= ab rN Application of Geochemistry in Geothermal Reservoir Development by Franco D'AMORE (Co-ordinator)eel LEX R UNITAR/UNOP CENTRE ON SMALL ENERGY RESOURCES ROME - ITALY APPLICATIONS OF GEOCHEMISTRY IN GEOTHERMAL RESERVOIR DEVELOPMENT SERIES OF TECHNICAL GUIDES ON THE USE OF GEOTHERMAL ENERGY by Franco D'AMORE (Co-ordinator) Rome, 1991 Nb 2) d+CHEMICAL TECHNIQUES IN GEOTHERMAL EXPLORATION W.F. GIGGENBACH Chemistry Division, DSIR, Private Bag, Petone, New Zealand INTRODUCTION ‘The application of chemical techniques has become an integral part of any geothermal exploration programme. Especially during the early, pre-drilling stages, geochemistry may provide information on deep conditions and processes not obtainable by geological or geophysical techniques. After all, the waters and gases discharged at the surface "have been there" and generally carry imprints of their deeper histories with them.. The constituents encountered in these fluids may be subdivided into two major groups according to the type of information provided: Chemically inert, non-reactive constituents form a group which may be called sracers, Once added to the fluid phases, ideally they should remain unchanged, providing a tag allowing their origins to be traced back to theit source components. ~—f~ Chemically reactive species, responding to changes in their environment in a controlled _-and well understood manner, form a group potentially useful as geoindicazors. Examples of the first group are, of course, the noble gases He and Ar, followed by the comparatively “conservative” constituents Cl, B, Li, Rb, Cs, and N;. The species of the second group, such as Na, K, Mg, Ca, and SiO,, take part in temperature-dependent interactions with the Al-silicate rock structure generally housing geothermal systems, or are, as e.g. Hy, H;S, CH,, and CO,, involved in temperature- and pressure-dependent redox reactions among one <2 another or with redox systems (Fell/Felll) of the rock phase. The boundaries between the two groups are not rigid. A constituent may under one set of conditions be quite inert, e.g. Cs at temperatures >250°C, but it is incorporated into secondary zeolites at lower temperatures. Each of the constituents of geothermal fluids behaves in its own peculiar way and therefore, if used to best advantage, will provide unique information. In this introduction to the application of chemical techniques in geothermal exploration, simple procedures are described allowing an initial assessment of the geothermal potential of an + area to be made by extracting much of the information carried by a given constituent in a comparatively straight-forward manner. The procedures frequently require an initial, “eyeball” _ assessment of correlations among sets of various constituents, a task most readily carried out by _ “use of triangular diagrams. A special effort, therefore, is made to point out the peculiarities of shis type of data presentation. The procedures are based on constituents analyzed most requently and by readily available techniques (Giggenbach and Goguel, 1989). 119W.F. Giggenbach Sets of analytical resuits for quite arbitrarily selected water and gas samples, spanning a wide range of tectonic, geological and hydrological environments, are given in Tables 1 and ' 2. For four high temperature geothermal areas (WK, NG, ZU, and MV), pairs of samples — representing well and associated spring or fumarole discharges are given. The two El Ruiz | samples are from a highly acid volcanic spring and a neutral chloride spring at lower levels. The Araro samples are likely to represent the natural outflow of chloride water from the Los Azufres geothermal field. The two samples from boiling springs at Manikaran and: Fang have no obvious volcanic-magmatic associations; the Yasur water is discharged from the complex housing the active volcano, the gas sample from an associated "geothermal" fumarole. The Paraso samples are from an extensive area of hot water discharges on this volcanic island; the Lake Nyos samples represent the deep, CO; charged waters there. The Waitangi Soda Spring samples are also produced from a highly CO, charged system. MO and MU are associated with natural gas discharges along the east and west coast of New Zealand, while the White Island samples are from a spring producing highly acidic, obviously volcanic waters. These data will be used as examples to illustrate the various procedures. Conclusions drawn here should in no way be considered prejudicial to any ongoing or future investigations. Table 1 The chemical composition of thermal and mineralized waters from New Zealand (WK, NG, MO, MU, We), Guatemala (ZU), Costa Rica (MV), Colombia (RA, RB), Mexico (AR), India (MA), Thailand (FN), Solomon Islands (PR), Vanuatu (YA) and Cameroon (LN) in mg/kg. \ area co pH Li Ma ok Rb Cs Mp Ca B HCO, sio, $0, ch wk wairaket, welt 1170 167 2.20 2 26 5 590 35.1970 lwkwairakei, "spring 1220 140 2:30 30 43 30 320 30° 2100 NG Ngawha, ‘welt 880 75 0.30 3 995 310 385 26 tec ING Nganha, spring 0 6% 0.29 11 850 330 150 © Gee 1290 zu 2unit, wett 1030 210 1.90 11 45 150 890 61 1700 zu Dunit, spring 260 37 0108 0:02 43 $ $00 200 © 195170 KV Miravatles, welt 1970 238 105 0260 7 se (40 $90 36 3300 RV Miravaltes, Spe. 1970-79 0121 0.16 2 48 910 112 © 120 2600 RA Ruiz, acid spring 62 3 280 226 0.37 0.04 155 216 8 = 156 106701350 IRB Ruiz, neutrals. 3% $10 78 4.56 0.62 5.1 48 19 175 180 1 1000, } JAR Araro, sprii 32 6 7OF 50 0.43 1112 O13 30 73 63 230 135 t010 IMA Manikiran, spring «94 *7.4«*T.2 STOOLS Oe SS 51 3 190 “7S 3 0] FW Fang, speing 99 9.0 0.6 122 8 9.16 0.29 OF 1 <1 145 195 eater IPR Parato, spring 56 $16 1:8 1210 178 9.74 9.09 26.6 289 16 6 150 205 2840 YA Yasur, spring 99 88 013 1270 7S 0.16 0:01 0.3 17 21 75 270 ©6280 aso | * Li Lake ives, Take B54 01 15S .006 Go) 38:0 30 <1 400 45 cle eal Ws Uaitangi soda spr. 49 7.3 1.7 285-26 0.11 0.07 8.9 17 3 265 178 43365, HO Merere, spring 47 710 416 $700 BE 0:10 .008 90.0 2360 57 (30 27 <3 15800 HU Maui, well 130 715 $16 7280 S40 0:71 0.08 48.0 190 15 630 36 18 12600) WI unice Tl. spring —'98. 018 2.9 5910 635 5.40 0.35 38003150 160 <1 - 4870 38700 ‘SW Seawater 4% 7.8 0.2 10560 380 0.13 <.01 1270 400 S$ 1460 ~~ — arta 19000 | ~ \ 120 iChemical Techniques in Geothermal Exploration Table 2 The chemical composition of gases associated with the water discharges of Table rs 1, on water-free basis in mmol/mol. Area tc co ws tearm lx uatrake’, welt 20 aks 100 0.0080 2.400 018s gas ic Wairaket fumarote fae 973 "7 orteeofig00 1300 14a Ne Noauho, sel 230 59 100.0080 2g00 Lom S250 NG Naawha, pool 20 900" 0.110 F400 0.02000 2Y unit, welt soo 96025 0.0020 4.300 0.060 80.2 Bb init, finarote a? 95036 (010u3 | aed 0200 AS wv wiravatles, welt 24659808 (8.0015 $300 9.080 80:3 hv miravatles, vent 98 85««§ (010025 200 01020 «$$. aa Et Ruiz, spr e298 26 0.00 <1 0.790 uk fe el Ruiz, spring 5% 953 & Loos © 0.060 OLs0 283.0 Aa Araro, ering % 97 “Y oroosa cote aces 57 Oe nk Mantkeran, spring 9 «985-—=«S« L400 LOTS acted 7 aL? Fx Fang, spring # 0 20 0.0710 3.800 0.400 2 48 PR paras, spring 36g Gloria dg cas “a |, YA Yasur,’ fumarate 5 7a. es O.oo0e 72.000, o'e00 53 Oa Uh Ske'yes, cies. gas 23 96 10,0000 ~O:00/ 01050 2 lus watcangi soda spring <9 980 by Piper (1944) some 45 years ago for the classification of natural waters. Its major disadvantage is the use of sums of constituents thus obliterating any information carried by an individual constituent. Aiso, the interpretative value of these diagrams is only minimal if applied to geothermal waters. They are usually only presented as such and do not appear to encourage further or deeper discussion of source components, formation processes or thermodynamic correlations. In Fig. 1 compositional ranges are indicated for several typical groups of thermal waters such as volcanic and steam-heated waters formed by the absorption of high temperature, HCl-containing volcanic, or lower temperature, H,S-containing "geothermal" vapors, into groundwater. Most geochemical techniques are not suitable for application to these generally quite acid waters. The group best suited comprises the neutral, low sulfate, high chloride "geothermal" waters along the Cl-HCO, axis, close to the Cl comer. In the case of albeit neutral, but high bicarbonate waters, considerable caution is required in the application of most “geoindicators". Fig. 1 not only allows the weeding out of unsuitable waters, but may already provide an initial indication of mixing relationships or geographic groupings, with e.g. Cl waters forming | acentral core grading into HCO; waters towards the margins of a thermal area. High SO, /~ steam-heated waters are usually encountered over the more elevated parts of a field. The degree of separation between data points for high chloride and bicarbonate waters gives already an idea of the relative degrees of interaction of the CO, charged fluids at lower temperatures, and of the ‘HCO; contents increasing with time and distance travelled underground. This interpretation is supported by the shift in the position of data points representing spring discharges to higher relative HCO,-contents as compared to the well discharges at Ngawha (NG), Miravalles (MV) and especially Zunil (ZU). The compositional area where ionic solute geoindicators may be applied with sufficient confidence is quite small (hatched area in Fig. 1) and illustrates the need for this initial classification procedure. Relative Li, Rb and Cs contents The distribution of data points in Fig. 1 stresses differences among waters, largely + brought about by comparatively shallow processes. An indication of the existence of a common origin, or of common, deep processes shaping the composition of surface water discharges, is = provided by use of less reactive, “conservative” components, added at depth, but not affected _~by shallow processes, such as the rare alkalies Li, Rb and Cs. Relative Li, Rb and Cs contents of Fig. 2 again are plotted in terms of a trilinear diagram. Because of the large differences in the analytical values for the three components, ‘~ normalizing or scaling factors had to be applied to achieve an even spread of data points over / the plot. Omission of these scaling factors would have led to "bunching" of points in the Li comer of the plot. 123W.F. Giggenbach Li Figure 2. Relative Li, Rb and Cs contents in the thermal water discharges on weight basis. ‘The numerical value given to these scaling factors depends on the choice of constellation pf data points to be given special attention. Generally speaking, triangular diagrams can only Hope with a spread of values for a given variable over two orders of magnitude. Any data points representing values outside this range are bunched along one of the axes with considerable loss pf detail or resolution. By varying the scaling factors, different groups of data points can be ‘hifted into the center of the diagram where resolution is highest; in other words they can be put Inder the magnifying glass. No matter which linear scaling factors are chosen, mixing lines ways remain straight. Coordinates for Fig. 2 were calculated according to S = cy + dey + 10ce, (4) "Li" = 100e/S ©) 124Chemical Techniques in Geothermal Exploration 7 "%-Cs" = 1000cq/S © In the application of this triangular plot, advantage is taken of its insensitivity to dilution by little mineralized ground water or steam loss due to boiling of the rising fluids. Because of this, data points for deep and shallow waters, having undergone any amount of dilution or steam-loss, plot on the same position. ‘The presentation also allows the composition of average * crustal rocks from basalts to rhyolites to be shown. Water-rock interaction in geothermal systems with close volcanic-magmatic associations may be described in terms of two somewhat hypothetical, but well-defined endmember processes (Giggenbach, 1988): Initial dissolution of crustal rocks in acid Waters formed e.g. through absorption of magmatic vapors into deeply circulating groundwater. The waters formed in this *fluid-dominated" alteration process contain most of the more soluble rock constituents in + proportions close to those of the original rock. The rock phase resulting from this process is heavily depleted in the more easily leached components. a Final equilibrium of the fluid phase with "the rock" in its thermodynamically stable mineral configuration formed through recrystallization of the original, thermadynamically unstable primary rock. The chemical composition of this secondary, stable rock phase closely (~poroaches, or is the same (isochemical) as that of the original rock. This process is likely to ome to completion only in stagnant systems of infinite age. ‘The composition of the fluids in such “rock-dominated" alteration systems, however, is for a wide range of Al-silicate rocks uniquely fixed and essentially only a function of temperature and salinity (chloride content). ‘The compositions of waters, gases and rocks in actual, dynamic hydrothermal alteration systems can be expected to correspond to the attainment of some steady state, intermediate between these two erdmember processes. By comparing the compositions encountered in thermal fluid discharges with these theoretical compositions, however, it is possible to assess the relative importance of the two processes in shaping the composition of a given discharge and of other processes active at depth within a geothermal system. a The data points of the waters in Fig. 2 are generally far removed from the compositional area of crustal rocks, pointing to the existence of a number of secondary processes affecting , even these three "conservative" constituents during their rise to the surface. In a detailed study of the behaviour of rare alkali elements during hydrothermal alteration in New Zealand's geothermal systems, Goguel (1983) found that Rb closely paralleled K in that it is already taken up at quite high temperatures (>300°) in most K-containing alteration products, such as illite. Cs is incorporated into secondary zeolites, especially at temperatures <250°. Li is to minor (degrees incorporated into secondary quartz and chlorite. Comparison of fresh and altered (andesite and rhyolite in drillcores from these systems showed that the rare alkali metals have actually been added during rock alteration rather than leached, or in other words that they must have been dissolved from rock well below drilled depth. The only waters with compositions close to those of crustal rocks are the two highly 125,W.F. Giggenbach acidic waters from White Island (WI) and Aguas Calientes (RA), indicating rock dissolution. All neutral waters have obviously lost Rb due to uptake in illite, shifting data points away from the Rb corner. Li/Cs ratios, especially of well discharges, are still close to those of the original rock. The increase in Li/Cs for spring discharges suggests removal of Cs through incorporation into zeolites at lower temperatures. The relative position of data points and the delineation of trends, therefore, allows e.g. the assessment of the position of thermal water discharges with respect to upflow (low Li/Cs) and outflow (high Li/Cs), and of relative degrees of water-rock interaction at high temperatures or acidities. Li/Cs ratios are also a function of rock type, lower in acid rocks as compared to basalts (Taylor, 1964). Relative Cl, Li and B contents The alkali metal probably least affected by secondary processes is Li. It may, therefore, be used as a "tracer" for the initial deep rock dissolution process and as reference to evaluate the possible origin of the other two important "conservative" constituents of thermal waters, Cl and B. Fig. 3 shows their relative contents for the wide variety of thermal waters listed in Table 1. cl/i00 O welts © savings i s Bi o 3 Figure 3 Relative Cl, Li and B contents in thermal waters on weight basis. For symbols see Table 1. 126Chemical Techniques in Geothermal Exploration Of all these, only the very low chloride water, discharged at Fang, plots close to the composition of crustal rocks, suggesting that its composition may be due to simple rock leaching. Relative Cl and B contents for all others are much higher suggesting either addition of these two elements before, during or after the rock dissolution process, or loss of Li. The latter is quite unlikely as there is no obvious major sink for this element in hydrothermal systems. Once added, Li remains largely in solution. It is, however, striking that both Cl and Bare added to the Li containing solutions in proportions close to those in crustal rocks. At high temperatures Cl occurs largely as HCI, and B 2s HxBQs. Both are volatile and able to be mobilized by high temperature steam. They are, therefore, quite likely to have been introduced * . with the magmatic vapors invoked above to lead to the formation of the deep acid brine responsible for rock dissolution. At lower temperatures the acidity of HCI increases rapidly, and it is soon converted by the rock to less volatile NaCl; B remains in its volatile form to be carried in the vapor phase even at lower temperatures. The distribution of data points for most of the geothermal systems with close volcanic-magmatic associations, such as Wairakei (WK), Miravalles (MV) and Zunil (ZU) in Fig. 3 then may be explained in terms of dissolution of rock in waters formed through absorption of high temperature, high pressure magmatic vapors in deeply circulating groundwaters. These vapors may contain Cl and B in proportions close to those of the rock contacted. Data points close to the Cl comer either represent waters formed through absorption of, in this case, low B/C magmatic vapors, or waters affected by the admixture of low B/CI seawater (SW, MU, MO). Absorption of high B/C] steam, 200°) silica contents appear to be governed by equilibrium with quartz, at lower temperatures with its microcrystalline form, chalcedony. A relationship allowing for this gradual transition, and adequate in evaluating silica temperatures for spring discharges, is given by t, = (1000/(4.55 - logesioa)) - 273 (14) where cs is in mg/kg. The K-Mg-Ca-geoindicator The remaining major cation in geothermal waters to be considered is Ca. Through the formation of calcite it is linked to the most important component of the vapor phase, CO,. In addition to temperature-dependent reactions with Al-silicates, its concentrations in thermal waters can be expected to be affected by variations in the fugacity or partial pressure of CO,. The Teaction governing CO; pressures in a “full equilibrium” system corresponds according to Giggenbach (1988) to Ca-Al,-silicate + K-feldspar + CO, = K-mica + calcite (15) ‘The temperature dependence of this univariant reaction is given with adequate precision Poo in bar, t in °C) by logPcor = 9.0168t - 3.78 (16) 130WF. Giggenbach shem(®C)_, 200°, | 3008 Figure Evaluation of K-Ca-CO,-pressures and K-Mg-temperatures. Data points for the high temperature well discharges plot above the full equilibrium line and above the calcite formation field. Such behaviour implies that the CO, contents of the deep, rising waters are too low 300° may reflect the high temperatures encountered in the deep well NG-13. The system may, however, also have been affected by loss of Ar, through even minor vapor loss, followed by H, re-equilibration. This process would shift data-points to higher values, towards the "vapor equilibration" line. A similar upward shift should be observed for vapor-dominated systems where some of the equilibration can be assutied to have taken place in the vapor phase. In the case of boiling spring and fumarole discharges, values Of Ly, appear to be almost perfectly quenched, thus providing valid information on conditions within the deep equilibration liquid phase. Application of eqn (26) depends vitally on the availability of reliable and uncontaminated values for x,,.. It therefore cant be expected to give best results for samples which plot farthest from air in Fig. 6. Also, in the application of eqn (26) to lower temperature systems, it is essential that H, and He are analytically separated. In many such systems He contents may far exceed H, and, if analysed together, may give rise to too high values of ty. Ar and He are readily analyzed by the techniques given in Giggenbach and Goguel (1989). The good correspondence of theoretical and observed temperatures suggests that the highly simplified framework, used to derive eqn (26), provides an adequate and possibly a generally valid model of the actual processes occurring in hydrothermal systems. AS the reference gas, Ar may be used as the reference gas, it may be used to derive a variety of other geoindicators. Within this introduction only some aspects of reactions involving the varbon gases will be discussed in some detail. Reactions involving CO,, CH, and CO Assuming feo2,, the mol-ratio of CO, to H,0 inthe deep equilibrium liquid phase, to be given by eqn (19), it may again be combined with r,,. to give the CO,/Ar geothermometer ~N ™~ : Lex = logt cod Xn) , a 1og(Peoal PrzoBeost ac.) 0.0277t - 7.53 + 2048/(t+273) 71) 0W.F. Giggenbach ro. equiliorium vapor HA ca ri addition of equilibrium 4 vapor or loss oF ergon 3 2 1 oO a BS tye 70(2.54 Ly a) -2 uF log (4, Mae) o 700° 0c xe CC)" Figure7 Evaluation of H,-Ar-temperatures. Values of Ly are plotted at the measured temperatures for springs, at deep temperatures for wells. Because of the quantitatively much larger amounts of CO, involved in any re-equilibration process, as compared to Hy, this geothermometer can be expected to get "out of step" much more readily. As with the Na-K-Mg-geothermometer (Fig. 4), combination of * two reactions, attaining equilibrium with different velocities, may provide a technique allowing /-~an assessment to be made of the overall state of attainment of equilibrium, possibly useful in any attempt at further thermodynamic evaluation. In Fig. 8, values of Ly, (ean (25)) are plotted versus L,, (eqn (27)). Again a full -~equilibrium line is defined for equilibration of all gases dissolved in a single liquid phase. The horizontal line correspands to compositions expected for equilibration in the vapor phase; te lines describe intermediate conditions, the addition of equilibrium vapor (Giggenbach, 1980), or the loss of Ar prior to re-equilibration. Lack of adjustment of CO, contents to lower 138Chemical Techniques in Geothermal Exploration temperature conditions, with Hy remaining in equilibrium, is indicated by a shift of data-points downwards. 4 H)/Ar-temp. -2 e&®@ Figure 8 Evaluation of H,-Ar, CO,-Ar equilibration conditions. Comparison with data reported in Table 2 shows that most high-temperature spring ane fumarole discharges fall close to the theoretical liquid phase, full equilibrium line. As discussed ~, above, the position of the Ngawha samples points to admixture of equilibrium vapor or loss 0. Ar. Data-points well below the full equilibrium line represent obviously “immature” vapors, _ far from overall equilibrium. For these, two temperatures may be read off Fig. 8: a Hy-A temperature, generally quite close to actually measured discharge temperatures, and a CO Ar 139W.F. Giggenbach temperature, possibly representing conditions in some deeper environment. The lack of ‘~tainment of full equilibrium for these vapors is likely to be due to their limited contact with peck, either because of a too rapid transition from the deep high-temperature zones to much ier shallow conditions or highly restricted porosities preventing access of the rising waters to fresh rock surfaces. An ubiquitous constituent of thermal vapors is CH,. Its use in geothermometers is controversial (Anérsson and Gunnlaugssson, 1985; Taran, 1986). It is obviously one of the slowest species (Giggenbach, 1987) to equilibrate. As such, it has the potential to form the basis for a very "deep" geothermometer, remembering well conditions long forgotten by the other, faster" constituents. In the derivation of any such geothermometer it is obvious that it should not b¢ combined with any such fast species lest the information carried by it be swamped or mutilated by the noise generated by any ill-chosen partner. In this case, CH, is best used in combination with another slow or non-reactive species such as Ar. Such a CH/Ar geothermometer is readily devised using the procedures outlined above. Because of the unique way in which CH, is linked to the other carbon species CO, ard CO, an approach involving all three is chosen here. In order to allow a species by species assessment of the effects of actual or potential secondary processes, special care is taken not to jump the three carbon species together into complex, multi-component equilibrium expressions. “~s technique chosen is based on a diagram already used earlier to evaluate reactions controlling tne composition of volcanic gases from White Island (Giggenbach, 1987) and consists of plotting IpetXeys/Xeoa) Versus log (Xco/Xcox) (Fig. 9)- Two major redox buffers are considered: that involving di- and tri-valent iron of the rock, marked (FeO)/(FeO, .) and that involving the coexistence of H,S and SO, of the magmatic vapor phase. The latter is likely to be active only in high temperature volcanic systems; its effects may, however, still be felt over the deeper high temperature parts of geathermal systems or in systems where the magmatic environment reaches shallow levels. For the rock buffer two curves are shown: one representing equilibration in the vapor phase, the other in the liquid pitase. Isotherms refer to attainment of equilibrium among all three species according to the reaction 3C0, + CH, = 4CO + 2H,0 (28) Where they cross a buffer line, these temperatures define equilibrium conditions also for this system, In the upper right-hand part of the diagram the isotherms refer to equilibration of tbgases in the vapor phase. On crossing the rock-buffer, vapor line, the short sections cu.wecting with the rock-buffer, liquid line describe the compositions of mixtures of liquid and vor equilibrated gases. Over the lower parts of the diagram, the isotherms correspond to the c..uposition of the three gases having equilibrated in a single liquid phase. Carbon monoxide is determined only rarely on geothermal vapor discharges, largely because of its very low concentrations in lower temperature (<280°) systems. The advent of specific and highly sensitive detectors for its analysis has led to the development of a number 140Chemical Techniques in Geothermat Exploration ™ } -8 7 -6 5-4 : logtreo/%eo,) ~ Figure 9 Evaluation of CH,, CO-CO, equilibration conditions. A of techniques exploiting the special properties of reactions involving CO, especially by Italian_ investigators (Bertrami er al., 1985; D'Amore ef al., 1987; Chiodini and Cini, 1989). I conjunction with CH, and CO, contents, data-points may be plotted in Fig. 9. Two examples representing Larderello, and 2 150° fumarole in the Campi Flegrei (CF) are shown, As 141W.F. Giggenbach expected, the Larderello vapors plot within the liquid-vapor coexistence field at temperatures somewhat higher than those measured at the wellhead pointing to equilibration at deeper, hotter Cyrels. The position of the point for the Campi Flegrei, below both rock-buffer lines, suggests equilibration under somewhat more oxidizing conditions possibly reflecting the effects of the presence of more oxidizing magmatic fluids at quite shallow levels, Fig. 9 actually allows the evaluation of six different apparent temperatures of “ equilibration depending on which environment or process is assumed to govern interaction . among the three gases. Assuming homogeneous equilibration of all three gases dissolved in a liquid phase, a temperature (1) of around 270° is indicated; if equilibrated in a vapor phase, the temperature (2) would be only about 220°. Assuming CO and CH, to have equilibrated independently, a CO-rock temperature (3) of 230° would be obtained if equilibrium was attained in a fiquid phase, only 145° (4) if equilibrated with rock in the vapor phase. A much higher temperature (5) would result if CO is assumed to have equilibrated deep within the system where redox conditions are still governed by the sulfur buffer. 7 Ina similar way, CH,/CO, ratios may be used to evaluate independent temperatures. For _ the Campi Flegrei (CF) only one temperature of around 420° is obwained, that for equilibrium ++ with the rock buffer. Because of values of B, approaching unity, liquid and vapor ratios at a Premperature >400° become identical. For most of the gases listed in Table 2, it is safe to assume equilibration with the rock in a single liquid phase and the rock-liquid line is likely to pply. Temperatures for most are >300°, probably reflecting the slow rates of methane ‘quilibration thus preserving deeper temperatures. They may be obtained from the simplified {lationship of the methane-carbon dioxide geothermometer tue = (4625/(10.4 + log(xcye/Xcoa))) - 273 (29) The values for the two low temperature formation waters, MU and MO, are with 140° and 86° quite reasonable and suggest that methane may eventually attain rock equilibrium, given enough time. Fig. 9 then allows a series of apparent equilibrium temperatures involving the three carbon gases to be evaluated without the need to make a prior, frequently quite arbitrary decision as to the actual circumstances of equilibration. * REFERENCES } Amérsson S. and Gunnlaugsson E. (1985) New gas geothermometers for geothermal ~ exploration - Calibration and application. Geochim. Cosmochim. Acta, 49, 1307-1325. prertrami R., Cioni R., Corazza E., D'Amore F, and Marini L. (1985) Carbon monoxide in geothermal gases. Reservoir temperature calculations at Larderello (Italy). Geothermal Res, Counc., Trans., 9, 299-303. cf Chiodini G. and Cioni R. 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(1987) Redox processes governing the chemistry of fumarolic gas discharges from White Island, New Zealand. Appl. Geochem., 2, 143-161. Giggenbach W.F. (1988) Geothermal solute equilibria. Derivation of Na-K-Mg-Ca-geoindicators. Geochim. Cosmochim. Acta, 52, 2749-2765, Giggenbach W.F. and Goguel R.L. (1989) Collection and analysis of geothermal and volcanic water and gas samples, DSIR New Zealand, Report No. CD 2387, pp. 53. Goguel R.L. (1983) The rare alkalies in hydrothermal alteration at Wairakei and Broadlands geothermal fields, New Zealand. Geochim. Cosmochim. Acta, 47, 429-437. Henley R.W., Truesdell A.H. and Barton P.B. (1984) Fluid-mineral equilibria in hydrothermal systems. Reviews in Econ. Geol., 1, 267. Matsuo S., Suzuki M. and Mizutani Y. (1978) Nitrogen to argon ratio in volcanic gases. Adv. Earth Planet., Sci., 3, 17- 25. Piper A.M. (1944) A graphic procedure in the geochemical interpretation of water-analyses. Amer. Geophys. Union, Trans., 25, 914-923. Seward T.M. (1974) Equilibrium and oxidation potential in geothermal waters at Broadlands, New Zealand. Amer. J. Sci., 274, 190-192. Taylor S.R. (1964) Abundance of chemical elements in the continental) crust, a new table. Geochim. Cosmochim. Acta, 28, 1273-1285. Taran Y. (1986) Gas geothermometers for hydrothermal systems. Geochemistry Int., pp. 111-126. 143W.F. Giggenbach Truesdell A.H. and Fournier R.O. (1977) Procedure for estimating the temperature of hot water component in a mixed water using a plot of diséolved silica versus enthalpy. J. Res., (> US Geol. Survey 5, pp. 49-52. ~ oe