Poto?nik P. (Ed.) Natural Gas
Подождите немного. Документ загружается.
Soil gas geochemistry: signicance and application in geological prospectings 201
Annunziatellis, A.; Ciotoli, G.; Lombardi, S. & Nolasco, F. (2003). Short- and long-term gas
hazard: the release of toxic gases in the Albani Hills volcanic area (central Italy).
Journal of Geochemical Exploration 77, 93-108.
Ball, T.K.; Cameron, D.G.; Colman, T.B. & Roberts, P.D. (1991). Behavior of radon in the
geological environment: a review. Q. J. Eng. Geol., 24, 169-182.
Baubron, J.C.; Allard, P. & Toutain, J.P. (1990). Diffuse volcanic emissions of carbon dioxide
from Vulcano Island, Italy. Nature, 344, 51–53.
Baubron, J.C.; Allard, P.; Sabroux, J.C.; Tedesco, D. & Toutain, J.P. (1991). Soil gas
emanations as precursory indicators of volcanic eruptions. J. Geol. Soc. London, 148,
571–576.
Baubron, J. C.; Rigo, A. & Toutain, J. P. (2002). Soil gas profiles as a tool to characterize
active tectonic areas: the Jaut Pass example (Pyrenees, France). Earth and Planetary
Science Lett., 196, 69-81.
Beaubien; S.L.; Ciotoli, G. & Lombardi, S. (2002). Carbon dioxide and radon gas hazard in
the Alban Hills area (central Italy). Journal of Volcanology and Geothermal Research,
123, 63-80
Blumetti, A.M.; Michetti, A.M. & Serva, L. (1988). The ground effects of the Fucino
earthquake of Jan. 13
th
, 1915: an attempt for the understanding of recent geological
evolution of some tectonic structure. In: Historical Seismicity of Central Eastern
Mediterranean Region. C. Margottini and L. Serva Eds., 297-319. Nuove Tecnologie,
l’Energie e l’Ambiente, Rome.
Blumetti A, .M.; Dramisa, F. & Michetti, A.M. (1993). Fault-generated mountain fronts in the
Central Apennines (CentraI ltaly): Geomorphological features and seismotectonic
implication. Earth Surf. Processes Landforms, 18, 203-223.
Capaccioni, B.; Tassi, F.; Vaselli, O. & Tedesco, D. (2007). Submarine gas burst at Panarea
Island (southern Italy) on 3 November 2002: A magmatic versus hydrothermal
episode. J. Geophys. Res., 112, B05201. doi:10.1029/2006JB0044359.
Charlet, J.M.; Doremus, P. & Quinif, Y. (1995). Radon methods used to discover uranium
mineralizations in the lower Devonian of the Ardenne Massif (Belgium). In: Gas
Geochemistry, C. Dubois Ed., Science Reviews, Northwood, 1–18.
Cox, M.E. (1980). Ground radon survey of an hawaiian geothermal area. Geophys. Res. Lett.,
7, 283–286.
Caramanna, G.; Voltattorni, N.; Caramanna, L.; Cinti, D.; Galli, G.; Pizzino, L. & Quattrocchi,
F. (2005). Scientific diving techniques applied to the geomorphological and
geochemical study of some submarine volcanic gas vents (Aeolian Islands,
southern Tyrrhenian sea, Italy). Proc. 24
th
Diving for Science Symp. American Academy
of Underwater sciences 11-12 March 2005 – Mystic – Connecticut (USA).
Ciotoli, G.; Guerra, M.; Lombardi, S. & Vittori, E. (1998). Soil gas survey for tracing
seismogenic faults: a case-study the Fucino basin (central Italy). J. Geophys. Res.,
103B, 23781- 23794.
Ciotoli, G.; Etiope, G.; Guerra, M. & Lombardi, S. (1999). The detection of concealed faults in
the Ofanto basin using the correlation between soil gas fracture surveys.
Tectonophysics, 299 (3–4), 321–332.
Ciotoli, G.; Lombardi, S. & Annunziatellis, A. (2007). Geostatistical analysis of soil gas data
in a high seismic intermontane basin: Fucino Plain, central Italy. J. Geophys. Res.,
112, B05407, doi:10.1029/2005JB004044.
Cocco, M.; Nostro, C. & Ekström, G. (2000). Static stress changes and fault interaction
during the 1997 Umbria-Marche earthquake sequence. J. of Seism., 4, N. 4, 501-516.
Crenshaw, W.B. ; Williams, S.N. & Stoiber, R.E. (1982). Fault location by radon and mercury
detection at an active volcano in Nicaragua. Nature, 300, 345–346.
Dayal, R. & Wilke, R.J. (1982). Role of clay minerals as backfill in radioactive waste disposal.
Proc. Int. Clay Conf. Bologna/Pavia, 1981, pp. 771--787.
D’Amore, F. ; Sabroux, J.C. & Zettwoog, P. (1978). Determination of characteristics of steam
reservoirs by radon-222 measurements in geothermal fluids. Pure Appl. Geophys.,
117, 253–261.
Del Pezzo, E. ; Gasparini, P. ; Mantovani, M.M. ; Martini, M. ; Capaldi, G. ; Gomes, Y.T. &
Pece, R. (1981). A case of correlation between Rn-222 anomalies and seismic activity
on a volcano (Vulcano island, southern Thyrrenian Sea). Geophys. Res. Lett., 8, 962–
965.
De Gregorio, S.; Diliberto, I.S.; Giammanco, S.; Gurrieri, S. & Valenza, M. (2002). Tectonic
control over large-scale diffuse degassing in Eastern Sicily (Italy). Geofluids, 2, 273–
284.
Di Filippo, M. & Toro, B. (1995). Gravity features. In: The Volcano of the Alban Hills, R. Trigila
Ed. , 283 pp.
Dubois, C.; Alvarez Calleja, A.; Bassot, S. & Chambaudet, A. (1995). Modelling the 3-
dimensional microfissure network in quartz in a thin section of granite. In: Gas
Geochemistry, C. Dubois Ed., Science Reviews, Northwood, pp. 357-368.
Duddridge, G. A.; Grainger, P. & Durrance, E. M. (1991). Fault detection using soil gas
geochemistry, Q. J. Eng. Geol., 24, 427-435.
Durrance, E. M. & Gregory, R .G. (1988). Fracture mapping in clays: Soil gas surveys at
Down Ampney, Gloucestershire. DOE Report: DOE/RW/88081, Dep. Of Energy,
Washington D.C.
Eremeev, A. N.; Sokolov, V.A. & Solovov, A.P. (1973). Application of helium surveying to
structural mapping and ore deposit forecasting. In: Geochemical Exploration, 1972, M.
J. Jones Ed., pp.183– 192, Inst. of Min. and Metall., London.
Etiope, G. & Lombardi, S. (1995). Soil gases as fault tracers in clay basins: a case history in
the Siena Basin (Central Italy). In: Gas Geochemistry, C. Dubois Ed., 19–29, Science
Reviews, Northwood.
Fleischer, R.L. ; Alter, H.W. ; Furnam, S.C. ; Price, P.B. & Walker, R.M. (1972). Particle track
etching. Science, 178, 255–263.
Fleischer, R.L. & Magro-Campero, A. (1985). Association of subsurface radon changes in
Alaska and the northeastern United States with earthquakes. Geochim. Cosmochim.
Acta, 49, 1061–1071.
Galadini, F. & Messina, P. (1994). Plio-Quatenary tectonics of the Fucino basin and
surrounding areas (CentraI ltaly), J. Geol.,5, 6(2), 73-99.
Gascoyne, M. ; Wuschke, D.M. & Durrance, E.M. (1993). Fracture detection and
groundwater flow characterization using He and Rn in soil gases, Manitoba,
Canada. Appl. Geochem., 8, 223– 233.
Gavshin, V.M.; Melgunov, M.S.; Sukhorukov, F.V.; Bobrov, V.A.; Kalugin, I.A. & Klerkx, J.
(2002). Disequilibrium between uranium and its progeny in the Lake Issyk-Kul
system (Kyrgyzstan) under a combined effect of natural and manmade processes.
J.Env. Radioact., 83, 1, 61-84.
Natural Gas202
Giraudi, C. (1989). Lake levels and climate for the last 30,000 years in the Fucino area
(Abruzzo, CentraI ltaly): A review. Palaeogeogr. Palaeoclimatol. Palaeoecol., 70, 249-
260.
Giralt, S. ; Klerkx, J. ; De Batist, M. ; Beck, C. ; Bobrov, V. ; Gavshin, V. ; Julià, R. ; Kalugin, I. ;
Kipfer, R. ; Lignier, V. ; Lombardi, S. ; Matychenkov, V. ; Peeters, F. ; Podsetchine,
V. ; Riera, S. ; Romanovsky, V. ; Sukhorukov, F. & Voltattorni, N. (2003). Are
environmental changes affecting the natural state of Lake Issyk-Kul ? Proceedings of
NATO Advanced Research Workshop on “Dying and dead seas”, Liege, 5-10 May 2003.
Gregory, R.G. & Durrance, E.M. (1985). Helium, carbon dioxide and oxygen soil gases:
small-scale varations over fractured ground. J. Geochem. Expl., 24, (1), 29-49.
Hickman, S.; Sibson, R. & Bruhn, R. (1995). Introduction to special section: Mechanical
involvement of fluids in faulting. J. Geophys. Res., 100, 12,831–12,840.
Hinkle, M. (1994). Environmental conditions affecting concentrations of He, CO
2
, O
2
and N
2
in soil gases. Appl. Geochem., 9, 53– 63.
Holub, R. F. & Brady, B. T. (1981). The effect of stress on radon emanation from rock, J.
Geophys. Res., 86, 1776–1784.
Hueckel, T. & Pellegrini, R. (2002). Reactive plasticity for clays: application to a natural
analog of long-term geomechanical effects of nuclear waste disposal. Engineering
Geology, 64, 195-215.
Irwin, W.P. & Barnes, I. (1980). Tectonic relations of carbon dioxide discharges and
earthquakes. J. Geophys. Res., 85, 3115–3121.
Kerrick, D.M.; McKibben, M.A.; Seward, T.M. & Caldeira, K. (1995). Convective
hydrothermal CO
2
emission from high heat flow regions. Chem. Geol., 121, 285–293.
King, C.Y. (1978). Radon emanation on San Andreas fault. Nature, 271, 516–519.
King, C.Y.; King, B.S.; Evans, W.C. & Zang, W. (1996). Spatial radon anomalies on active
faults in California, Appl. Geochem., 11, 497-510.
Klusman, R.W. (1993). Soil Gas and Related Methods for Natural Resource Exploration.
Wiley, Chichester, 483 pp.
Leoni, L.; Polizzano, C.; Sartori F. & Sensi, L. (1984). Chemical and mineralogical
transformation induced in Pliocene clays by a small subvolcanic body and
consequence for the storage of radioactive wastes. N. Jb. Mineral. Mh., 155-168.
Lewicki, J.L.; Evans, W.C.; Hilley, G.E.; Sorey, M.L.; Rogie, J.D. & Brantley, S.L. (2003).
Shallow soil CO
2
flow along the San Andreas and Calaveras Faults, California.
Journal of Geophysical Research, 108, B4, 14 pp.
Lombardi., S.; Etiope, G.; Guerra, M.; Ciotoli, G.; Grainger, P.; Duddridge, G.A.; Gera, F.;
Chiantore, V.; Pensieri, R.; Grindrod, P. & Impey, M. (1996). The refinement of soil
gas analysis as a geological investigative technique. Final Report. Work carried out
under a cost sharing contract with the European Atomic Energy Community in the
framework of its 4th R&D program on Management and Storage of Radioactive
Waste (1990-1994), Part A, Task 4: Disposal of Radioactive Waste. EUR 16929 EN.
Lombardi, S. & Voltattorni, N. (2010). Rn, He and CO
2
soil gas geochemistry for the study of
active and inactive faults. Applied Geochemistry, 25, 1206-1220.
Manini, E., Luna, G., Corinaldesi, C., Zeppilli, D., Bortoluzzi, G., Caramanna, G., Raffa, F. &
Danovaro, R. (2008). Prokaryote diversity and virus abundance in shallow
hydrothermal vents of the Mediterranean Sea (Panarea Island) and the Pacific
Ocean ( North Sulawesi-Indonesia). Microbial Ecology, 55, 626-639.
Morawska, L. & Phillips, C.R. (1993). Dependance of the radon emanation coefficient on
radium distribution and internal structure of the material. Geochim. Cosmochim.
Acta, 57, 1783-1797.
Nijman, W. (1971). Tectonics of the Velino-Sirente area, Abruzzi, Central Italy, Proc. K,: Ned.
Akad. Wet., Ser. B, 74(2), 156-184.
Pinault, J. L. & Baubron, J. C. (1996). Signal processing of soil gas radon, atmospheric
pressure, moisture, and soil temperature data: a new approach for radon
concentration modeling, J. Geophys. Res., 101, B2, 3157-3171.
Rahn, T.A.; Fessenden, J.E. & Wahlen, M. (1996). Flux chamber measurements of anomalous
CO
2
emission from the flanks of Mammoth Mountain, California. Geophys. Res.
Lett., 23, 1861–1864.
Reimer, G.M. & Gundersen, L.C.S. (1989). A direct correlation among indoor Rn, soil gas Rn
and geology in the Reading Prong near Boyertown, Pennsylvania. Health Phys., 57,
155-160.
Reimer, G.M. (1990). Reconnaissance techniques for determining soil gas radon
concentrations: an example from Prince Geoges County, Maryland. Geophys. Res.
Lett., 17, 809– 8012.
Segovia, N. ; De la Cruz Reyna, S. ; Mena, M. ; Ramos, E. ; Monnin, M. & Seidel, J.L. (1989).
Radon in soil anomaly observed at Los Azufres Geothermal field, Michoacan: a
possible precursor of the 1985 Mexico earthquake (Ms D 8.1). Natural Hazards, 1,
319–329.
Shapiro, M.H. ; Melvin, J.D. ; Tombrello, T.A. ; Fong-Liang, J. ; Gui-Ru, L. ; Mendenhall,
M.H. & Rice, A. (1982). Correlated radon and CO
2
variations near the San-Andreas
fault. Geophys. Res. Lett., 9, 503–506.
Shapiro, M.H. ; Melvin, J.D. ; Copping, N.A. ; Tombrello, T.A. & Whitcombe, J.H. (1989).
Automated radon–thoron monitoring for earthquake prediction research. In: Radon
Monitoring in Radioprotection, Environmental Radio-Activity and Earth Sciences. ICTP,
Trieste, pp. 137–153.
Sugisaki, R.; Anno, H.; Aedachi, M. & Ui, H. (1980). Geochemical features of gases and rocks
along active faults. Geochem. J., 14, 101–112.
Sugisaki, R. (1983). Origin of hydrogen and carbon dioxide in fault gases and its relation to
fault activity. J. Geol., 91, 239-258.
Tanner, A.B. (1964). Radon migration in the ground: A supplementary review. In: The
Natural Radiation Environment, vol. I, T.F. Gesell and W.M. Lowder Eds., pp. 5-56,
Univ. of Tex., Austin.
Thomas, D.M. ; Cox, M.E. & Cuff, K.E. (1986). The association between ground gas radon
variations and geologic activity in Hawaii. J. Geophys. Res., 91, 12186–12198.
Thomas, D. (1988). Geochemical precursors to seismic activity. Pure Appl. Geophys., 126, 241–
265.
Toutain, J.P. ; Baubron, J.C. ; Le Bronec, J. ; Allard, P. ; Briole, P. ; Marty, B. ; Miele, G. ;
Tedesco, D. & Luongo, G. (1992). Continuous monitoring of distal gas emanations
at Vulcano, southern Italy. Bull. Volcanol., 54, 147–155.
Voltattorni, N.; Lombardi, S. & Beaubien, S.E. (2004). Evaluation of radioactive elements
migration from uranium mines in Kyrghystan (Central Asia). Proceeding oft he 32
nd
International Geological Congress, Firenze, Fortezza da Basso, 20-28 Agosto 2004.
Soil gas geochemistry: signicance and application in geological prospectings 203
Giraudi, C. (1989). Lake levels and climate for the last 30,000 years in the Fucino area
(Abruzzo, CentraI ltaly): A review. Palaeogeogr. Palaeoclimatol. Palaeoecol., 70, 249-
260.
Giralt, S. ; Klerkx, J. ; De Batist, M. ; Beck, C. ; Bobrov, V. ; Gavshin, V. ; Julià, R. ; Kalugin, I. ;
Kipfer, R. ; Lignier, V. ; Lombardi, S. ; Matychenkov, V. ; Peeters, F. ; Podsetchine,
V. ; Riera, S. ; Romanovsky, V. ; Sukhorukov, F. & Voltattorni, N. (2003). Are
environmental changes affecting the natural state of Lake Issyk-Kul ? Proceedings of
NATO Advanced Research Workshop on “Dying and dead seas”, Liege, 5-10 May 2003.
Gregory, R.G. & Durrance, E.M. (1985). Helium, carbon dioxide and oxygen soil gases:
small-scale varations over fractured ground. J. Geochem. Expl., 24, (1), 29-49.
Hickman, S.; Sibson, R. & Bruhn, R. (1995). Introduction to special section: Mechanical
involvement of fluids in faulting. J. Geophys. Res., 100, 12,831–12,840.
Hinkle, M. (1994). Environmental conditions affecting concentrations of He, CO
2
, O
2
and N
2
in soil gases. Appl. Geochem., 9, 53– 63.
Holub, R. F. & Brady, B. T. (1981). The effect of stress on radon emanation from rock, J.
Geophys. Res., 86, 1776–1784.
Hueckel, T. & Pellegrini, R. (2002). Reactive plasticity for clays: application to a natural
analog of long-term geomechanical effects of nuclear waste disposal. Engineering
Geology, 64, 195-215.
Irwin, W.P. & Barnes, I. (1980). Tectonic relations of carbon dioxide discharges and
earthquakes. J. Geophys. Res., 85, 3115–3121.
Kerrick, D.M.; McKibben, M.A.; Seward, T.M. & Caldeira, K. (1995). Convective
hydrothermal CO
2
emission from high heat flow regions. Chem. Geol., 121, 285–293.
King, C.Y. (1978). Radon emanation on San Andreas fault. Nature, 271, 516–519.
King, C.Y.; King, B.S.; Evans, W.C. & Zang, W. (1996). Spatial radon anomalies on active
faults in California, Appl. Geochem., 11, 497-510.
Klusman, R.W. (1993). Soil Gas and Related Methods for Natural Resource Exploration.
Wiley, Chichester, 483 pp.
Leoni, L.; Polizzano, C.; Sartori F. & Sensi, L. (1984). Chemical and mineralogical
transformation induced in Pliocene clays by a small subvolcanic body and
consequence for the storage of radioactive wastes. N. Jb. Mineral. Mh., 155-168.
Lewicki, J.L.; Evans, W.C.; Hilley, G.E.; Sorey, M.L.; Rogie, J.D. & Brantley, S.L. (2003).
Shallow soil CO
2
flow along the San Andreas and Calaveras Faults, California.
Journal of Geophysical Research, 108, B4, 14 pp.
Lombardi., S.; Etiope, G.; Guerra, M.; Ciotoli, G.; Grainger, P.; Duddridge, G.A.; Gera, F.;
Chiantore, V.; Pensieri, R.; Grindrod, P. & Impey, M. (1996). The refinement of soil
gas analysis as a geological investigative technique. Final Report. Work carried out
under a cost sharing contract with the European Atomic Energy Community in the
framework of its 4th R&D program on Management and Storage of Radioactive
Waste (1990-1994), Part A, Task 4: Disposal of Radioactive Waste. EUR 16929 EN.
Lombardi, S. & Voltattorni, N. (2010). Rn, He and CO
2
soil gas geochemistry for the study of
active and inactive faults. Applied Geochemistry, 25, 1206-1220.
Manini, E., Luna, G., Corinaldesi, C., Zeppilli, D., Bortoluzzi, G., Caramanna, G., Raffa, F. &
Danovaro, R. (2008). Prokaryote diversity and virus abundance in shallow
hydrothermal vents of the Mediterranean Sea (Panarea Island) and the Pacific
Ocean ( North Sulawesi-Indonesia). Microbial Ecology, 55, 626-639.
Morawska, L. & Phillips, C.R. (1993). Dependance of the radon emanation coefficient on
radium distribution and internal structure of the material. Geochim. Cosmochim.
Acta, 57, 1783-1797.
Nijman, W. (1971). Tectonics of the Velino-Sirente area, Abruzzi, Central Italy, Proc. K,: Ned.
Akad. Wet., Ser. B, 74(2), 156-184.
Pinault, J. L. & Baubron, J. C. (1996). Signal processing of soil gas radon, atmospheric
pressure, moisture, and soil temperature data: a new approach for radon
concentration modeling, J. Geophys. Res., 101, B2, 3157-3171.
Rahn, T.A.; Fessenden, J.E. & Wahlen, M. (1996). Flux chamber measurements of anomalous
CO
2
emission from the flanks of Mammoth Mountain, California. Geophys. Res.
Lett., 23, 1861–1864.
Reimer, G.M. & Gundersen, L.C.S. (1989). A direct correlation among indoor Rn, soil gas Rn
and geology in the Reading Prong near Boyertown, Pennsylvania. Health Phys., 57,
155-160.
Reimer, G.M. (1990). Reconnaissance techniques for determining soil gas radon
concentrations: an example from Prince Geoges County, Maryland. Geophys. Res.
Lett., 17, 809– 8012.
Segovia, N. ; De la Cruz Reyna, S. ; Mena, M. ; Ramos, E. ; Monnin, M. & Seidel, J.L. (1989).
Radon in soil anomaly observed at Los Azufres Geothermal field, Michoacan: a
possible precursor of the 1985 Mexico earthquake (Ms D 8.1). Natural Hazards, 1,
319–329.
Shapiro, M.H. ; Melvin, J.D. ; Tombrello, T.A. ; Fong-Liang, J. ; Gui-Ru, L. ; Mendenhall,
M.H. & Rice, A. (1982). Correlated radon and CO
2
variations near the San-Andreas
fault. Geophys. Res. Lett., 9, 503–506.
Shapiro, M.H. ; Melvin, J.D. ; Copping, N.A. ; Tombrello, T.A. & Whitcombe, J.H. (1989).
Automated radon–thoron monitoring for earthquake prediction research. In: Radon
Monitoring in Radioprotection, Environmental Radio-Activity and Earth Sciences. ICTP,
Trieste, pp. 137–153.
Sugisaki, R.; Anno, H.; Aedachi, M. & Ui, H. (1980). Geochemical features of gases and rocks
along active faults. Geochem. J., 14, 101–112.
Sugisaki, R. (1983). Origin of hydrogen and carbon dioxide in fault gases and its relation to
fault activity. J. Geol., 91, 239-258.
Tanner, A.B. (1964). Radon migration in the ground: A supplementary review. In: The
Natural Radiation Environment, vol. I, T.F. Gesell and W.M. Lowder Eds., pp. 5-56,
Univ. of Tex., Austin.
Thomas, D.M. ; Cox, M.E. & Cuff, K.E. (1986). The association between ground gas radon
variations and geologic activity in Hawaii. J. Geophys. Res., 91, 12186–12198.
Thomas, D. (1988). Geochemical precursors to seismic activity. Pure Appl. Geophys., 126, 241–
265.
Toutain, J.P. ; Baubron, J.C. ; Le Bronec, J. ; Allard, P. ; Briole, P. ; Marty, B. ; Miele, G. ;
Tedesco, D. & Luongo, G. (1992). Continuous monitoring of distal gas emanations
at Vulcano, southern Italy. Bull. Volcanol., 54, 147–155.
Voltattorni, N.; Lombardi, S. & Beaubien, S.E. (2004). Evaluation of radioactive elements
migration from uranium mines in Kyrghystan (Central Asia). Proceeding oft he 32
nd
International Geological Congress, Firenze, Fortezza da Basso, 20-28 Agosto 2004.
Natural Gas204
Voltattorni, N. ; Sciarra, A. ; Caramanna, G. ; Cinti, D. ; Pizzino, L. & Quattrocchi, F. (2009).
Gas geochemistry of natural analogues for the studies of geological CO
2
sequestration. Applied Geochemistry, 24, 1339–1346.
Voltattorni, N.; Lombardi, S. & Rizzo, S. (2010).
222
Rn and CO
2
soil- gas geochemical
characterization of thermally altered clays at Orciatico (Tuscany, Central Italy).
Applied Geochemistry, 25, 1248-1256.
Wattananikorn, K. ; Techakosit, S. & Jitaree, N. (1995). A combination of soil gas radon
measurements in uranium exploration. Nucl. Geophys.,9, 643–652.
Woith, H. ; Pekdeger, A. & Zschau, J. (1991). Ground water radon anomalies in space and
time: a contribution to the joint Turkish–German earthquake prediction project. In:
Earthquake Prediction: State of the Art. EUG, Strasbourg.
Adsorption of methane in porous materials as the basis for the storage of natural gas 205
Adsorption of methane in porous materials as the basis for the storage
of natural gas
Cecilia Solar, Andrés García Blanco, Andrea Vallone and Karim Sapag
X
Adsorption of methane in porous materials
as the basis for the storage of natural gas
Cecilia Solar, Andrés García Blanco, Andrea Vallone and Karim Sapag
Laboratorio de Sólidos Porosos-Instituto de Física Aplicada-CONICET, Dpto. de Física-
Universidad Nacional de San Luis
San Luis, Argentina
1. Introduction
It is well known that the natural gas (NG) is a substance of fossil origin from the decomposition
of organic matter. It is found trapped under the terrestrial surface in stratus that avoid the natural
release to atmosphere. These underground deposits can be oceanic or terrestrial.
The NG is a homogeneous mixture, having variable proportions of hydrocarbons, being the
main constitute the methane (CH
4
), which content generally ranges from 55 to 98 % in
volume. Also, it contains ethane (C
2
H
6
), propane (C
3
H
8
) and heavier constitutes. Although it
can be found in gas phase or in solution with oil, under normal atmospheric conditions,
remains in gas phase. It may have some impurities or substances that are not hydrocarbons,
such as Hydrogen Sulfide, Nitrogen and Carbon Dioxide (Figure 1). According to its origin,
natural gas is classified in associated and non-associated, being the first, the one which remains
in contact and/or dissolved with the oil from the deposit. The non-associated gas can be
found in deposits lacking oil crude at the initial conditions of pressure and temperature.
Fig. 1. Principal constitutes of Natural Gas (in percentage).
10
Natural Gas206
From the fossil fuels, the cleanest is the natural gas. Its combustion, similarly to other fuels,
produces mainly CO
2
and water vapor. The emissions of CO
2
are 25-30% lower than the
generated by the fuel-oil and a 40-50% lower than charcoal (Figure 2) per unit of produced
energy (Natural Gas and Climate Change Policy, 1998; Comisión Nacional de Energía, 1999).
0
20
40
60
80
100
120
55,9
91,3
78,573,3
102
kg CO2/GJ
Lignite Antracite Fuel Oil Diesel Natural Gas
Fig. 2. CO
2
Emissions in the combustion (Kg per GJ).
At worldwide scale, the resources of natural gas are abundant. However, as oil, they are
highly concentrated in a reduced number of countries and deposits. Some data reported in
the BP Statistical Review of World Energy, 2009, revealed interesting information: three
countries (Russia, Iran and Qatar), hold the 56% of the world reserves (WR). Almost the 50%
of the WR are distributed in 25 deposits around the world and the countries that are
members of the OPEC (Organization of the Petroleum Exporting Countries), control the 50%
of the WR. The percentage distribution of the WR by the end of 2008 is shown in Figure 3.
Fig. 3. The percentage distribution of the world reserves of natural gas by the end of 2008
according to the Statistical Review of World Energy, 2009.
As it may be seen from Figure 3, the world reserves of natural gas, although
heterogeneously, are distributed throughout the world, constituting an advantage to be able
to supply the local requirements. During the last few decades, the volume of discovered gas
has been decreasing but it still keeps the necessary volume to ensure their existence for
many years. Additionally, the estimations of these reserves are progressing as new
techniques of exploitation, exploration and extraction, are discovered. It is estimated that a
substantial quantity of natural gas remains undiscovered (World Energy Outlook, 2009).
The NG has vast diversity of applications: in industry, trade, energy generation, residential
sector and terrestrial transport, and its use have shown an important growth over the last
few years (MacDonald & Quinn, 1998; Inomata et al., 2002; Prauchner & Rodríguez-Reinoso,
2008).
Regarding the particular use as fuel for transport units, such as cars, autobuses and trucks,
the natural gas vehicle (NGV) shows diverse environmental benefits. One of them is the
reduction of post combustion contaminants, lowering the maintenance costs compared to
traditional fuels (Cook et al., 1999; Lozano-Castelló et al., 2002a; Alcañiz-Monge et al., 1997).
The environmental advantages at using the NGV are numerous. However, from the point of
view of the combustion products, it can be remarked: i) it does not contain lead or heavy
metals traces, avoiding their emission to the atmosphere, ii) lack of suspended solid particles
that are present when using gasoline affecting health (increase of respiratory and
cardiovascular diseases), iii) absence of sulfur and subsequently no sulfur dioxide (SO
2
)
emissions, typical contaminant from transport. Compared to liquid fuels, the emissions of
the NGV combustion produce up to 76% less CO, 75% less NOx, 88% less hydrocarbons and
30% less CO
2
. Furthermore, the physicochemical properties of the natural gas enable the use
of catalysts for the combustion of gases, obtaining excellent results and minimizing even
more the emissions (Sun et al., 1997).
The advantages of NG have promoted its use in the automotive fleet of many countries,
which exceeds six millions of vehicles at present. The advance in the technology for the
NGV use has not been standardized throughout the world. This is due to differences
regarding the availability of energy resources, contamination levels, fuel pricing policies,
applied auditing and, definitely, the set of government actions able to generate expectative
among the potential users.
Country Vehicles
Pakista
n
2,000.000
Ar
g
entine
1,678.000
Brazil
1,467.000
Ital
y
433,000
Colombia
251,000
India
225,000
EE.UU
130,200
German
y
54,200
Ja
p
a
n
24,700
France
8,400
Table 1. Estimated Natural Gas Vehicles in different countries.
Adsorption of methane in porous materials as the basis for the storage of natural gas 207
From the fossil fuels, the cleanest is the natural gas. Its combustion, similarly to other fuels,
produces mainly CO
2
and water vapor. The emissions of CO
2
are 25-30% lower than the
generated by the fuel-oil and a 40-50% lower than charcoal (Figure 2) per unit of produced
energy (Natural Gas and Climate Change Policy, 1998; Comisión Nacional de Energía, 1999).
0
20
40
60
80
100
120
55,9
91,3
78,573,3
102
kg CO2/GJ
Lignite Antracite Fuel Oil Diesel Natural Gas
Fig. 2. CO
2
Emissions in the combustion (Kg per GJ).
At worldwide scale, the resources of natural gas are abundant. However, as oil, they are
highly concentrated in a reduced number of countries and deposits. Some data reported in
the BP Statistical Review of World Energy, 2009, revealed interesting information: three
countries (Russia, Iran and Qatar), hold the 56% of the world reserves (WR). Almost the 50%
of the WR are distributed in 25 deposits around the world and the countries that are
members of the OPEC (Organization of the Petroleum Exporting Countries), control the 50%
of the WR. The percentage distribution of the WR by the end of 2008 is shown in Figure 3.
Fig. 3. The percentage distribution of the world reserves of natural gas by the end of 2008
according to the Statistical Review of World Energy, 2009.
As it may be seen from Figure 3, the world reserves of natural gas, although
heterogeneously, are distributed throughout the world, constituting an advantage to be able
to supply the local requirements. During the last few decades, the volume of discovered gas
has been decreasing but it still keeps the necessary volume to ensure their existence for
many years. Additionally, the estimations of these reserves are progressing as new
techniques of exploitation, exploration and extraction, are discovered. It is estimated that a
substantial quantity of natural gas remains undiscovered (World Energy Outlook, 2009).
The NG has vast diversity of applications: in industry, trade, energy generation, residential
sector and terrestrial transport, and its use have shown an important growth over the last
few years (MacDonald & Quinn, 1998; Inomata et al., 2002; Prauchner & Rodríguez-Reinoso,
2008).
Regarding the particular use as fuel for transport units, such as cars, autobuses and trucks,
the natural gas vehicle (NGV) shows diverse environmental benefits. One of them is the
reduction of post combustion contaminants, lowering the maintenance costs compared to
traditional fuels (Cook et al., 1999; Lozano-Castelló et al., 2002a; Alcañiz-Monge et al., 1997).
The environmental advantages at using the NGV are numerous. However, from the point of
view of the combustion products, it can be remarked: i) it does not contain lead or heavy
metals traces, avoiding their emission to the atmosphere, ii) lack of suspended solid particles
that are present when using gasoline affecting health (increase of respiratory and
cardiovascular diseases), iii) absence of sulfur and subsequently no sulfur dioxide (SO
2
)
emissions, typical contaminant from transport. Compared to liquid fuels, the emissions of
the NGV combustion produce up to 76% less CO, 75% less NOx, 88% less hydrocarbons and
30% less CO
2
. Furthermore, the physicochemical properties of the natural gas enable the use
of catalysts for the combustion of gases, obtaining excellent results and minimizing even
more the emissions (Sun et al., 1997).
The advantages of NG have promoted its use in the automotive fleet of many countries,
which exceeds six millions of vehicles at present. The advance in the technology for the
NGV use has not been standardized throughout the world. This is due to differences
regarding the availability of energy resources, contamination levels, fuel pricing policies,
applied auditing and, definitely, the set of government actions able to generate expectative
among the potential users.
Country Vehicles
Pakista
n
2,000.000
Ar
g
entine
1,678.000
Brazil
1,467.000
Ital
y
433,000
Colombia
251,000
India
225,000
EE.UU
130,200
German
y
54,200
Ja
p
a
n
24,700
France
8,400
Table 1. Estimated Natural Gas Vehicles in different countries.
Natural Gas208
Table 1 summarizes the number of natural gas vehicles in some representative countries
according to the Dirección de Tecnología, Seguridad y Eficiencia Energética, 2006.
In spite of the advantages showed by the NG in comparison to liquid fuels, there is an
important disadvantage: its low-energy density (heat of combustion/volume), which
constitutes a limitation for some applications. Therefore, under standard conditions of
pressure and temperature, the distance traveled by a vehicle per unit of fuel volume, using
NG, corresponds to the 0.12% of the trajectory with gasoline. Consequently, the storage of
this fuel, whether in quantity or density, plays an important role for its use in diverse kinds
of transport.
An alternative is to increase the density, for example, liquefying the NG. The liquefied
natural gas (LNG) is stored at the boiling point, 112K (-161ºC) in a cryogenic tank at a
pressure of 0.1MPa, where the energy density is approximately a 72% of the total gasoline.
This means that 1 volume of LNG corresponds to 600 volumes of natural gas under STP (600
v/v) conditions (Cracknell et al., 1993; Menon & Komarneni, 1998). However, this storage
method shows multiple inconveniences, mainly because the LNG increases inevitably the
temperature within the tank. Thus, the pressure rises and could result in a dangerous
situation. Moreover, the filling of the tank must be performed by an expert on cryogenic
liquids handling.
A widely used commercial method considered to increase the energy density of the natural
gas is to compress and store it as compressed natural gas (CNG). For this case, the NG can
be found as a supercritical fluid at room temperature and it becomes compressed at a
maximum pressure around 20-25 MPa, reaching a density 230 times higher (230 v/v) than
the one obtained for the natural gas under STP conditions (Menon & Komarneni, 1998;
Lozano-Castelló et al., 2002b). In this case, the energy density is approximately 25% of the
one from gasoline. A disadvantage is the risk of carrying highly compressed gas (20MPa)
within the vehicle. Modifications such as thick-walled tanks and complex safety valves
would be required.
The use of adsorbent materials, such as activated carbons and zeolites, among others
(Rodriguez-Reinoso & Molina-Sabio, 1992; Parkyns & Quinn, 1995; Sircar et al., 1996;
Alcañiz-Monge et al., 1997; Lozano-Castello et al., 2002c; Almansa et al., 2004; Marsh &
Rodriguez-Reinoso, 2006; Mentasty et al., 1991; Triebe et al., 1996), for the storage of natural
gas at low pressures, is known as adsorbed natural gas (ANG). Pressures are relatively low,
of the order of 2 to 4 MPa at room temperature, which represents an interesting alternative
for the transport and applications at large scale. The technology, in contrast with the other
two, is not well developed and is still at scientific level. At this stage, the studies on storage
by the ANG method are carried out using the methane, major constituent of the NG. It has
been found that the density of the compressed methane at 3.4MPa can be increased in a
factor higher than 4 by the use of adsorbents, reaching a relation of methane storage of 180
v/v, which is equivalent to compressed gas at more than 16MPa (Cook et al., 1999; Alcañiz-
Monge et al., 1997).
Through this chapter, basic concepts regarding adsorption and adsorbents are reviewed as
well as their application for the particular study of methane storage, starting point of the
ANG process. In addition, the methodology for the study is described and shows the
scientific advance in this field, reporting results from our research group and from other
laboratories.
2. Adsorption basics and methodology of study
Adsorption is a phenomenon in which surface plays an important role, unlike absorption
where molecules can penetrate the solid structure. The occurrence of this phenomenon in
gas-solid interactions is our major focus of interest.
The surfaces of solids, even those homogeneous, have imperfections. These defects are the
result of many circumstances, mainly its composition and the interaction that takes place
among the molecules that constitute their atmosphere. Figure 4 shows a classical schema of
this situation, according to the description made by Somorjai, 1994.
Fig. 4. Scheme of common defects on the apparently homogeneous solid surfaces.
Generally, the properties of the surfaces of the solids differ from their bulk for many
reasons. Some of which are enlisted below:
The perturbation of the superficial electron density is different to the one from the
bulk. This is caused by the loss of structural periodicity in the perpendicular
direction of the surface.
The presence of decompensated forces on the surface due to the lack of neighbor
atoms (producing potential wells, nearby molecules are attracted).
Vibrational properties on the surface are different (geometrical and energetic
effects, producing curvatures) from the ones on the rest of the solid.
Some phenomena can occur: Relaxation or Superficial Reconstruction, which means
that the superficial atoms show geometrical and energetic differences to the atoms
from the bulk.
These reasons promote the presence of attractive potentials, which are able to attract
molecules from the surrounding leaded by thermodynamic parameters, particularly,
pressure P and temperature T of the gas-solid system. Moreover, superficial centers can take
place showing additional electrostatic effects and creating new attractive or repulsive
“sites”. Therefore, when one or more molecules from a fluid approach the surface, they
could be trapped and nucleation, motion and the formation of layers in the interface, would
take place. This process is named Adsorption.
“Adsorption of a gas onto a solid surface” can be defined as the gain of one or more
constituents of the gas in the region of the gas-solid interface. Figure 5 shows a schema that
represents the process.
The adsorption phenomenon involves an increment of the gas density in the neighborhood
of the contact surface and since the process is spontaneous, the change in the free energy of
Gibbs is smaller than zero. Given that the entropy change is also below zero (a decrease in
Adsorption of methane in porous materials as the basis for the storage of natural gas 209
Table 1 summarizes the number of natural gas vehicles in some representative countries
according to the Dirección de Tecnología, Seguridad y Eficiencia Energética, 2006.
In spite of the advantages showed by the NG in comparison to liquid fuels, there is an
important disadvantage: its low-energy density (heat of combustion/volume), which
constitutes a limitation for some applications. Therefore, under standard conditions of
pressure and temperature, the distance traveled by a vehicle per unit of fuel volume, using
NG, corresponds to the 0.12% of the trajectory with gasoline. Consequently, the storage of
this fuel, whether in quantity or density, plays an important role for its use in diverse kinds
of transport.
An alternative is to increase the density, for example, liquefying the NG. The liquefied
natural gas (LNG) is stored at the boiling point, 112K (-161ºC) in a cryogenic tank at a
pressure of 0.1MPa, where the energy density is approximately a 72% of the total gasoline.
This means that 1 volume of LNG corresponds to 600 volumes of natural gas under STP (600
v/v) conditions (Cracknell et al., 1993; Menon & Komarneni, 1998). However, this storage
method shows multiple inconveniences, mainly because the LNG increases inevitably the
temperature within the tank. Thus, the pressure rises and could result in a dangerous
situation. Moreover, the filling of the tank must be performed by an expert on cryogenic
liquids handling.
A widely used commercial method considered to increase the energy density of the natural
gas is to compress and store it as compressed natural gas (CNG). For this case, the NG can
be found as a supercritical fluid at room temperature and it becomes compressed at a
maximum pressure around 20-25 MPa, reaching a density 230 times higher (230 v/v) than
the one obtained for the natural gas under STP conditions (Menon & Komarneni, 1998;
Lozano-Castelló et al., 2002b). In this case, the energy density is approximately 25% of the
one from gasoline. A disadvantage is the risk of carrying highly compressed gas (20MPa)
within the vehicle. Modifications such as thick-walled tanks and complex safety valves
would be required.
The use of adsorbent materials, such as activated carbons and zeolites, among others
(Rodriguez-Reinoso & Molina-Sabio, 1992; Parkyns & Quinn, 1995; Sircar et al., 1996;
Alcañiz-Monge et al., 1997; Lozano-Castello et al., 2002c; Almansa et al., 2004; Marsh &
Rodriguez-Reinoso, 2006; Mentasty et al., 1991; Triebe et al., 1996), for the storage of natural
gas at low pressures, is known as adsorbed natural gas (ANG). Pressures are relatively low,
of the order of 2 to 4 MPa at room temperature, which represents an interesting alternative
for the transport and applications at large scale. The technology, in contrast with the other
two, is not well developed and is still at scientific level. At this stage, the studies on storage
by the ANG method are carried out using the methane, major constituent of the NG. It has
been found that the density of the compressed methane at 3.4MPa can be increased in a
factor higher than 4 by the use of adsorbents, reaching a relation of methane storage of 180
v/v, which is equivalent to compressed gas at more than 16MPa (Cook et al., 1999; Alcañiz-
Monge et al., 1997).
Through this chapter, basic concepts regarding adsorption and adsorbents are reviewed as
well as their application for the particular study of methane storage, starting point of the
ANG process. In addition, the methodology for the study is described and shows the
scientific advance in this field, reporting results from our research group and from other
laboratories.
2. Adsorption basics and methodology of study
Adsorption is a phenomenon in which surface plays an important role, unlike absorption
where molecules can penetrate the solid structure. The occurrence of this phenomenon in
gas-solid interactions is our major focus of interest.
The surfaces of solids, even those homogeneous, have imperfections. These defects are the
result of many circumstances, mainly its composition and the interaction that takes place
among the molecules that constitute their atmosphere. Figure 4 shows a classical schema of
this situation, according to the description made by Somorjai, 1994.
Fig. 4. Scheme of common defects on the apparently homogeneous solid surfaces.
Generally, the properties of the surfaces of the solids differ from their bulk for many
reasons. Some of which are enlisted below:
The perturbation of the superficial electron density is different to the one from the
bulk. This is caused by the loss of structural periodicity in the perpendicular
direction of the surface.
The presence of decompensated forces on the surface due to the lack of neighbor
atoms (producing potential wells, nearby molecules are attracted).
Vibrational properties on the surface are different (geometrical and energetic
effects, producing curvatures) from the ones on the rest of the solid.
Some phenomena can occur: Relaxation or Superficial Reconstruction, which means
that the superficial atoms show geometrical and energetic differences to the atoms
from the bulk.
These reasons promote the presence of attractive potentials, which are able to attract
molecules from the surrounding leaded by thermodynamic parameters, particularly,
pressure P and temperature T of the gas-solid system. Moreover, superficial centers can take
place showing additional electrostatic effects and creating new attractive or repulsive
“sites”. Therefore, when one or more molecules from a fluid approach the surface, they
could be trapped and nucleation, motion and the formation of layers in the interface, would
take place. This process is named Adsorption.
“Adsorption of a gas onto a solid surface” can be defined as the gain of one or more
constituents of the gas in the region of the gas-solid interface. Figure 5 shows a schema that
represents the process.
The adsorption phenomenon involves an increment of the gas density in the neighborhood
of the contact surface and since the process is spontaneous, the change in the free energy of
Gibbs is smaller than zero. Given that the entropy change is also below zero (a decrease in
Natural Gas210
the freedom degree of the gas molecules during the process), the enthalpy change is lower
than zero. Thus, the process is exothermic (Rouquerol et al., 1999).
Fig. 5. Representation of the adsorption process of a gas on a solid surface for a given
pressure, P and temperature, T.
When the adsorption process is reversible it means physical adsorption or physisorption,
our major focus of interest for the study of natural gas storage. In this case, the result of the
adsorption heats or enthalpy changes in the process are not elevated values, being for the
methane about 16 KJoule/mol (Cook et al., 1999). The interaction forces occurring between
the solid surface (adsorbent) and the adsorbed gas (adsorbate) are Van der Waals type,
where prior to adsorption, the gas is called adsorbable. Moreover, adsorbate-adsorbate
interaction may take place and is neglected in some studies when compared to the
adsorbate-adsorbent interaction. It can also be considered that in average, these interactions
do not impact the whole process.
The net interaction potential that the molecules surrounding the surface may experience, can
be represented as seen in Figure 6, where the energy of interaction of one particle at a
distance z of the surface, is the sum of the interaction of each molecule(i) with each atom (j)
of the solid, given by equation 1.
j
ij
zE
)(
(1)
Figure 6 represents a particle with a kinetic energy E
k
approaching to the solid surface.
Fig. 6. Representation of the interaction potential that molecules nearby to the surface may
sense.
The particle may detect the phonons excitation and subsequently, the potential attraction of
the solid, which has a minimum (value) at a distance Z
0
, representing the minimal distance
of approaching to the solid.
The energy of the adsorbate-adsorbent interaction can be expressed using several terms.
Some of them are described in the following equation:
QdipPRD
EEEEEzE
)(
(2)
where E
D
represents the dispersive potential (attractive); E
R
, the repulsive; E
P
, the one
caused by the polarizability; E
dip
, the dipolar and E
Q,
the quadrupolar interactions
(Rouquerol et al., 1999).
Considering only the first two terms, a Lennard-Jones (L-J) potential would take place,
which involve the Van der Waals attractive forces and the Pauli repulsive forces.
2.1 Quantification of the Adsorption
Assuming a system set at a given temperature where a gas becomes into contact with a solid
surface occupying a volume V at a pressure P
i
prior to the adsorption, while a part of the
adsorbable gas passes to the adsorbed state, keeping V and T unchanged, it should be noted
a pressure decrease, followed by a stabilization of the system to a final equilibrium at
pressure P
eq
. Figure 7 represents the adsorption process at constant V and T.
Fig. 7. Scheme of the Adsorption process.
Once the pressure change (P
i
-P
eq
) is determined by an equation of state that represents the
gases under study, it is possible to calculate the quantity of moles that are no longer in gas
phase but in the adsorbed phase at that pressure. The same can also be expressed in terms of
adsorbed volume or grams of adsorbate, which is usually reported in standard conditions of
temperature and pressure. Whether P
i
is increased, a new P
eq
is obtained as well as a new
adsorbed quantity, maintaining unchanged the temperature and volume of the system.
Thereby, the relation between the adsorbed amount and the pressure may be graphically
found at constant temperature, reported as adsorption isotherm. This method, called
volumetric or manometric, is the most widely used to measure the adsorption of gases and
was selected for our laboratory to study adsorption processes. By the gravimetric method,
the adsorbed quantity is measured from the mass gain during the process.