Helium isotopic distribution of Australian natural gases
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1 Helium isotopic distribution of Australian natural gases Chris Boreham 1, Dianne Edwards 1 and Robert Poreda 2 1 Geoscience Australia, Canberra, ACT 2 University of Rochester, Rochester, NY 19 th Australian Organic Geochemistry Conference, Fremantle, 4-7 December 2016
2 Acknowledgment Isotope and Organic Geochemistry Lab at GA Junhong Chen Ziqing Hong Jacob Sohn Neel Jinadasa Prince Palatty Industry for access to gas samples
3 Talk Outline Distribution of natural gases composition and carbon isotopes Helium abundance and isotopes sources age control other Noble gases Helium processing - from wellhead to sales molecular and isotopic fractionation Conclusions
4 Helium distribution GA samples Over 1000 gases 821 with measurable [He] > % (1 ppm) 300 Total frequency = 821 Frequency economic He extraction? 50 Amadeus Basin > 10% He 0 to >1 Helium (%)
5 Location of natural gases for He isotopes 150 samples 11 basins Cenozoic to Cambrian (source and reservoir)
6 Natural Gas: mol. composition 5 4 Amadeus biodegradation Bass ln (C 2 /C 3 ) 3 2 kerogen cracking (1 o ) gas Bonaparte Bowen Browse Carnarvon Cooper 1 oil cracking (2 o ) gas Gippsland Gunnedah Crust ln (C 1 /C 2 ) modified after Tao et al. OG 2014 Otway Perth
7 Natural Gas: mol. composition and C-isotopes Amadeus Bass -5 Bonaparte δ 13 C 2 - δ 13 C biodegradation Bowen Browse Carnarvon Cooper Gippsland -25 Gunnedah -30 Otway Perth C 2 /C 3
8 Natural Gas: mol. composition and C-isotopes 5 Primary cracking Abiogenic 0 NSO cracking Amadeus Bass -5 Oil cracking biodegraded Bonaparte Bowen δ 13 C 2 - δ 13 C Browse Carnarvon Cooper Gippsland Gunnedah Otway Perth C 2 /C 3
9 Helium ( 3 He, 4 He)
10 4 He (α particle) crust and mantle sources Pb-206 stable α Po day 206 Pb 208 Pb Pb-208 stable 232 Thorium decay Thorium decay γ Po µsec β Tl-208 α 3 min β Uranium decay β Bi day γ β Pb yr Bi min γ β 160 µsec Po-214 Pb-212 α 10.6 hr β Bi-214 γ 19.7 min Po-216 α 0.15 sec Pb-214 Rn-220 α 27 min 238 Uranium decay γ β α 55 sec Po min γ Re-224 α 3.6 day α Rn-222 Th-228 α 3.8 day 1.9 yr γ Ra-226 β α 1602 yr γ Ac hr β α Re yr α 250,000 yr U-234 Th x10 16 yr β Th-230 Pa-234 U ,000 yr 232 Th γ min Rate determining step: t½ = billion yr γ β Th yr α percentage of radioactive material remaining 238 U 4.5x yr Rate determining step: t½ = 4.5 billion yr Radioactive Decay for U-238 Number of half lives time for U billion years
11 3 He sources Mantle primordial 3 He Crust 6 Li + n 3 H Tritium (t½ = 12.3 yr) Cosmic ray interaction with N & O
12 Helium sources R/Ra = 3 He/ 4 He sample / 3 He/ 4 He air ( 3 He/ 4 He air = 1.4 x 10-6 ) 3 He/ 4 He ~ (R/Ra ~ 8) Mantle Crust 3 He/ 4 He ~ (R/Ra ~ 0.02) degassing Meteoric water Air Saturated Water (ASW) 3 He/ 4 He = (R/Ra = 1) Air Cosmic ray? (R/Ra ~ 0.985)
13 He isotopes vs CO 2 10 R/Ra Mantle Amadeus Bass Bonaparte Bowen Browse Carnarvon Cooper Gippsland Gunnedah Otway Perth Crustal CO 2 %
14 He isotopes vs CO 2 10 R/Ra Mantle Amadeus Bass Bonaparte Bowen Browse Carnarvon Cooper Gippsland Gunnedah Otway Perth Crustal CO 2 %
15 He isotopes vs CO 2 1.0E E E+10 Crustal CO 2 Crustal CO 2 Amadeus Bass Bonaparte CO 2 / 3 He 1.0E E E+07 Mantle CO 2 Altered (CO 2 loss) Age Mantle CO 2 Bowen Browse Carnarvon Cooper Gippsland Gunnedah Otway Perth 1.0E+06 CO 2 loss CO 2 loss 1.0E R/Ra
16 He isotopes vs CO 2 isotopes 1.0E E+11 Amadeus 1.0E+10 Bass CO 2 / 3 He 1.0E E E E+06 Bonaparte Bowen Browse Carnarvon Cooper Gippsland Gunnedah Otway Perth 1.0E δ 13 CO 2
17 He isotopes vs CO 2 isotopes 1.0E E E+10 biodegradation CO 2 / 3 He 1.0E E+08 Carnarvon 1.0E E E δ 13 CO 2
18 Crust = 0.02Ra He isotopes vs Age (source rock) 10 coal seam gas (later input)? Amadeus Bass R/Ra 1? biodegraded : meteoric (Ra = 1) mixing high CO 2 (44%) Bonaparte Bowen Browse Carnarvon Cooper 0.1 Gippsland Gunnedah Otway Perth Age Ma
19 4 He ppm vs Age (source rock) Magee and Mt Kitty He ppm Air (5.2 ppm) Amadeus Bass Bonaparte Bowen Browse Carnarvon Cooper Gippsland Gunnedah Otway Perth Age Ma
20 Noble gas isotopes ( 3,4 He 20,21,22 Ne, 36,38,40 Ar, 78,80,82,,83,84 Kr, 124,126,128,129,130,131,132,134,136 Xe) Ne/ 4 He E-05 Air/ASW Mantle Amadeus Bass Bonaparte Bowen Browse Carnarvon Cooper Gippsland Gunnedah Otway Perth Crust 1E R/Ra
21 Helium Processing: from wellhead to sales gas
22 Geological factors for high [Helium] (USA experience straight from wellhead) He source - basement source has a larger source volume - hot (U, Th) sediment sources Partitioning of dissolved He in pore water with migrating gas phase - lower gas-water ratio higher [He] - old water: age of water in rock is more important than age of rock itself; look for old reservoirs with saline water Shallow depth and low geothermal gradients - more He partitioned into gas at low P, low T and high salinity Low maturity - less dilution by large volumes of generated hc gases Migration front: at edges of prolific petroleum systems - first gas strips most He from pore water Modified from A. A. Brown, Formation of High Helium Gases: A Guide for Explorationists. Search and Discovery Article 80115
23 Helium from Liquefied Natural Gas (LNG) Global (USA, Russia, Poland, Algeria, Qatar, Australia) % He Qatar: 0.04% He - extraction is economic because of large volume He extracted from concentrated gases separated from LNG Australia: 3 rd largest exported of LNG (2014) projected to be No. 1 exporter Qatar s North Field holds around ¼ of known global helium reserves LNG plant -
24 Australian LNG Natural gases Darwin LNG 2005 Prelude Ichthys NW Shelf Venture 1989 Greater Gorgon Pluto 2012 Wheatstone Coal Seam Gas Australian Pacific 2015 Qld Curtis LNG 2014 Gladstone LNG
25 Australia s only commercial He extraction plant Gas field He up to 0.28% CO % N % C % Darwin LNG
26 ConocoPhillips Optimized Cascade LNG process: Darwin LNG (DLNG) Bayu-Undan: DLNG feed gas DLNG Rejected N 2 DLNG Rejected CO 2 DLNG LNG DLNG NGL modified from
27 Darwin LNG (ConocoPhillips) Rejected N 2 Feed gas Darwin Helium (BOC) - Rejected CO 2 to incinerator Darwin LNG feed gas - NGL - LNG condensate predominately methane - Rejected N 2 ( tail gas ) to Darwin Helium (BOC)
28 Darwin Helium (BOC) plant Darwin Helium feed gas : 3.0% He, 0.1% H 2 ; 3.2% CH 4, 93.6% N % He (P5) modified from Dan Wilson and Jeremy Armstrong, Darwin Helium (BOC), Oct 16
29 Helium extraction: isotopic fractionation Bayu-Undan (He = av. 0.18%) (N 2 /He = av. 33) R/Ra = Rejected N 2 / He-concentrate (He = 3.0%) (N 2 /He = 31) R/Ra = He-pure (He = %) R/Ra = LNG no expected isotopic fract. Bayu-Undan (av. C 1 = 80.2%) av. δ 13 C 1 = δd = δ 13 C 1-7 (isotopically lighter) δd +8 (isotopically heavier) Rejected N 2 / He-concentrate (C 1 = 3.2%; 0.1% total) δ 13 C 1 = δd = Isotopic fractionations are consistent with the relative gas-liquid phase partitioning of CH 4, 13 CH 4 and CDH 3 Bigeleisen et al., Vapour pressures of isotopic methanes, J. Chem Phys (1967)
30 Conclusions 1/5 th of Australian gases have [He] > 0.05% potential for economic resource from LNG commercial for Bonaparte gas extraction (av. 0.18% He; 3.4% N 2 )? others areas (low N 2 /He and high [He] in N 2 -reject gas) Amadeus Basin has highest [He] (>10 mole%); rel. small reserves Crustal origin ( 4 He) is dominant Amadeus Basin with highest radiogenic 4 He Notable exceptions: Otway with recent volcanism ( 3 He), and Gunnedah (CSG) with intrusions(?) ( 3 He) CO 2 both linked and decoupled from He source linked: e.g. Otway decoupled: e.g. Carnarvon with carbonate decomposition and precipitation CO 2 loss is pervasive: carbonate mineral precipitation? Increasing source/reservoir age leads to greater overprint by crustal 4 He
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