectively. Dithia-, trithia-, tetrathia-diamondoids

243

are first reported in the present study. Thiadiamondoids and corresponding

244

diamondoids have similar distribution in GCGC-TOFMS data, but later on 1st

245

and 2nd dimension retention time. Dithia-, trithia-, tetrathia-diamondoids have 12


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larger molecular weight, which are distributed later on 1st dimension retention

247

time, but are similar on 2nd dimension retention time. Diamondoids substituted

248

by the same number of sulfur atom distribute regularly. The possible location of

249

polythiadiamondoids can be predicted base on the regularity (Fig 3). Wei et al.27

250

considered the formation of thiadiamondoids might be accompanied by

251

diamondoidthiols.

252

diamondoidthiols or polythiadiamondoidthiols have been detected from ZS1C

253

condensate.

254

thiadiamondoids cannot only rely on their prominent fragment ions. For

255

example, adamantanethiols and thiaadamantanes have the same molecular

256

weight, same structure of diamondoids, thus they distribute close in

257

GCGC-TOFMS. The diamondoidthiols and thiadiamondoids were discussed

258

together in the present study.

259

3.5.1 Thiadiamondoids

However,

the

and

differentiation

diamantanethiols,

of

diamondthiols

even

from

Distribution of thiadiamondoids (substitute by 1 S atom) is showed in Fig.

260 261

Adamantanethiols

4a.

262 263

Fig. 4. Thiadiamondoids GC×GC-MS analysis of the ZS1C condensate.

264 265

Thiaadamantanes and adamantanethiols: 43 thiaadamantanes of ZS1C

266

condensate have been identified (Fig. 4b) with 23 more than the previous study 13


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267

of ZS1C condensate30,32. Newly recognized thiaadamantane products are the C1-,

268

C2-, C3-, C4- and C5-thiaadamantane groups comprised 1, 2, 2, 2 and 5 isomers,

269

respectively. Eleven (11) adamantanethiols were distinguished, which have the

270

unique fragment ions of 135, 149 and 163. Total concentration of

271

thiaadamantanes and adamantanethiols is 10.9 mg/g (Fig. 4b, Fig. S3).

272

Thiadiamantanes and diamantanethiols: a total of 53 alkyl-thiadiamantanes

273

have been detected. The C0-, C1-, C2-, C3- and C4-thiadiamantane groups

274

comprised 1, 9, 20, 18 and 5 isomers, respectively. Two diamantanethiols with

275

unique fragmental ions of 187, 201 have been identified. Total concentration of

276

thiadiamantanes and diamantanethiols is 9.9 mg/g (Fig. 4c, Fig. S4).

277

Thiatriamantanes and triamantanethiols: 17 alkyl-thiadiamantanes were

278

detected in the ZS1C condensate. The C0-, C1-, C2- and C3-thiatriamantane

279

groups comprised 3, 8, 5 and 1 isomers, respectively. Three (3) distinguishable

280

triamantanethiols have the unique fragmental ions of 239, 253 and 267. Total

281

concentration of thiatriamantanes and triamantanethiols is 0.7 mg/g (Fig. 4d, Fig.

282

S5). In addition to the prominent fragmental ions of 77, 91 and 105, there are

283

also fragmental ions of 128, 143 and 157 in the mass spectra of thiatriamantanes.

284

The position of alkyl-thiatriamantanes in GCGC-TOFMS data is the first time

285

to be reported here.

286 287

No thiatetramantanes have been identified in the condensate. 3.5.2 Dithiadiamondoids 14


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Distribution of dithiadiamondoids is showed in Fig. 5a. The position of all

289

dithiadiamondoids in GCGC-TOFMS data is the first time to be reported here.

290

There are 36 dithiaadamantanes identified from ZS1C condensate (Fig. 5b). The

291

total concentration of dithiaadamantanes is 2.5 mg/g (Fig. 5b, Fig. S6). Because

292

of the same molecular weight and similar distribution with 2-ring aromatic

293

hydrocarbons,

294

identification of dithiaadamantanes is based on the regular distribute of all

295

dithiadiamondoids and prominent fragmental ion of the mass spectra.

296

Dithiadiamantanes and dithiatriamantanes are easier to be recognized in

297

GCGC-TOFMS, which have the unique fragmental ions of 141 and 155

298

(mostly formed by the break of two bridgehead sulfur atoms). A total of 34

299

alkyl-dithiadiamantanes

300

thiadiamantaness and diamantanethiols is 1.0 mg/g (Fig. 5c, Fig. S7).

301

Alkyl-dithiatriamantanes

302

alkyl-dithiatriamantanes being detected from ZS1C condensate. The total

303

concentration of dithiatriamantanes is 0.06 mg/g (Fig. 5d, Fig. 6). No

304

dithiatetramantanes have been identified in the studied condensate.

dithiaadamantanes

were

were

were

detected.

identified

difficult

The

to

differentiate.

total

for the

first

The

concentration

time

with

of

11

305 306

Fig. 5. Dithiadiamondoids GC×GC-MS analysis of the ZS1C condensate.

307

Fig. 6. Mass spectra of representative dithiatriamantanes of ZS1C

308

condensate. Peak numbers correspond to those in Fig. 5d. 15


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

309 310

3.5.3 Trithiadiamondoids

311

Distribution of trithiadiamondoids and tetrathiadiamondoids was showed in

312

Fig. 7a. The position of all trithiadiamondoids and tetrathiadiamondoids in

313

GCGC-TOFMS data are the first time to be reported with 43 different

314

trithiaadamantanes being identified from ZS1C condensate (Fig. 7b, Fig. S8).

315

The total concentration of trithiaadamantanes is 2.5 mg/g. The identification of

316

dithiaadamantanes is based on the regular distribute of all trithiadiamondoids,

317

the concentration of compounds, and the prominent fragmental ion of the mass

318

spectra. Trithiadiamantanes are easier to be recognized in GCGC-TOFMS with

319

5 components being detected. Concentration of trithiadiamantane is 0.25 mg/g

320

(Fig. 7c, Fig. 8).

321 322 323 324 325

Fig. 7. Trithiadiamondoids and tetrathiadiamondoids GC×GC-MS analysis of ZS1C condensate. Fig. 8. Mass spectra of representative trithiadiamantanes of ZS1C condensate. Peak No. correspond to those in Fig. 7c.

326 327

3.5.4 Tetrathiaadamantanes

328

Tetrathiaadamantanes with 6 substations and tetrathiadiamantanes with 3

329

substations were detected from ZS1C condensate (Fig. 7d, e, f, Fig 9). 16


Page 16 of 67

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Energy & Fuels

330

Concentration of tetrathiaadamantanes and tetrathiadiamantanes are 0.025 mg/g,

331

0.025 mg/g, respectively. The mass spectra of tetrathiaadamantanes is influenced

332

by other compounds because of low concentration, with obscure prominent

333

fragmental ions. Tetrathiadiamantanes are identified in the oil for the first time

334

(Fig. 7f, Fig. 10). All their mass spectra have fragmental ions 77, 91 and 105

335

with high reliability.

336 337 338 339 340

Fig. 9. Mass spectra of representative tetrathiaadamantanes of ZS1C condensate. Peak No. correspond to those in Fig. 7e. Fig. 10. Mass spectra of representative tetrathiadiamantanes of ZS1C condensate. Peak No. correspond to those in Fig. 7f.

341 342

4. Discussion

343

4.1 The origin of diamondoids

344

Diamondoid compounds are continually generated and concentrated during

345

thermal cracking of crude oils at high temperatures2, therefore, the concentration

346

of diamondoid compounds is indicative for the extent of crude oil cracking1-2,36.

347

We have

348

alkyl-triamantanes, 9 alkyl-tetramantanes and 3 alkyl-pentamantanes from well

349

ZS1C condensate. This condensate sample contains highest number of

350

diamondoid compounds (281 in total) in the worldwide studies, indicating the

detected 145

alkyl-adamantanes, 74

17


alkyl-diamantanes, 50

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

351

high extent of thermal cracking. Alkyl-adamantanes has the highest

352

concentration (125.7 mg/g), which is almost 67.0% of all diamondoids (Table

353

S1), illustrating they are more stable than other diamondoid compounds.

354

According to the compositional and isotopic character of natural gas in well

355

ZS1C, the methane content reaches 62.7% while that of ethane is less than 0.5%

356

and the dryness coefficient (C1/C1+) is 0.987, representing a dry gas. Carbon

357

isotope values of the natural gas is relatively heavy, with δ13C1 of -42‰ and the

358

value δ13C2-δ13C1 less than 10‰, reflecting a high maturity37. Compared with

359

natural gases from Ordovician strata38, the gas from well ZS1C is classified as

360

oil-cracking gas at high temperatures, which is consistent with the high extent of

361

oil cracking indicated by the high concentration of diamondoid compounds.

362

4.2 The origin and implication of thiadiamondoids

363

Thiadiamondoids are molecular indicator of TSR3,26,39-41. Thiadiamondoids

364

share the same skeleton as diamondoids but with the bridgehead carbon replaced

365

by sulfur. Thiadiamondoid compounds with high abundance and diverse types

366

were detected in the condensate from well ZS1C (discussed in former section).

367

Thiadiamondoid compounds with extremely high concentration have not been

368

reported in previous studies, indicates the reservoir has been severely altered by

369

TSR.

370

In view of the compositional character of natural gas from well ZS1C, the

371

non-hydrocarbon gas content is relatively high, with CO2 of 24.2% and H2S of 18


Page 18 of 67

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Energy & Fuels

372

8.27%, suggesting a natural gas with high abundance of H2S generated through

373

TSR42. The extremely light carbon isotope values of CO2 (-30.18‰) indicates

374

the organic-inorganic interaction through TSR. TSR is a reservoir alteration

375

process in which organic matters or hydrocarbons are oxidized by sulfate,

376

ultimately yielding CO2 and H2S. TSR is well documented and can be

377

represented by the formula (1):

378

Hydrocarbon + CaSO4 → CaCO3 + H2S + CO2 + H2O

(1)

379

Because TSR is a chemical reaction between hydrocarbon and sulfate driven

380

by thermal dynamic, the organic-inorganic interaction and the isotopic

381

fractionation occurs in the TSR process. The CO2 was sourced from the

382

hydrocarbons participated in the reaction through TSR as its carbon isotope

383

value was similar to the natural gas which is -33‰32.

384

As to the sulfur isotopic character, the δ34S of thiadiamondoid compounds

385

varies in a range of 40.3‒45.1‰, whilst that of the sulfate in Cambrian strata

386

ranges from 32.0‒37.0‰ and that of the hydrogen sulfide is about 33.5‰. The

387

sulfur of hydrogen sulfide and thiadiamondoid compounds are sourced from

388

sulfate in the strata (Fig. 11), and they are considered to share the similar

389

isotopic values. Nevertheless, the δ34S of thiadiamondoid compounds is much

390

heavier than that of the sulfate from the Cambrian strata, thus, the δ34S

391

enrichment should be related to the severe sulfur isotopic fractionation caused

392

by TSR7. The light sulfur isotope was extracted and transferred to hydrogen 19


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 67

393

sulfide or other unstable organosulfur compounds, meanwhile, the heavy sulfur

394

isotope was concentrated in the thiadiamondoid compounds which were more

395

thermally stable. Therefore, the detection of thiadiamondoid compounds with

396

high abundance and diverse types, coupled with the extremely heavier sulfur

397

isotope, represents the occurrence of severe TSR and also indicates the high

398

concentration of hydrogen sulfide in deep oil-gas.

399 400

Fig. 11. Possible schemes for the formation thiadiamondoids and

401

diamondoidthiols

(thiadiamondoidthiols)

during

thermochemical

402

reduction (TSR) in Petroleum. R=nCH3(n=0, 1, 2, 3, ...)

sulfate

403 404

5. Conclusions

405

A series of diamondoid and thiadiamondoid compounds with extremely high

406

abundance and diverse types were detected in the condensate from the first

407

discovery well that penetrated oil-gas in deep Cambrian strata of the Tarim

408

Basin. The number of diamondoid compounds reaches 282 and that of

409

thiadiamondoid compounds is 268. This is a very unique condensate sample

410

which contains the most diamondoid and thiadiamondoid compounds in the oils

411

worldwide.

412 413

Various diamondoids and thiadiamondoids have been detected through GC×GC-TOFMS

analysis

with

some

2

cages

20


of

thiadiamondoids:

Page 21 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

414

dithiatriamantanes and tetrathiadiamantanes being detected for the first time in

415

this study. The detection of the polythiadiamondoid unravels the complexity of

416

TSR. Sulfuration reaction of different cages of diamondoids may occur

417

separately. Polythiadiamondoid are the production of the deep sulfuration of

418

diamondoids, accompanied by large amount of H2S generation at the same time.

419

According to the comprehensive analysis of sulfur and carbon isotopes and

420

hydrocarbon composition, these compounds are residues resulted from thermal

421

cracking at high temperatures and severe TSR alteration. Gas reservoirs

422

containing high abundance of hydrogen sulfide are the major exploration targets

423

in the deep Cambrian reservoirs of the Tarim Basin.

424

21


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

425

Reference:

426

1. Dahl, J.E.P.; Liu, S.G.; Carlson, R.M.K. Science 2003, 299, 96-99.

427

2. Wei, Z.B.; Moldowan, J.M.; Zhang, S.C.; Hill, R.; Jarvie, D.M.; Wang,

428

H.T.; Song, F.Q.; Fago, F. Org. Geochem. 2007a, 38, 227-249.

429

3. Wei, Z.B.; Mankiewicz, P.J. Org. Geochem. 2011, 42, 121-133.

430

4. Wei, Z.B.; Walters, C.C.; Moldowan, J.M.; Mankiewicz, P.J.; Pottorf, R.J.;

431

Xiao, Y.T.; Maze, W.; Nguyen, P.T.H.; Madincea, M.E.; Phan, N.T.; Peters,

432

K.E. Org. Geochem. 2012, 44, 53-70.

433 434

5. Walters, C.C.; Wang, F.C.; Qian, K.N.; Wu, C.P.; Mennito, A.S.; Wei, Z.B. Geochim. Cosmochim. Acta 2015, 153, 37-71.

435

6. Zhu, G.Y.; Wang, H.; Weng, N. Mar. Petro. Geol. 2016, 69, 1-12.

436

7. Cai, C.F.; Amrani, A.; Worden, R.H.; Xiao, Q.L.; Wang, T.K.; Gvirzman,

437

Z.; Li, H.X.; Said-Ahmad, W.; Jia, L.Q. Geochim. Cosmochim. Acta

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2016a, 182, 88-108.

439

8. Landa, S.; Machacek, V. Chem. Comm. in Germany. 1933.

440

9. Prelog, V.; Seiwerth, R.; 1941. Über die Synthese des Adamantans.

441

Berichte Der Deutschen Chemischen Gesellschaft, in Germany, 1933, 74,

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1644-1648.

443 444 445

10. Birch, S.F.; Cullum, T.V.; Dean, R.A.; Denyer, R.L.; 1952. Nature 170, 629-630. 11. Barnes, J.E.; Dalziel, J.A.W.; Ross, S.D. Spectrochim. Acta Part A 27, 22


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1971, 1671-1676. 12. Graham, W.D.; Schleyer, P.vR.; Hagaman, E.W.; Wenkert, E. J. Am. Chem. Soc. 1973, 95, 5785-5786.

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13. Janko, J.; Popl, M. J. Chomatogra. 1974, 89, 319-324.

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14. Mccabe, P.H.; Nelson, C.R.; Routledge, W. Tetrahedron 1977, 33,

451 452 453 454 455

1755-1757. 15. Aczel, T.; Gorbaty, M.L.; Maa, P.S.; Schlosberg, R.H. Fuel 1979, 58, 228-230. 16. Clark, T.; Knox, T.M.O.; Mckervey, M.A.; Mackle, H.; Rooney, J.J. J. Am. Chem. Soc. 1979, 101, 2404-2410.

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17. Mckervey, M.A. Tetrahedron 1980, 36, 971-992.

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18. Williams, J.A.; Bjoroy, M.; Dolcater, D.L.; Winters, J.C. Org. Geochem.

458 459 460 461 462 463 464

1986, 10, 451-461. 19. Rollmann, L.D.; Green, L.A.; Bradway, R.A.; Timken, H.K.C. Catal. Today 1996, 31, 163-169. 20. Chen, J.H.; Fu, J.M.; Sheng, G.Y.; Liu, D.H.; Zhang, J.J. Org. Geochem. 1996, 25, 179-190. 21. Dahl, J.E.P.; Moldowan, J.M.; Peters, K.; Claypool, G.; Rooney, M.; Michael, G.; Mello, M.; Kohnen, M. Nature 1999, 399, 54-56.

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22. Wingert, W.S. Fuel 1992, 71, 37-43.

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23. Wei, Z.B.; Moldowan, J.M.; Paytan, A. Org. Geochem. 2006, 37, 891-911. 23


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467 468

24. Zhu, G.Y.; Wang, H.T.; Weng N, Huang H. P.; Liang, H.B.; Ma, S.P. Org. Geochem. 2013, 63, 8-17.

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25. Dahl, J.E.; Moldowan, J.M.; Wei, Z.B.; Lipton, P.A.; Denisevich, P.; Gat,

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R.; Liu, A.G.; Schreiner, P.R.; Carlson, R.M.K. Angew. Chem. Int. Ed.

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2010, 49, 9881-9885.

472 473 474 475

26. Hanin, S.; Adam, P.; Kowalewski, I.; Huc, A.Y.; Carpentier, B.; Albrecht, P. Chem. Comm. 2002, 16, 1750-1751. 27. Wei, Z.B.; Moldowan, J.M.; Fago, F.; Dahl, J.E.; Cai, C.F.; Peters, K.E. Energy Fuels 2007b, 21, 3431-3436.

476

28. Gvirtzman, Z.; Said-Ahmad, W.; Ellis, G.S.; Hill, R.J.; Moldowan, J.M.;

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Wei, Z.B.; Amrani, A. Geochim. Cosmochim. Acta 2015, 167, 144-161.

478

29. Wang, M.; Zhu, G.Y.; Ren, L.M.; Liu, X.X.; Zhao, S.Q.; Shi, Q. Energy

479 480 481 482 483

Fuels 2015, 29, 4842-4849. 30. Cai, C.F.; Xiao, Q.L.; Fang, C.C.; Wang, T.K.; He, W.X.; Li, H.X. Org. Geochem. 2016b, 101, 49-62. 31. Zhu, G.Y.; Weng, N.; Wang, H.T, Yang, H.J.; Zhang, S.C.; Su, J.; Liao, F.R.; Zhang, B.; Ji, Y.G. Mar. Petro. Geol. 2015a, 62, 14-27.

484

32. Zhu, G.Y.; Huang, H.P.; Wang, H.T. Energy Fuels 2015b, 29, 1332-1344.

485

33. Zhu, G.Y.; Wang, H.T.; Weng, N.; Yang H.J.; Zhang, K.; Liao, F.R.; Yuan,

486 487

N. Mar. Petro. Geol. 2015c, 65, 103-113. 34. Zhang, S. C.; Huang, H.P.; Su, J.; Liu, M.; Wang, X.M.; Hu, J. Org. 24


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Geochem. 2015, 86, 5-18. 35. Oldenburg, T.B.P.; Brown, M.; Bennett, B.; Larter, S.R. Org. Geochem. 2014, 75, 151-168. 36. Zhang, S.C.; Su, J.; Wang, X.W.; Zhu, G.Y.; Yang, H.J.; Liu, K.Y.; Li, Z.X. Org. Geochem. 2011, 42, 1394-1410.

493

37. Dai, J.X.; Zou, C.N.; Zhang, S.C.; Li, J.; Ni, Y.Y.; Hu, G.Y.; Luo, X.; Tao,

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S.Z.; Zhu, G.Y.; Mi, J.K.; Li, Z.S.; Hu, A.P.; Yang, C.; Zhou, Q.H.; Shuai,

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Y.H.; Zhang, Y.; Ma, C.H. Sci. China, Ser. D 2008, 38, 1329-1341.

496 497

38. Zhu, G.Y, Zhang, B.T.; Yang, H.J.; Su, J.; Han, J.F. Org. Geochem. 2014, 74, 85-97.

498

39. Galimberti, R.; Zecchinello, F.; Nali, M.; Gigantiello, N.; Caldiero, L. The

499

22nd International Meeting of Organic Geochemists (IMOG) Seville,

500

Spain, Abstracts Book Part 2005, 1, 229-230.

501 502

40. Zhu, G.Y.; Zhang, S.C.; Huang, H.P.; Liang, Y.B.; Meng, S. C.; Li, Y.G. Appl. Geochem. 2011, 26, 1261-1273.

503

41. Jiang, N.H.; Zhu, G.Y.; Zhang, S.C. Chin. Sci. Bull. 2008, 53(3), 396-401.

504

42. Zhu, G.Y.; Zhang, S.C.; Liang, Y.B.; Dai, J.X.; Li, J. Sci. China, Ser. D

505 506 507 508

2005, 48, 1037-1046. 43. Li, M.; Zhang, S.; Jiang, C.; Zhu, G.; Fowler, M.; Achal, S.; Milovic, M.; Robinson, R.; Larter, S. Org. Geochem. 2008, 39, 1144-1149. 44. Greenwood, P.F.; Amrani, A.; Sessions, A.; Raven, M.R.; Holman, A.; 25


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

509

Dror, G.; Grice, K.; McCulloch, M.T.; Adkins, J.F. in, Grice, K. (Ed.),

510

Principles and Practice of Analytical Techniques in Geosciences. Royal

511

Society of Chemistry, UK, 2015, 285-312.

512 513 514 515

45. Garcia, C.L.; Becchi, M.; Grenier-Loustalot, M. F.; Paїsse, O.; Szymanski, R. Appl. Geochem. 2002, 74, 3849-57. 46. Asif, M.; Alexander, R.; Fazeelat, T.; Pierce, K. Org. Geochem. 2009, 40, 895-901.

516

26


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Energy & Fuels

517

Fig. 1. GC×GC-TOFMS 2D contour chromatogram of ZS1C condensate.

518

a: Alkanes; b: Cycloalkanes; c: Benzene; d: Tetrahydro-naphthalene; e:

519

Benzo[b]thiophene and naphthalene; f: Fluorene; g: Phenanthrene and

520

Dibenzothiophene; h: Phenanthrothiophene; i: Benzo[b]naphthothiophene

521 522 523 524

Fig. 2. Diamondoid hydrocarbons GC×GC-MS analysis of ZS1C condensate. a:

m/z

525

135+136+149+163+177+191+205+188+187+201+215+229+243+257+240+23

526

9+253+267+281+292+291+305+319+303+344+343+358

527

highlighting

528

135+136+149+163+177+191+205 chromatogram highlighting adamantanes; c:

529

m/z 188+187+201+215+229+243+257 chromatogram highlighting diamantanes;

530

d: m/z 240+239+253+267+281 chromatogram highlighting triamantanes; e: m/z

531

292+291+305+319+303 chromatogram highlighting tetramantanes; f: m/z

532

344+343+358 chromatogram highlighting pentamantanes.

diamondoid

hydrocarbons

with

chromatogram

1-5

cages;

b:

m/z

533 534 535 536 537

Fig. 3. OSCs detected in ZS1C condensate collectively highlighted in the 2D GC×GC contour chromatograms. a:

Tetrahydrothiophene

and

thiophene;

b:

Benzothiophene;

c:

Dibenzothiophene; d: Phenanthrothiophene and Benzo[b]naphthothiophene; e, f, 27


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 67

538

g: thiaadamantanes, thiadiamantanes, thiatriamantanes; h, i, j: dithiaadamantanes,

539

dithiadiamantanes,

540

trithiadiamantanes; m, n: tetrathiaadamantanes, tetrathiadiamantanes

dithiatriamantanes;

k,

l:

trithiaadamantanes,

541 542

Fig. 4. Thiadiamondoids GC×GC-MS analysis of the ZS1C condensate.

543

a:

m/z

544

168+182+196+210+224+238+206+220+234+248+262+258+272+286+300

545

chromatogram highlighting

546

168+182+196+210+224+238 chromatogram highlighting thiaadamantanes; c:

547

m/z 206+220+234+248+262 chromatogram highlighting thiadiamantanes; d:

548

m/z 258+272+286+300 chromatogram highlighting thiatriamantanes

thiadiamondoids

with

1-3

cages;

b:

m/z

549 550

Fig. 5. Dithiadiamondoids GC×GC-MS analysis of the ZS1C condensate. a:

551

m/z 186+200+214+228+224+238+252+266+280+276+290+304 chromatogram

552

highlighting thiadiamondoids with 1-3 cages; b: m/z 186+200+214+228

553

chromatogram highlighting dithiaadamantanes; c: m/z 224+238+252+266+280

554

chromatogram

555

chromatogram highlighting dithiatriamantanes

highlighting

dithiadiamantanes;

d:

m/z

276+290+304

556 557 558

Fig. 6. Mass spectra of representative dithiatriamantanes of ZS1C condensate. Peak numbers correspond to those in Fig. 5d. 28


Page 29 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

559 560 561 562

Fig. 7. Trithiadiamondoids and tetrathiadiamondoids GC×GC-MS analysis of ZS1C condensate. a:

m/z

190+204+218+232+246+260+242+256+270 thiadiamondoids

with

1-2

cages;

chromatogram

563

highlighting

b:

m/z

564

190+204+218+232+246+260 chromatogram highlighting trithiaadamantanes; c:

565

m/z 242+256+270 chromatogram highlighting trithiadiamantanes; d: m/z

566

208+222+236+260+274 chromatogram highlighting thiadiamondoids with 1-2

567

cages; e: m/z 208+222+236 chromatogram highlighting tetrathiaadamantanes; f:

568

m/z 260 chromatogram highlighting tetrathiadiamantanes

569 570 571

Fig. 8. Mass spectra of representative trithiadiamantanes of ZS1C condensate. Peak No. correspond to those in Fig. 7c.

572 573 574

Fig. 9. Mass spectra of representative tetrathiaadamantanes of ZS1C condensate. Peak No. correspond to those in Fig. 7e.

575 576 577

Fig. 10. Mass spectra of representative tetrathiadiamantanes of ZS1C condensate. Peak No. correspond to those in Fig. 7f.

578 579

Fig. 11. Possible schemes for the formation thiadiamondoids and 29


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(thiadiamondoidthiols)

Page 30 of 67

580

diamondoidthiols

during

581

reduction (TSR) in Petroleum. R=nCH3(n=0, 1, 2, 3, ...)

582

30


thermochemical

sulfate

Page 31 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

583

Energy & Fuels

Fig. 1

584

585 586

31


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

587

Fig. 2

588

589 590

32


Page 32 of 67

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591

Energy & Fuels

Fig. 3

592

593 594

33


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

595

Fig. 4

596

597 598

34


Page 34 of 67

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599

Energy & Fuels

Fig. 5

600

601 602

35


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

603

Fig. 6

604

605 606

36


Page 36 of 67

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607

Energy & Fuels

Fig. 7

608

609 610

37


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

611

Fig. 8

612

613 614

38


Page 38 of 67

Page 39 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

615

Energy & Fuels

Fig. 9

616

617 618

39


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

619

Fig. 10

620 621

40


Page 40 of 67

Page 41 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

622

Energy & Fuels

Fig. 11

623

624 625

41


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 42 of 67

626

Supplementary Figure S1. The family of diamondoids.

627

a:adamantane; b: diamantane; c: triamantane; d,e,f: three isomers of

628

tetramantane; g-l: six isomers of pantamantane.

629 630

Supplementary Figure S2. Mass spectra of representative tetramantanes

631

and pentamantanes of ZS1C condensate. Peak No. correspond to those in Figure

632

1e, f.

633 634

Supplementary Figure S3. Mass spectra of representative thiaadamantane

635

and adamantanethiols of ZS1C condensate. Peak No. correspond to those in

636

Figure 4b.

637 638

Supplementary Figure S4. Mass spectra of representative thiadiamantane

639

and diamantanethiols of ZS1C condensate. Peak No. correspond to those in

640

Figure 4c.

641 642 643

Supplementary Figure S5. Mass spectra of representative thiatriamantanes of ZS1C condensate. Peak No. correspond to those in Figure 4d.

644 645 646

Supplementary

Figure

S6.

Mass

spectra

of

representative

dithiaadamantanes of ZS1C condensate. Peak No. correspond to those in Figure 42


Page 43 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

647

Energy & Fuels

5b.

648

Supplementary

649

Figure

S7.

Mass

spectra

of

representative

650

dithiadiamantanes of ZS1C condensate. Peak No. correspond to those in Figure

651

5c.

652

Supplementary

653

Figure

S8.

Mass

spectra

of

representative

654

trithiaadamantanes of ZS1C condensate. Peak No. correspond to those in Figure

655

7b.

656

43


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

657

Supplementary Figure S1

658

659 660

44


Page 44 of 67

Page 45 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

661

Energy & Fuels


662

663 664

45


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

665


666

667 668

46


Page 46 of 67

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669

Energy & Fuels


670

671 672

47


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

673


674

675 676

48


Page 48 of 67

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677

Energy & Fuels


678

679 680

49


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

681


682

683 684

50


Page 50 of 67

Page 51 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

685

Energy & Fuels


686

687 688

51


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 52 of 67

TABLES

Table S1. Diamondoids detected in well ZS1C condensate. Peak No. correspond to GC-GC-MS assigned peaks in Fig 2. A=Adamantanes, D=Diamantanes, T=Triamantanes, TET=Tetramantanes, PENT=pentamantanes Compouds D16-Adamantane

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

Concentration mg/g

I.S.-1

2490 , 2.390

I.S.

C10D16

152

0.642

Adamantane

A-1

2538 , 2.420

A

C10H16

136

1.970

1-methyladamantane

A-2

2634 , 2.300

A

C11H18

135

4.646

2-methyladamantane

A-3

2922 , 2.420

A

C11H18

135

0.582

1,3-dimethyl-adamantane

A-4

2706 , 2.200

A

C12H20

149

3.098

1,4-dimethyladamantane (cis)

A-5

2976 , 2.290

A

C12H20

149

2.696

1,4-dimethyladamantane (trans)

A-6

3000 , 2.290

A

C12H20

149

0.702

1,2-dimethyl-adamantane

A-7

3114 , 2.380

A

C12H20

149

0.689

1-ethyladamantane

A-8

3216 , 2.360

A

C12H20

135

4.932

C2-adamantane

A-9

3246 , 2.420

A

C12H20

149

0.987

C2-adamantane

A-10

3276 , 2.440

A

C12H20

149

1.949

2-ethyladamantane

A-11

3336 , 2.410

A

C12H20

135

1.287

1,3,5-trimethyladamantane

A-12

2766 , 2.070

A

C13H22

163

1.577


A-13

3036 , 2.160

A

C13H22

163

0.121

1,3,4-trimethyladamantane (cis)

A-14

3150 , 2.230

A

C13H22

163

0.355

1,3,4-trimethyladamantane(trans)

A-15

3174 , 2.240

A

C13H22

163

1.347

1-ethyl-3-methyl-adamantane

A-16

3276 , 2.229

A

C13H22

149

4.622


A-17

3294 , 2.260

A

C13H22

163

3.547

C3-adamantane

A-18

3516 , 2.340

A

C13H22

149

3.229

C3-adamantane

A-19

3558 , 2.360

A

C13H22

149

2.660

C3-adamantane

A-20

3618 , 2.389

A

C13H22

149

1.571

C3-adamantane

A-21

3642 , 2.420

A

C13H22

149

1.857

C3-adamantane

A-22

3666 , 2.210

A

C13H22

149

2.076

C3-adamantane

A-23

3666 , 2.410

A

C13H22

149

1.603

C3-adamantane

A-24

3318 , 2.310

A

C13H22

163

2.073

C3-adamantane

A-25

3384 , 2.260

A

C13H22

163

1.297

C3-adamantane

A-26

3408 , 2.320

A

C13H22

163

2.567

C3-adamantane

A-27

3432 , 2.340

A

C13H22

163

4.167

C3-adamantane

A-28

3456 , 2.360

A

C13H22

163

2.681

C3-adamantane

A-29

3480 , 2.370

A

C13H22

163

0.136

C3-adamantane

A-30

3504 , 2.361

A

C13H22

163

0.842

C3-adamantane

A-31

3540 , 2.440

A

C13H22

163

0.246

C3-adamantane

A-32

3666 , 2.280

A

C13H22

163

1.270

C3-adamantane

A-33

3678 , 2.290

A

C13H22

163

2.552

C3-adamantane

A-34

3564 , 2.420

A

C13H22

163

1.192


Page 53 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Compouds

Concentration

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

1,3,5,7-tetramethyl-adamantane

A-35

2808 , 1.970

A

C14H24

177

0.421


A-36

3198 , 2.120

A

C14H24

177

2.102

C4-adamantane

A-37

3312 , 2.170

A

C14H24

177

0.227

1-ethyl-3,5-dimethyl-adamantane

A-38

3318 , 2.130

A

C14H24

163

1.290

C4-adamantane

A-39

3342 , 2.180

A

C14H24

177

1.176


A-40

3354 , 2.200

A

C14H24

177

1.338


A-41

3438 , 2.190

A

C14H24

177

2.170

C4-adamantane

A-42

3690 , 2.269

A

C14H24

149

0.175

C4-adamantane

A-43

3702 , 2.280

A

C14H24

149

0.719

C4-adamantane

A-44

3864 , 2.320

A

C14H24

149

0.225

C4-adamantane

A-45

3900 , 2.320

A

C14H24

149

0.614

C4-adamantane

A-46

3942 , 2.320

A

C14H24

149

0.914

C4-adamantane

A-47

3978 , 2.379

A

C14H24

149

0.728

C4-adamantane

A-48

3990 , 2.369

A

C14H24

149

0.563

C4-adamantane

A-49

3564 , 2.210

A

C14H24

163

1.998

C4-adamantane

A-50

3582 , 2.210

A

C14H24

163

1.688

C4-adamantane

A-51

3714 , 2.290

A

C14H24

163

1.915

C4-adamantane

A-52

3750 , 2.300

A

C14H24

163

0.212

C4-adamantane

A-53

3774 , 2.310

A

C14H24

163

0.152

C4-adamantane

A-54

3798 , 2.300

A

C14H24

163

2.811

C4-adamantane

A-55

3822 , 2.370

A

C14H24

163

1.140

C4-adamantane

A-56

3882 , 2.370

A

C14H24

163

0.397

C4-adamantane

A-57

3918 , 2.390

A

C14H24

163

0.420

C4-adamantane

A-58

3930 , 2.400

A

C14H24

163

0.518

C4-adamantane

A-59

3954 , 2.410

A

C14H24

163

0.604

C4-adamantane

A-60

3462 , 2.200

A

C14H24

177

2.415

C4-adamantane

A-61

3576 , 2.260

A

C14H24

177

0.598

C4-adamantane

A-62

3594 , 2.280

A

C14H24

177

1.976

C4-adamantane

A-63

3696 , 2.160

A

C14H24

177

0.717

mg/g

1-ethyl-3,5,7-trimethyl-adamantane

A-64

3348 , 2.040

A

C15H26

177

0.889

1,2,3,5,7,-pentamethyl-adamantane

A-65

3366 , 2.080

A

C15H26

191

0.643

C5-adamantane

A-66

4290 , 2.309

A

C15H26

149

0.302

C5-adamantane

A-67

4338 , 2.320

A

C15H26

149

0.287

C5-adamantane

A-68

3936 , 2.180

A

C15H26

163

0.752

C5-adamantane

A-69

4080 , 2.270

A

C15H26

163

0.845

C5-adamantane

A-70

3702 , 2.100

A

C15H26

163

1.390

C5-adamantane

A-71

4008 , 2.240

A

C15H26

163

0.275

C5-adamantane

A-72

4020 , 2.250

A

C15H26

163

0.409

C5-adamantane

A-73

4158 , 2.260

A

C15H26

163

0.831

C5-adamantane

A-74

4182 , 2.320

A

C15H26

163

0.474

C5-adamantane

A-75

4194 , 2.330

A

C15H26

163

0.094

C5-adamantane

A-76

3708 , 2.160

A

C15H26

177

1.000

C5-adamantane

A-77

3726 , 2.160

A

C15H26

177

1.205

C5-adamantane

A-78

3828 , 2.170

A

C15H26

177

1.260


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Compouds

Page 54 of 67 Concentration

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

C5-adamantane

A-79

3846 , 2.240

A

C15H26

177

0.520

C5-adamantane

A-80

3942 , 2.240

A

C15H26

177

1.200

C5-adamantane

A-81

3534 , 2.210

A

C15H26

177

0.991

C5-adamantane

A-82

4068 , 2.270

A

C15H26

177

0.595

C5-adamantane

A-83

4152 , 2.320

A

C15H26

177

0.666

C5-adamantane

A-84

3570 , 2.110

A

C15H26

191

0.560

C5-adamantane

A-85

3582 , 2.140

A

C15H26

191

0.381

C5-adamantane

A-86

3606 , 2.140

A

C15H26

191

0.342

C5-adamantane

A-87

3744 , 2.210

A

C15H26

191

0.936

C5-adamantane

A-88

3762 , 2.220

A

C15H26

191

1.216

C5-adamantane

A-89

3792 , 2.170

A

C15H26

191

0.329

C5-adamantane

A-90

3834 , 2.230

A

C15H26

191

0.605

C5-adamantane

A-91

3840 , 2.080

A

C15H26

191

0.395

C5-adamantane

A-92

3864 , 2.120

A

C15H26

191

0.225

C5-adamantane

A-93

4170 , 2.200

A

C15H26

191

0.668

C6-adamantane

A-94

4458 , 2.220

A

C16H28

149

0.221

C6-adamantane

A-95

4668 , 2.310

A

C16H28

149

0.136

C6-adamantane

A-96

4092 , 2.110

A

C16H28

163

0.364

C6-adamantane

A-97

4314 , 2.190

A

C16H28

163

0.181

C6-adamantane

A-98

4614 , 2.300

A

C16H28

163

0.116

C6-adamantane

A-99

4062 , 2.130

A

C16H28

177

0.449

C6-adamantane

A-100

4080 , 2.140

A

C16H28

177

0.557

C6-adamantane

A-101

4170 , 2.170

A

C16H28

177

0.188

C6-adamantane

A-102

4194 , 2.200

A

C16H28

177

0.274

C6-adamantane

A-103

4272 , 2.210

A

C16H28

177

0.270

C6-adamantane

A-104

4482 , 2.260

A

C16H28

177

0.597

C6-adamantane

A-105

4494 , 2.250

A

C16H28

177

0.327

C6-adamantane

A-106

3888 , 1.990

A

C16H28

177

0.004

C6-adamantane

A-107

4176 , 2.140

A

C16H28

177

0.398

C6-adamantane

A-108

3876 , 2.120

A

C16H28

191

0.235

C6-adamantane

A-109

4116 , 2.160

A

C16H28

191

0.055

C6-adamantane

A-110

4302 , 2.280

A

C16H28

191

0.352

C6-adamantane

A-111

4314 , 2.280

A

C16H28

191

0.211

C6-adamantane

A-112

4392 , 2.260

A

C16H28

205

0.056

C6-adamantane

A-113

4068 , 2.180

A

C16H28

205

0.054

C6-adamantane

A-114

3900 , 2.200

A

C16H28

205

0.178

C6-adamantane

A-115

3942 , 2.130

A

C16H28

205

0.039

C6-adamantane

A-116

4134 , 2.170

A

C16H28

205

0.122

C6-adamantane

A-117

3906 , 2.130

A

C16H28

205

0.093

C6-adamantane

A-118

3912 , 2.090

A

C16H28

205

0.158

C6-adamantane

A-119

4140 , 2.190

A

C16H28

205

0.126

C7-adamantane

A-120

4362 , 2.170

A

C17H30

149

0.026

C7-adamantane

A-121

4476 , 2.110

A

C17H30

163

0.104

C7-adamantane

A-122

4536 , 2.160

A

C17H30

177

0.096


mg/g

Page 55 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Compouds

Concentration

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

C7-adamantane

A-123

4632 , 2.180

A

C17H30

177

0.068

C7-adamantane

A-124

4464 , 2.170

A

C17H30

191

0.053

C7-adamantane

A-125

4512 , 2.190

A

C17H30

191

0.193

C7-adamantane

A-126

4776 , 2.250

A

C17H30

191

0.156

C7-adamantane

A-127

4500 , 2.130

A

C17H30

192

0.026

C7-adamantane

A-128

4176 , 2.040

A

C17H30

205

0.050

C7-adamantane

A-129

4626 , 2.270

A

C17H30

205

0.104

C7-adamantane

A-130

4296 , 2.160

A

C17H30

205

0.221

C7-adamantane

A-131

4218 , 2.110

A

C17H30

219

0.036

C7-adamantane

A-132

4320 , 2.160

A

C17H30

219

0.006

C8-adamantane

A-133

4836 , 2.230

A

C18H32

149

0.168

C8-adamantane

A-134

5016 , 2.200

A

C18H32

177

0.033

C8-adamantane

A-135

4818 , 2.150

A

C18H32

205

0.061

C8-adamantane

A-136

4584 , 2.120

A

C18H32

205

0.017

C8-adamantane

A-137

4890 , 2.190

A

C18H32

205

0.049

C8-adamantane

A-138

4896 , 2.220

A

C18H32

205

0.040

C8-adamantane

A-139

4962 , 2.220

A

C18H32

205

0.038

C8-adamantane

A-140

4494 , 2.020

A

C18H32

205

0.040

C8-adamantane

A-141

4614 , 2.130

A

C18H32

219

0.054

C9-adamantane

A-142

5136 , 2.170

A

C19H34

205

0.010

C9-adamantane

A-143

5094 , 2.160

A

C19H34

219

0.018

C9-adamantane

A-144

4884 , 2.050

A

C19H34

233

0.002

mg/g

Diamantane

D-1

4320 , 2.930

D

C14H20

188

4.532

4-methyldiamantane

D-2

4380 , 2.739

D

C15H22

187

3.617

1-methyldiamantane

D-3

4512 , 2.880

D

C15H22

187

3.929

3-methyldiamantane

D-4

4602 , 2.880

D

C15H22

187

1.437

4,9-dimethyldiamantane

D-5

4428 , 2.570

D

C16H24

201

1.599

1,4+2,4-dimethyldiamantane

D-6

4530 , 2.670

D

C16H24

201

2.073


D-7

4548 , 2.690

D

C16H24

201

2.009

C2-diamantane

D-8

4602 , 2.670

D

C16H24

201

0.063


D-9

4644 , 2.700

D

C16H24

201

2.398

C2-diamantane

D-10

4704 , 2.810

D

C16H24

201

1.148

C2-diamantane

D-11

4722 , 2.760

D

C16H24

201

0.325

C2-diamantane

D-12

4734 , 2.720

D

C16H24

201

0.027

C2-diamantane

D-13

4746 , 2.810

D

C16H24

201

3.393

C2-diamantane

D-14

4776 , 2.820

D

C16H24

201

1.811

C2-diamantane

D-15

4794 , 2.890

D

C16H24

201

0.988

C2-diamantane

D-16

4830 , 2.830

D

C16H24

201

0.613

C2-diamantane

D-17

4854 , 2.868

D

C16H24

201

1.294

C2-diamantane

D-18

5160 , 2.800

D

C16H24

201

0.149

C2-diamantane

D-19

5202 , 2.930

D

C16H24

201

0.065

C2-diamantane

D-20

5430 , 2.710

D

C16H24

201

0.080

C2-diamantane

D-21

5178 , 2.850

D

C16H24

201

0.351

C2-diamantane

D-22

5190 , 2.840

D

C16H24

201

0.325


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Compouds


Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

n-ethyl-diamantane

D-23

4866 , 2.790

D

C16H24

187

0.885

n-ethyl-diamantane

D-24

4914 , 2.830

D

C15H22

187

0.399

mg/g

n-ethyl-diamantane

D-25

4938 , 2.900

D

C16H24

187

0.878

1,4,9-trimethyldiamantane

D-26

4560 , 2.510

D

C17H26

215

1.202

3,4,9-trimethyldiamantane

D-27

4788 , 2.630

D

C17H26

215

3.331

C3-diamantane

D-28

4908 , 2.630

D

C17H26

201

0.563

C3-diamantane

D-29

4938 , 2.700

D

C17H26

201

0.516

C3-diamantane

D-30

4950 , 2.720

D

C17H26

201

0.728

C3-diamantane

D-31

4992 , 2.700

D

C17H26

201

0.339

C3-diamantane

D-32

5016 , 2.740

D

C17H26

201

0.683

C3-diamantane

D-33

5118 , 2.750

D

C17H26

201

0.831

C3-diamantane

D-34

5136 , 2.840

D

C17H26

201

0.237

C3-diamantane

D-35

5076 , 2.770

D

C17H26

215

0.101

C3-diamantane

D-36

4686 , 2.600

D

C17H26

215

0.496

C3-diamantane

D-37

4704 , 2.630

D

C17H26

215

0.440

C3-diamantane

D-38

4716 , 2.650

D

C17H26

215

0.487

C3-diamantane

D-39

4764 , 2.610

D

C17H26

215

0.816

C3-diamantane

D-40

4836 , 2.640

D

C17H26

215

0.025

C3-diamantane

D-41

4872 , 2.640

D

C17H26

215

1.046

C3-diamantane

D-42

4890 , 2.700

D

C17H26

215

1.661

C3-diamantane

D-43

4902 , 2.730

D

C17H26

215

0.391

C3-diamantane

D-44

4932 , 2.750

D

C17H26

215

0.668

C3-diamantane

D-45

4962 , 2.750

D

C17H26

215

0.256

C3-diamantane

D-46

4968 , 2.740

D

C17H26

215

0.275

C3-diamantane

D-47

4974 , 2.750

D

C17H26

215

0.227

C3-diamantane

D-48

4986 , 2.760

D

C17H26

215

0.876

C3-diamantane

D-49

5046 , 2.760

D

C17H26

215

0.259

C3-diamantane

D-50

5064 , 2.800

D

C17H26

215

0.152

C3-diamantane

D-51

5112 , 2.870

D

C17H26

215

0.121

C3-diamantane

D-52

5118 , 2.860

D

C17H26

215

0.132

C3-diamantane

D-53

5154 , 2.890

D

C17H26

215

0.130

C3-diamantane

D-54

5160 , 2.900

D

C17H26

215

0.206

C3-diamantane

D-55

5166 , 2.890

D

C17H26

215

0.075

C3-diamantane

D-56

5082 , 2.790

D

C17H26

215

0.068

C3-diamantane

D-57

4758 , 2.620

D

C17H26

215

0.103

C3-diamantane

D-58

5070 , 2.790

D

C17H26

215

0.117

C4-diamantane

D-59

4950 , 2.540

D

C18H28

215

0.238

C4-diamantane

D-60

5064 , 2.560

D

C18H28

215

0.119

C4-diamantane

D-61

4698 , 2.460

D

C18H28

229

0.282

C4-diamantane

D-62

4812 , 2.490

D

C18H28

229

0.193

C4-diamantane

D-63

4896 , 2.540

D

C18H28

229

0.470

C4-diamantane

D-64

4938 , 2.590

D

C18H28

229

0.106

C4-diamantane

D-65

4980 , 2.550

D

C18H28

229

0.174

C4-diamantane

D-66

5010 , 2.640

D

C18H28

229

0.292


Page 57 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Compouds

Concentration

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

C4-diamantane

D-67

5094 , 2.650

D

C18H28

229

0.403

C4-diamantane

D-68

5124 , 2.660

D

C18H28

229

1.101

C4-diamantane

D-69

5238 , 2.560

D

C18H28

229

0.097

C4-diamantane

D-70

5274 , 2.590

D

C18H28

229

0.087

C4-diamantane

D-71

5274 , 2.790

D

C18H28

229

0.174

C5-diamantane

D-72

4866 , 2.390

D

C19H30

243

0.030

C5-diamantane

D-73

5448 , 2.730

D

C19H30

243

0.254

C5-diamantane

mg/g

D-74

5502 , 2.720

D

C19H30

243

0.051

Triamantane

T-1

5658 , 3.360

T

C18H24

240

1.212

9-methyltriamantane

T-2

5676 , 3.140

T

C19H26

239

0.826

5-methyltriamantane

T-3

5790 , 3.260

T

C19H26

239

0.446

C1-triamantane

T-4

5814 , 3.270

T

C19H26

239

0.318

8-methyltriamantane

T-5

5850 , 3.280

T

C19H26

239

0.175

16-methyltriamantane

T-6

5880 , 3.290

T

C19H26

239

0.124

C1-triamantane

T-7

5970 , 3.440

T

C19H26

239

0.243

9,15-dimethyltriamantane

T-8

5700 , 2.900

T

C20H28

253

0.173


T-9

5790 , 3.060

T

C20H28

253

0.157


T-10

5802 , 3.040

T

C20H28

253

0.282

3,9-+4,9-+6,9-+7,9-Dimethyltriamantane

T-11

5826 , 3.060

T

C20H28

253

0.177

9,14-Dimethyltriamantane

T-12

5868 , 3.070

T

C20H28

253

0.130

C2-triamantane

T-13

5892 , 3.080

T

C20H28

253

0.080

C2-triamantane

T-14

5910 , 3.170

T

C20H28

253

0.067

C2-triamantane

T-15

5952 , 3.210

T

C20H28

253

0.133

C2-triamantane

T-16

5970 , 3.170

T

C20H28

253

0.210

C2-triamantane

T-17

5994 , 3.170

T

C20H28

253

0.134

C2-triamantane

T-18

6024 , 3.280

T

C20H28

253

0.069

C2-triamantane

T-19

6036 , 3.190

T

C20H28

253

0.055

C2-triamantane

T-20

6108 , 2.960

T

C20H28

253

0.013

C2-triamantane

T-21

6150 , 3.330

T

C20H28

253

0.029

C2-triamantane

T-22

6174 , 3.340

T

C20H28

253

0.017

C2-triamantane

T-23

6186 , 3.100

T

C20H28

253

0.016

C2-triamantane

T-24

6210 , 3.490

T

C20H28

253

0.009

C2-triamantane

T-25

6264 , 3.120

T

C20H28

253

0.012

n-ethyl-triamantane

T-26

6090 , 3.190

T

C20H28

239

0.080

n-ethyl-triamantane

T-27

6120 , 3.280

T

C20H28

239

0.019

n-ethyl-triamantane

T-28

6174 , 3.290

T

C20H28

239

0.008

5,9,15-Trimethyltriamantane

T-29

5802 , 2.830

T

C21H30

267

0.113

C3-triamantane

T-30

5892 , 2.930

T

C21H30

267

0.024

C3-triamantane

T-31

5904 , 2.970

T

C21H30

267

0.041

C3-triamantane

T-32

5940 , 2.960

T

C21H30

267

0.030

C3-triamantane

T-33

5964 , 2.940

T

C21H30

267

0.010

C3-triamantane

T-34

5976 , 2.950

T

C21H30

267

0.076

C3-triamantane

T-35

5994 , 3.050

T

C21H30

267

0.039

C3-triamantane

T-36

6006 , 2.960

T

C21H30

267

0.040

C3-triamantane

T-37

6036 , 3.050

T

C21H30

267

0.017


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Compouds


Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

C3-triamantane

T-38

6048 , 3.000

T

C21H30

267

0.020

C3-triamantane

T-39

6054 , 3.040

T

C21H30

267

0.016

C3-triamantane

T-40

6066 , 3.090

T

C21H30

267

0.063

C3-triamantane

T-41

6078 , 3.080

T

C21H30

267

0.036

C3-triamantane

T-42

6108 , 3.080

T

C21H30

267

0.090

C3-triamantane

T-43

6126 , 3.110

T

C21H30

267

0.015

C3-triamantane

T-44

6132 , 3.090

T

C21H30

267

0.019

C3-triamantane

T-45

6138 , 3.110

T

C21H30

267

0.018

C3-triamantane

T-46

6144 , 3.100

T

C21H30

267

0.027

C3-triamantane

T-47

6186 , 3.230

T

C21H30

267

0.011

C3-triamantane

T-48

6216 , 3.200

T

C21H30

267

0.015

C3-triamantane

T-49

6234 , 3.190

T

C21H30

267

0.025

C3-triamantane

T-50

6252 , 3.230

T

C21H30

267

0.015

tetraadamantane

TET-1

6654 , 3.720

TET

C22H28

292

0.039

tetraadamantane

TET-2

6828 , 3.800

TET

C22H28

292

0.032

tetraadamantane

TET-3

6966 , 4.070

TET

C22H28

292

0.011

C1-tetraadamantane

TET-4

6648 , 3.450

TET

C23H30

291

0.037

C1-tetraadamantane

TET-5

6738 , 3.590

TET

C23H30

291

0.003

C1-tetraadamantane

TET-6

6828 , 3.580

TET

C23H30

291

0.007

C1-tetraadamantane

TET-7

6930 , 3.750

TET

C23H30

291

0.007

C2-tetraadamantane

TET-8

6642 , 3.200

TET

C24H32

305

0.004

C2-tetraadamantane

TET-9

6726 , 3.330

TET

C24H32

305

0.002

Pentamantane

PENT-1

7392 , 3.960

PENT

C26H32

344

0.003

Pentamantane

PENT-2

7842 , 4.470

PENT

C26H32

344

0.001

C1-Pentamantane

PENT-3

7362 , 3.660

PENT

C28H34

358

0.001


mg/g

Page 59 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Table S2. Concentration of organic sulfur compounds detected in well ZS1C condensate. BT= Benzo[b]thiophenes, DBT= Dibenzothiophenes, PT= Phenanthrothiophenes Compouds 1-Octadecanethiol Benzo[b]thiophene Benzo[b]thiophene, methylBenzo[b]thiophene, methylBenzo[b]thiophene, methylBenzo[b]thiophene, methylBenzo[b]thiophene, methylBenzo[b]thiophene, dimethylBenzo[b]thiophene, dimethylBenzo[b]thiophene, dimethylBenzo[b]thiophene, dimethylBenzo[b]thiophene, dimethylBenzo[b]thiophene, dimethylBenzo[b]thiophene, dimethylBenzo[b]thiophene, dimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, trimethylBenzo[b]thiophene, tetramethylBenzo[b]thiophene, tetramethylDibenzothiophene Dibenzothiophene, 4-methylDibenzothiophene, 1-methylDibenzothiophene, 3-methylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, dimethylDibenzothiophene, trimethylDibenzothiophene, trimethyl-

R.T. (s)

Classifications

Formula

Quant Masses

6270 , 2.280 2940 , 3.380 3360 , 3.290 3396 , 3.210 3402 , 3.250 3426 , 3.270 3450 , 3.370 3732 , 3.270 3804 , 3.190 3804 , 3.330 3846 , 3.260 3888 , 3.260 4026 , 3.390 3780 , 3.130 3870 , 3.230 4146 , 3.230 4158 , 3.100 4188 , 3.170 4200 , 3.040 4230 , 3.110 4236 , 3.150 4278 , 3.140 4284 , 3.190 4344 , 3.180 4410 , 3.250 4512 , 3.130 4668 , 3.090 5046 , 4.030 5382 , 3.923 5442 , 3.880 5502 , 4.130 5652 , 3.830 5688 , 3.830 5730 , 3.800 5754 , 3.780 5796 , 3.850 5814 , 3.990 5820 , 3.870 5850 , 3.970 5862 , 3.950 5898 , 3.920 5934 , 3.760 6072 , 3.710

I.S. BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT BT DBT DBT DBT DBT DBT DBT DBT DBT DBT DBT DBT DBT DBT DBT DBT DBT

C18H38S C8H6S C9H8S C9H8S C9H8S C9H8S C9H8S C10H10S C10H10S C10H10S C10H10S C10H10S C10H10S C10H10S C10H10S C11H12S C11H12S C11H12S C11H12S C11H12S C11H12S C11H12S C11H12S C11H12S C11H12S C12H14S C12H14S C12H8S C13H10S C13H10S C13H10S C14H12S C14H12S C14H12S C14H12S C14H12S C14H12S C14H12S C14H12S C14H12S C14H12S C15H14S C15H14S

70 134 147 147 147 147 147 147 147 147 147 147 147 161 161 147 147 161 161 161 161 161 161 161 161 175 175 184 198 198 198 212 212 212 212 212 212 212 212 212 212 226 226


Concentration mg/g 0.769 4.091 5.535 4.701 1.729 2.654 11.764 0.657 1.640 1.619 4.134 1.349 0.662 4.290 16.019 0.541 0.874 3.589 0.691 6.152 4.742 0.957 3.129 1.258 0.772 0.830 0.643 163.741 141.162 111.727 21.478 1.934 38.389 26.854 78.370 31.343 15.360 2.598 18.857 1.351 3.819 1.236 8.913

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Compouds Dibenzothiophene, trimethylDibenzothiophene, trimethylDibenzothiophene, trimethylDibenzothiophene, trimethylDibenzothiophene, trimethylDibenzothiophene, tetramethylDibenzothiophene, tetramethylPhenaleno[1,9-bc]thiophene 1-Methylphenanthro[4,5bcd]thiophene Anthra(2,3-b)thiophene

Page 60 of 67

R.T. (s)

Classifications

Formula

Quant Masses

6102 , 3.760 6102 , 3.880 6138 , 3.910 6192 , 3.850 6228 , 3.840 6324 , 3.560 6444 , 3.760 6060 , 4.680

DBT DBT DBT DBT DBT DBT DBT PT

C15H14S C15H14S C15H14S C15H14S C15H14S C16H16S C16H16S C14H8S

226 226 226 226 226 240 240 208

Concentration mg/g 1.035 4.135 10.833 7.215 1.086 2.739 1.174 2.363

6330 , 4.440

PT

C15H10S

222

1.465

6786 , 4.810

PT

C16H10S

234

1.940


Page 61 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Table S3. Thiadiamondoids detected in well ZS1C condensate. Peak No. correspond to GCGC-MS assigned peaks in Fig 4,5,7. TA=thiaadamantanes, TD=thiadiamantanes, TT=thiatriamantanes, dTA=dithiaadamantanes, dTD =dithiadiamantanes, dTT=dithiatriamantanes, tTA=trithiaadamantanes, tTD=trithiadiamantanes, tetTA=tetrathiaadamantanes, tetTD=tetrathiadiamantanes. Compounds

Concentration

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

5-methyl-2-thiaadamantane 1-methyl-2-thiaadamantane

TA-1 TA-2

3462 , 2.950 3540 , 2.990

TA TA

C10H16S C10H16S

168 168

0.451 0.424

C1-n-thiaadamantane

TA-3

3762 , 3.130

TA

C10H16S

168

0.006

Adamantane-n-thiol Adamantane-n-thiol 5,7-dimethyl-2-thiaadamantane 1,5-dimethyl-2-thiaadamantane 1,3-dimethyl-2-thiaadamantane

AT-1 AT-2 TA-4 TA-5 TA-6

3564 , 2.990 3834 , 3.170 3432 , 2.690 3522 , 2.760 3594 , 2.790

AT AT TA TA TA

C10H16S C10H16S C11H18S C11H18S C11H18S

168 168 182 182 182

0.044 0.008 0.850 2.455 0.684

C2-2-thiaadamantane

TA-7

3720 , 2.850

TA

C11H18S

182

0.144

C2-2-thiaadamantane

TA-8

3780 , 2.890

TA

C11H18S

182

0.049

C2-2-thiaadamantane

TA-9

3816 , 2.900

TA

C11H18S

182

0.098

C2-2-thiaadamantane

TA-10

3834 , 2.900

TA

C11H18S

182

0.045

C2-2-thiaadamantane

TA-11

3930 , 3.010

TA

C11H18S

182

0.006

C2-2-thiaadamantane

TA-12

3990 , 3.050

TA

C11H18S

182

0.011

C1-adamantane-n-thiol

AT-3

3624 , 2.790

AT

C11H18S

182

0.030


AT-4

3870 , 2.922

AT

C11H18S

182

0.021


AT-5

3900 , 2.970

AT

C11H18S

182

0.013


AT-6

3966 , 3.010

AT

C11H18S

182

0.005

C3-2-thiaadamantane

TA-13

3474 , 2.540

TA

C12H20S

196

1.254

C3-2-thiaadamantane

TA-14

3558 , 2.600

TA

C12H20S

196

1.047

C3-2-thiaadamantane

TA-15

3732 , 2.620

TA

C12H20S

196

0.084

C3-2-thiaadamantane

TA-16

3768 , 2.650

TA

C12H20S

196

0.483

C3-2-thiaadamantane

TA-17

3804 , 2.680

TA

C12H20S

196

0.326

C3-2-thiaadamantane

TA-18

3864 , 2.730

TA

C12H20S

196

0.037

C3-2-thiaadamantane

TA-19

3882 , 2.750

TA

C12H20S

196

0.115

C3-2-thiaadamantane

TA-20

3906 , 2.770

TA

C12H20S

196

0.089

C3-2-thiaadamantane

TA-21

3930 , 2.760

TA

C12H20S

196

0.096

C3-2-thiaadamantane

TA-22

3948 , 2.790

TA

C12H20S

196

0.025

C3-2-thiaadamantane

TA-23

3972 , 2.790

TA

C12H20S

196

0.065

C3-2-thiaadamantane

TA-24

4002 , 2.800

TA

C12H20S

196

0.044

C3-2-thiaadamantane

TA-25

4014 , 2.760

TA

C12H20S

196

0.030

C3-2-thiaadamantane

TA-26

4050 , 2.800

TA

C12H20S

196

0.236

C3-2-thiaadamantane

TA-27

4128 , 2.830

TA

C12H20S

196

0.095

C2-adamantane-2-thiol

AT-7

3666 , 2.620 AT ACS Paragon Plus Environment

C12H20S

196

0.005

mg/g

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Compouds


Peak No.

R.T. (s)

Classifications

Formula

Quant Masses


AT-8

3918 , 2.730

AT

C12H20S

196

0.002


AT-9

3996 , 2.780

AT

C12H20S

196

0.004


AT-10

4062 , 2.850

AT

C12H20S

196

0.004


AT-11

4152 , 2.830

AT

C12H20S

196

0.009

C4-2-thiaadamantane

TA-28

3504 , 2.400

TA

C13H22S

210

0.274

C4-2-thiaadamantane

TA-29

3840 , 2.520

TA

C13H22S

210

0.185

C4-2-thiaadamantane

TA-30

3876 , 2.540

TA

C13H22S

210

0.134

C4-2-thiaadamantane

TA-31

3912 , 2.580

TA

C13H22S

210

0.187

C4-2-thiaadamantane

TA-32

3954 , 2.571

TA

C13H22S

210

0.129

C4-2-thiaadamantane

TA-33

3990 , 2.570

TA

C13H22S

210

0.074

C4-2-thiaadamantane

TA-34

4074 , 2.620

TA

C13H22S

210

0.313

C4-2-thiaadamantane

TA-35

4164 , 2.630

TA

C13H22S

210

0.020

C4-2-thiaadamantane

TA-36

4404 , 2.720

TA

C13H22S

210

0.015

C4-2-thiaadamantane

TA-37

4410 , 2.800

TA

C13H22S

210

0.015

C4-2-thiaadamantane

TA-38

4278 , 2.710

TA

C13H22S

210

0.041

C5-2-thiaadamantane

TA-39

3990 , 2.470

TA

C14H24S

224

0.023

C5-2-thiaadamantane

TA-40

4032 , 2.490

TA

C14H24S

224

0.016

C5-2-thiaadamantane

TA-41

4212 , 2.510

TA

C14H24S

224

0.013

C5-2-thiaadamantane

TA-42

4326 , 2.580

TA

C14H24S

224

0.011

C5-2-thiaadamantane

TA-43

4008 , 2.410

TA

C14H24S

224

0.069

3-thiadiamantane

TD-1

5130 , 3.830

TD

C13H18S

206

2.282

C1-3-thiadiamantane

TD-2

5094 , 3.470

TD

C14H20S

220

1.242

C1-3-thiadiamantane

TD-3

5166 , 3.510

TD

C14H20S

220

0.861

C1-3-thiadiamantane

TD-4

5226 , 3.650

TD

C14H20S

220

0.037

C1-3-thiadiamantane

TD-5

5238 , 3.630

TD

C14H20S

220

0.717

C1-3-thiadiamantane

TD-6

5304 , 3.700

TD

C14H20S

220

0.363

C1-3-thiadiamantane

TD-7

5322 , 3.660

TD

C14H20S

220

0.121

C1-3-thiadiamantane

TD-8

5352 , 3.690

TD

C14H20S

220

0.035

C1-3-thiadiamantane

TD-9

5364 , 3.710

TD

C14H20S

220

0.203

C1-3-thiadiamantane

TD-10

5376 , 3.730

TD

C14H20S

220

0.235

Diamantane-n-thiol

DT-1

5202 , 3.510

DT

C14H20S

220

0.002

C2-3-thiadiamantane

TD-11

5130 , 3.210

TD

C15H22S

234

0.485

C2-3-thiadiamantane

TD-12

5172 , 3.300

TD

C15H22S

234

0.673

C2-3-thiadiamantane

TD-13

5226 , 3.330

TD

C15H22S

234

0.107

C2-3-thiadiamantane

TD-14

5250 , 3.390

TD

C15H22S

234

0.120

C2-3-thiadiamantane

TD-15

5262 , 3.350

TD

C15H22S

234

0.244

C2-3-thiadiamantane

TD-16

5310 , 3.380

TD

C15H22S

234

0.064

C2-3-thiadiamantane

TD-17

5322 , 3.410

TD

C15H22S

234

0.057

C2-3-thiadiamantane

TD-18

5328 , 3.380

TD

C15H22S

234

0.243

C2-3-thiadiamantane

TD-19

5346 , 3.370

TD

C15H22S

234

0.114

C2-3-thiadiamantane

TD-20

5358 , 3.360

TD

C15H22S

234

0.063

C2-3-thiadiamantane

TD-21

5394 , 3.450

TD

C15H22S

234

0.140

C2-3-thiadiamantane

TD-22

5418 , 3.530

TD

C15H22S

234

0.060

C2-3-thiadiamantane

TD-23

5424 , 3.490 TD ACS Paragon Plus Environment

C15H22S

234

0.069

mg/g

Page 63 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Compouds

Concentration

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

C2-3-thiadiamantane

TD-24

5454 , 3.500

TD

C15H22S

234

0.094

C2-3-thiadiamantane

TD-25

5478 , 3.520

TD

C15H22S

234

0.060

C2-3-thiadiamantane

TD-26

5484 , 3.530

TD

C15H22S

234

0.032

C2-3-thiadiamantane

TD-27

5502 , 3.550

TD

C15H22S

234

0.116

C2-3-thiadiamantane

TD-28

5520 , 3.550

TD

C15H22S

234

0.093

C2-3-thiadiamantane

TD-29

5526 , 3.580

TD

C15H22S

234

0.053

C2-3-thiadiamantane

TD-30

5538 , 3.550

TD

C15H22S

234

0.015

C2-diamantane-n-thiol

DT-2

5250 , 3.320

DT

C15H22S

248

0.001

C3-3-thiadiamantane

TD-31

5172 , 3.040

TD

C16H24S

248

0.147

C3-3-thiadiamantane

TD-32

5196 , 3.050

TD

C16H24S

248

0.085

C3-3-thiadiamantane

TD-33

5250 , 3.110

TD

C16H24S

248

0.021

C3-3-thiadiamantane

TD-34

5310 , 3.190

TD

C16H24S

248

0.016

C3-3-thiadiamantane

TD-35

5334 , 3.230

TD

C16H24S

248

0.031

C3-3-thiadiamantane

TD-36

5358 , 3.230

TD

C16H24S

248

0.064

C3-3-thiadiamantane

TD-37

5388 , 3.180

TD

C16H24S

248

0.030

C3-3-thiadiamantane

TD-38

5406 , 3.180

TD

C16H24S

248

0.058

C3-3-thiadiamantane

TD-39

5424 , 3.180

TD

C16H24S

248

0.030

C3-3-thiadiamantane

TD-40

5448 , 3.250

TD

C16H24S

248

0.123

C3-3-thiadiamantane

TD-41

5466 , 3.230

TD

C16H24S

248

0.014

C3-3-thiadiamantane

TD-42

5490 , 3.310

TD

C16H24S

248

0.007

C3-3-thiadiamantane

TD-43

5502 , 3.310

TD

C16H24S

248

0.026

C3-3-thiadiamantane

TD-44

5532 , 3.280

TD

C16H24S

248

0.029

C3-3-thiadiamantane

TD-45

5580 , 3.240

TD

C16H24S

248

0.081

C3-3-thiadiamantane

TD-46

5598 , 3.380

TD

C16H24S

248

0.021

C3-3-thiadiamantane

TD-47

5700 , 3.360

TD

C16H24S

248

0.010

C3-3-thiadiamantane

TD-48

5760 , 3.430

TD

C17H26S

248

0.005

C4-3-thiadiamantane

TD-49

5412 , 3.040

TD

C17H26S

262

0.054

C4-3-thiadiamantane

TD-50

5262 , 2.918

TD

C17H26S

262

0.008

C4-3-thiadiamantane

TD-51

5340 , 2.990

TD

C17H26S

262

0.004

C4-3-thiadiamantane

TD-52

5442 , 3.000

TD

C17H26S

262

0.010

C4-3-thiadiamantane

TD-53

5556 , 3.120

TD

C17H26S

262

0.005

n-thiatriamantane n-thiatriamantane n-thiatriamantane triamantane-n-thiol

TT-1 TT-2 TT-3 TT-4

6312 , 4.280 6366 , 4.280 6378 , 4.320 6246 , 3.880

TT TT TT TT

C17H22S C17H22S C17H22S C18H24S

258 258 258 272

0.101 0.027 0.176 0.050

C1-n-thiatriamantane

TT-5

6318 , 3.930

TT

C18H24S

272

0.083


TT-6

6372 , 3.950

TT

C18H24S

272

0.012


TT-7

6390 , 3.990

TT

C18H24S

272

0.040


TT-8

6426 , 4.070

TT

C18H24S

272

0.024


TT-9

6432 , 4.140

TT

C18H24S

272

0.025


TT-10

6468 , 4.080

TT

C18H24S

272

0.027


TT-11

6486 , 4.150

TT

C18H24S

272

0.012


TT-12

6552 , 4.160

TT

C18H24S

272

0.008

Triamantane-n-thiol

TT-13

6558 , 4.280

TT

C18H24S

272

0.017


mg/g

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Compounds


Peak No.

R.T. (s)

Classifications

Formula

Quant Masses


TT-14

6264 , 3.580

TT

C19H26S

286

0.014


TT-15

6330 , 3.610

TT

C19H26S

286

0.013

triamantane-n-thiol

TT-16

6348 , 3.750

TT

C19H26S

286

0.007


TT-17

6378 , 3.710

TT

C19H26S

286

0.007


TT-18

6414 , 3.750

TT

C19H26S

286

0.010


TT-19

6480 , 3.860

TT

C19H26S

286

0.015


TT-20

6360 , 3.450

TT

C20H28S

300

0.005

C1-dithiaadamantane

dTA-1

4188 , 2.800

dTA

C9H14S2

186

0.083

C1-dithiaadamantane

dTA-2

4284 , 2.880

dTA

C9H14S2

186

0.019

C2-dithiaadamantane

dTA-3

4176 , 2.620

dTA

C10H16S2

200

0.027

C2-dithiaadamantane

dTA-4

4278 , 2.690

dTA

C10H16S2

200

0.056

C2-dithiaadamantane

dTA-5

4308 , 2.700

dTA

C10H16S2

200

0.012

C2-dithiaadamantane

dTA-6

4320 , 2.740

dTA

C10H16S2

200

0.072

C2-dithiaadamantane

dTA-7

4362 , 2.730

dTA

C10H16S2

200

0.025

C2-dithiaadamantane

dTA-8

4446 , 2.800

dTA

C10H16S2

200

0.086

C2-dithiaadamantane

dTA-9

4476 , 2.830

dTA

C10H16S2

200

0.331

C3-dithiaadamantane

dTA-10

4296 , 2.540

dTA

C11H18S2

214

0.048

C3-dithiaadamantane

dTA-11

4338 , 2.560

dTA

C11H18S2

214

0.057

C3-dithiaadamantane

dTA-12

4488 , 2.670

dTA

C11H18S2

214

0.041

C3-dithiaadamantane

dTA-13

4518 , 2.680

dTA

C11H18S2

214

0.184

C3-dithiaadamantane

dTA-14

4578 , 2.730

dTA

C11H18S2

214

0.113

C3-dithiaadamantane

dTA-15

4620 , 2.780

dTA

C11H18S2

214

0.226

C3-dithiaadamantane

dTA-16

4686 , 2.770

dTA

C11H18S2

214

0.062

C3-dithiaadamantane

dTA-17

4734 , 2.810

dTA

C11H18S2

214

0.108

C4-dithiaadamantane

dTA-18

4344 , 2.430

dTA

C12H20S2

228

0.024

C4-dithiaadamantane

dTA-19

4476 , 2.480

dTA

C12H20S2

228

0.056

C4-dithiaadamantane

dTA-20

4590 , 2.560

dTA

C12H20S2

228

0.067

C4-dithiaadamantane

dTA-21

4602 , 2.590

dTA

C12H20S2

228

0.058

C4-dithiaadamantane

dTA-22

4626 , 2.610

dTA

C12H20S2

228

0.083

C4-dithiaadamantane

dTA-23

4662 , 2.600

dTA

C12H20S2

228

0.113

C4-dithiaadamantane

dTA-24

4734 , 2.620

dTA

C12H20S2

228

0.026

C4-dithiaadamantane

dTA-25

4746 , 2.670

dTA

C12H20S2

228

0.122

C4-dithiaadamantane

dTA-26

4824 , 2.740

dTA

C12H20S2

228

0.058

C5-dithiaadamantane

dTA-27

4464 , 2.370

dTA

C13H22S2

242

0.008

C5-dithiaadamantane

dTA-28

4482 , 2.370

dTA

C13H22S2

242

0.025

C5-dithiaadamantane

dTA-29

4680 , 2.480

dTA

C13H22S2

242

0.042

C5-dithiaadamantane

dTA-30

4686 , 2.500

dTA

C13H22S2

242

0.033

C5-dithiaadamantane

dTA-31

4746 , 2.500

dTA

C13H22S2

242

0.042

C5-dithiaadamantane

dTA-32

4800 , 2.540

dTA

C13H22S2

242

0.041

C5-dithiaadamantane

dTA-33

4842 , 2.560

dTA

C13H22S2

242

0.038

C5-dithiaadamantane

dTA-34

4926 , 2.620

dTA

C13H22S2

242

0.087

C5-dithiaadamantane

dTA-35

4968 , 2.630

dTA

C13H22S2

242

0.052

C6-dithiaadamantane

dTA-36

4932 , 2.470

dTA

C14H24S2

256

0.022

dithiadiamantane

dTD-1

5580 , 3.580 dTD ACS Paragon Plus Environment

C12H16S2

224

0.241

mg/g

Page 65 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Compounds

Concentration

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

C1-dithiadiamantane

dTD-2

5520 , 3.370

dTD

C13H18S2

238

0.060

C1-dithiadiamantane

dTD-3

5526 , 3.360

dTD

C13H18S2

238

0.045

C1-dithiadiamantane

dTD-4

5610 , 3.340

dTD

C13H18S2

238

0.141

C1-dithiadiamantane

dTD-5

5640 , 3.390

dTD

C13H18S2

238

0.035

C1-dithiadiamantane

dTD-6

5658 , 3.460

dTD

C13H18S2

238

0.043

C1-dithiadiamantane

dTD-7

5778 , 3.480

dTD

C13H18S2

238

0.008

C1-dithiadiamantane

dTD-8

5814 , 3.530

dTD

C13H18S2

238

0.018

C1-dithiadiamantane

dTD-9

5862 , 3.530

dTD

C13H18S2

238

0.020

C1-dithiadiamantane

dTD-10

5880 , 3.550

dTD

C13H18S2

238

0.018

C1-dithiadiamantane

dTD-11

5898 , 3.600

dTD

C13H18S2

238

0.008

C1-dithiadiamantane

dTD-12

5940 , 3.580

dTD

C13H18S2

238

0.009

C2-dithiadiamantane

dTD-13

5526 , 2.990

dTD

C14H20S2

252

0.033

C2-dithiadiamantane

dTD-14

5538 , 3.150

dTD

C14H20S2

252

0.023

C2-dithiadiamantane

dTD-15

5544 , 3.140

dTD

C14H20S2

252

0.022

C2-dithiadiamantane

dTD-16

5586 , 3.230

dTD

C14H20S2

252

0.045

C2-dithiadiamantane

dTD-17

5658 , 3.160

dTD

C14H20S2

252

0.053

C2-dithiadiamantane

dTD-18

5676 , 3.230

dTD

C14H20S2

252

0.028

C2-dithiadiamantane

dTD-19

5712 , 3.120

dTD

C14H20S2

252

0.008

C2-dithiadiamantane

dTD-20

5718 , 3.100

dTD

C14H20S2

252

0.010

C2-dithiadiamantane

dTD-21

5754 , 3.290

dTD

C14H20S2

252

0.007

C2-dithiadiamantane

dTD-22

5766 , 3.280

dTD

C14H20S2

252

0.014

C2-dithiadiamantane

dTD-23

5778 , 3.190

dTD

C14H20S2

252

0.008

C2-dithiadiamantane

dTD-24

5790 , 3.350

dTD

C14H20S2

252

0.026

C2-dithiadiamantane

dTD-25

5808 , 3.370

dTD

C14H20S2

252

0.020

C2-dithiadiamantane

dTD-26

5898 , 3.350

dTD

C14H20S2

252

0.017

C2-dithiadiamantane

dTD-27

5904 , 3.340

dTD

C14H20S2

252

0.022

C2-dithiadiamantane

dTD-28

5922 , 3.350

dTD

C14H20S2

252

0.027

C2-dithiadiamantane

dTD-29

6018 , 3.440

dTD

C14H20S2

252

0.008

C3-dithiadiamantane

dTD-30

5592 , 3.020

dTD

C15H22S2

266

0.018

C3-dithiadiamantane

dTD-31

5808 , 3.150

dTD

C15H22S2

266

0.034

C3-dithiadiamantane

dTD-32

5820 , 3.150

dTD

C15H22S2

266

0.009

C3-dithiadiamantane

dTD-33

5856 , 3.160

dTD

C15H22S2

266

0.018

C3-dithiadiamantane

dTD-34

6036 , 3.280

dTD

C15H22S2

266

0.007

dithiatriamantane dithiatriamantane dithiatriamantane

dTT-1 dTT-2 dTT-3

6678 , 3.900 6744 , 4.060 6816 , 4.220

dTT dTT dTT

C16H20S2 C16H20S2 C17H22S2

276 276 290

0.001 0.007 0.037

C1-dithiatriamantane

dTT-4

6744 , 3.920

dTT

C17H22S2

290

0.002


dTT-5

6756 , 3.740

dTT

C17H22S2

290

0.002


dTT-6

6810 , 3.900

dTT

C17H22S2

290

0.003


dTT-7

6840 , 3.830

dTT

C17H22S2

290

0.002


dTT-8

6942 , 4.140

dTT

C17H22S2

290

0.001


dTT-9

7002 , 4.110

dTT

C17H22S2

290

0.002


dTT-10

7062 , 4.190

dTT

C17H22S2

290

0.002


dTT-11

6768 , 3.570 dTT ACS Paragon Plus Environment

C18H24S2

304

0.001

mg/g

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Compounds


Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

trithiaadamantane

tTA-1

4266 , 2.720

tTA

C7H10S3

190

0.437

C1-trithiaadamantane

tTA-2

4278 , 2.540

tTA

C8H12S3

204

0.364


tTA-3

4308 , 2.560

tTA

C8H12S3

204

0.200


tTA-4

4404 , 2.620

tTA

C8H12S3

204

0.103


tTA-5

4542 , 2.660

tTA

C8H12S3

204

0.053


tTA-6

4308 , 2.400

tTA

C9H14S3

218

0.272


tTA-7

4404 , 2.460

tTA

C9H14S3

218

0.123


tTA-8

4476 , 2.450

tTA

C9H14S3

218

0.072


tTA-9

4620 , 2.530

tTA

C9H14S3

218

0.047


tTA-10

4620 , 2.590

tTA

C9H14S3

218

0.019


tTA-11

4668 , 2.580

tTA

C9H14S3

218

0.043


tTA-12

4728 , 2.580

tTA

C9H14S3

218

0.041


tTA-13

4392 , 2.310

tTA

C10H16S3

232

0.011


tTA-14

4398 , 2.270

tTA

C10H16S3

232

0.025


tTA-15

4416 , 2.330

tTA

C10H16S3

232

0.039


tTA-16

4464 , 2.300

tTA

C10H16S3

232

0.034


tTA-17

4482 , 2.300

tTA

C10H16S3

232

0.056


tTA-18

4530 , 2.280

tTA

C10H16S3

232

0.010


tTA-19

4572 , 2.360

tTA

C10H16S3

232

0.043


tTA-20

4578 , 2.370

tTA

C10H16S3

232

0.045


tTA-21

4602 , 2.360

tTA

C10H16S3

232

0.026


tTA-22

4626 , 2.430

tTA

C10H16S3

232

0.036


tTA-23

4632 , 2.410

tTA

C10H16S3

232

0.023


tTA-24

4650 , 2.410

tTA

C10H16S3

232

0.042


tTA-25

4668 , 2.420

tTA

C10H16S3

232

0.029


tTA-26

4680 , 2.390

tTA

C10H16S3

232

0.031


tTA-27

4740 , 2.430

tTA

C10H16S3

232

0.071


tTA-28

4764 , 2.490

tTA

C10H16S3

232

0.030


tTA-29

4776 , 2.450

tTA

C10H16S3

232

0.041


tTA-30

4788 , 2.520

tTA

C10H16S3

232

0.037


tTA-31

4890 , 2.520

tTA

C10H16S3

232

0.008


tTA-32

4554 , 2.230

tTA

C11H18S3

246

0.005


tTA-33

4578 , 2.220

tTA

C11H18S3

246

0.008


tTA-34

4632 , 2.230

tTA

C11H18S3

246

0.007


tTA-35

4716 , 2.230

tTA

C11H18S3

246

0.008


tTA-36

4716 , 2.260

tTA

C11H18S3

246

0.008


tTA-37

4740 , 2.250

tTA

C11H18S3

246

0.005


tTA-38

4746 , 2.260

tTA

C11H18S3

246

0.008


tTA-39

4812 , 2.330

tTA

C11H18S3

246

0.009


tTA-40

4818 , 2.320

tTA

C11H18S3

246

0.009


tTA-41

4860 , 2.380

tTA

C11H18S3

246

0.010


tTA-42

4914 , 2.390

tTA

C11H18S3

246

0.008


tTA-43

5166 , 2.480

tTA

C11H18S3

246

0.005

trithiadiamantane

tTD-1

5748 , 3.180 tTD ACS Paragon Plus Environment

C11H14S3

242

0.168

mg/g

Page 67 of 67 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Compounds

Concentration

Peak No.

R.T. (s)

Classifications

Formula

Quant Masses

C1-trithiadiamantane

tTD-2

5784 , 2.970

tTD

C12H16S3

256

0.038


tTD-3

5928 , 3.090

tTD

C12H16S3

256

0.007


tTD-4

5952 , 3.130

tTD

C12H16S3

256

0.013


tTD-5

5850 , 2.880

tTD

C13H18S3

270

0.019

C1-tetrathiaadamantane

tetTA-1

4362 , 2.960

tetTA

C6H8S4

208

0.003


tetTA-2

4434 , 2.820

tetTA

C7H10S4

222

0.009


tetTA-3

4482 , 2.840

tetTA

C7H10S4

222

0.003


tetTA-4

4500 , 2.860

tetTA

C7H10S4

222

0.005


tetTA-5

4620 , 2.960

tetTA

C7H10S4

222

0.002


tetTA-6

4734 , 2.850

tetTA

C8H11S4

236

0.003

tetrathiadiamantane tetrathiadiamantane tetrathiadiamantane

tetTD-1 tetTD-2 tetTD-3

5694 , 3.380 5742 , 3.440 5790 , 3.500

tetTD tetTD tetTD

C10H12S4 C10H12S4 C10H12S4

260 260 260

0.005 0.014 0.006


mg/g

Discovery of high-abundance diamondoids and thiadiamondoids and

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