Geouids (2008) 8, 252262

doi: 10.1111/j.1468-8123.2008.00229.x

Effects of changes in reservoir thermodynamic conditions on 222Rn composition of discharged uids: study for two wells at Los Azufres geothermal eld (Mexico)
N1, V. M. ARELLANO1, E. PORTUGAL1 AND N. SEGOVIA2 R. M. BARRAGA ctricas, Gerencia de Geotermia, Cuernavaca, Mor., Mexico; 2Universidad Nacional Auto noma Instituto de Investigaciones Ele n, DF, Mexico xico, Instituto de Geof sica, Coyoaca de Me
1

ABSTRACT
Rn anomalies that occurred at the time of the 19 September 1985 M8.1 Michoacan, Mexico, earthquake in uids from two wells of Los Azufres, geothermal eld were studied considering (i) the changes in well-bottom thermodynamic conditions (pressure, enthalpy and steam water ratio) and (ii) the discharged mass ow rates. In the studied steam well the anomalously high 222Rn concentration (as compared with background data) was observed on 11 September and was due to an important compressive process, which formed two-phase uids at reservoir, where usually single steam occurred. This caused the increase in 222Rn, as it remained in the steam. The compressive process was partially induced by changes in the production conditions at wellhead (because a well test was being developed) when sampling, but it was also seismic-induced, as similar 222Rn anomalies were observed in other steam wells for which stable conditions at sampling were maintained. Another case is given for a two-phase well where anomalously low 222Rn values (compared to background data) were recorded in September October 1985. As stable conditions were maintained during sampling (19831986), 222Rn data were correlated to ?twb> the total mass ow rates produced by the well. Results suggested that the well produced two types of liquidsteam mixtures with a common end-member regarding the liquid, but implying two end-member uids with different 222Rn contents. The most 222Rn enriched end-member was regarded as the original reservoir steam while that with relatively lower 222Rn concentration was stated as likely constituted by a mixture of reservoir and reinjection uids. From the linear correlations, 222Rn contents for both end-members were estimated while the 222 Rn composition of the reservoir liquid feeding the studied well was estimated to be negligible compared to steam from the intersection of both curves. As one anomalously low 222Rn value was measured for a sample collected on the 12 September 1985, it seemed that a seismic-induced process increased the reservoir permeability just before the earthquake allowing the liquid to reach the production zones of some two-phase wells. This interpretation was supported by the behaviour of gas species (CO2 and N2) and dD in the two-phase well studied and injection mass ow rates in one probably-related reinjection well. Key words: geothermal reservoir uids, liquidsteam mixtures, conditions Received 14 March 2008; accepted 25 September 2008 n Reyes, Instituto de Investigaciones Ele ctricas, Gerencia de Geotermia, a Barraga Corresponding author: Rosa Mar Reforma 113, Col. Palmira, 62490, Cuernavaca, Mor., Mexico. Email: rmb@iie.org.mx. Tel: +52 (777) 3623811 ext. 7318. Fax: +52 (777) 3623804. Geouids (2008) 8, 252262
222 222

Rn, seismicity, wellbottom in thermodynamic

INTRODUCTION
Seismic events induce changes in the chemical and isotopic compositions of uids from springs and wells, which, in turn, reect changes in deep hydrological conditions
2008 The Authors Journal compilation 2008 Blackwell Publishing Ltd

promoted by the seismic-related compressive extensive stresses. The changes in deep hydrological conditions of geothermal systems can be either temporary or permanent and may include the admixture of uids from different sources to the exploited aquifer (Favara et al. 2001;

Effects of changes in reservoir thermodynamic conditions on Balderer et al. 2002; Caracausi et al. 2005; Cai et al. 2007). In many cases, there are changes in the thermodynamic properties of the reservoir uids, producing phase changes. When phase changes occur in the reservoir, volatile and non-volatile species are re-distributed between liquid and vapour giving different compositions for the uids sampled at the surface, compared with the ambient compositions. According to Semprini & Kruger (1984), temporal 222Rn variations in uids from geothermal wells are useful to trace phase changes in the reservoir. Signicant 222Rn anomalies were observed in uids from n state Mexico, geothermal eld the Los Azufres, Michoaca wells in September 1985, 1 week before the occurrence of n the earthquake (Ms = 8.1) with its epicentre at Michoaca Coast and related to the subduction of the Cocos Plate under the North American Plate. Such uid geochemical anomalies were documented and related to the earthquake together with 222Rn variations in the soil (Segovia et al. 1989; Santoyo et al. 1991). Pressure tests and other measurements were routinely performed in the wells, to assess the reservoir characteristics and estimate the potential energy resource. The 222Rn anomalies at Los Azufres geothermal uids occurred during the development stage of the eld. This provided an opportunity to study the behaviour of geochemical species under different conditions including induced changes in well-pressures. Thus, data gathered from well-tests helped to understand geochemical anomalies, as those related to seismicity, because most of them could occur as a consequence of pressure changes (Segovia et al. 1989; Santoyo et al. 1991; Walia et al. 2005).

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Rn composition of discharged uids 253

In 2005, a study was carried out to investigate the thermodynamic conditions of Los Azufres uids at bottomhole conditions by using historical production data gathered by Comision Federal de Electricidad (Arellano et al. 2005). The objective of the present study was to correlate 222 Rn data of two wells of Los Azufres geothermal eld to variations in well-bottom conditions (enthalpy, pressure and steam water ratio) and ow parameters to better understand the 222Rn behaviour observed in September 1985.

THE LOS AZUFRES GEOTHERMAL FIELD

The Los Azufres geothermal eld is an intensely fractured, two-phase, volcanic hydrothermal system located in the northern portion of the Mexican Volcanic Axis, in the state n at an average elevation of 2800 masl of Michoaca (Fig. 1). Currently, it is the second biggest geothermal rrez-Negeld in the country, generating 188 MWe (Gutie n 2007). The geothermal eld consists of two wellr dened areas of production, Maritaro in the north and Tejamaniles in the south, separated by a distance of several kilometres. No surface manifestations occur within the intervening area (Arellano et al. 2005). Arellano et al. (2005) reported that, in its natural state, the Los Azufres geothermal eld consists of a deep aquifer where the ascending uid starts boiling at approximately 1200 masl. The two-phase liquid-dominant region extends upwards from 1200 masl to approximately 1700 masl where steam becomes the dominant phase. The two-phase steam-dominated region extends until approximately

Fig. 1. Location of the Los Azufres geothermal eld. Sketch of the studied and injection wells together with several faults from North and South zones are indicated. AZ- was removed from the name of the wells.

2008 The Authors Journal compilation 2008 Blackwell Publishing Ltd, Geouids, 8, 252262

 N et al. 254 R. M. BARRAGA 2400 masl where a region of dry or superheated steam is located. A geochemical model for the Los Azufres reservoir was proposed by Nieva et al. (1987). This model was based on the spatial distribution of chemical and isotopic species at reservoir conditions. As the concentration of volatile species (CO2) was higher in shallower strata and concentrations of non-volatile species (e.g. chloride) increased with depth, the model established the occurrence of a convective process produced by reservoir steam separation with partial condensation, to explain the distributions of the chemical species. According to the geochemical model, this behaviour seems to be dominant in the south zone while, for the north, the presence of two different liquid phases (with slightly different oxygen isotopic compositions) was proposed. The separated water in the Los Azufres two-phase wells is sodium-chloride type with neutral pH at separating conditions. The deep reservoir uid contains up to 1600 ppm of chloride and the concentration of CO2 (in & molar) has been calculated between 0.3 and 8.3 (Nieva et al. 1987). The pH of uids in the reservoir is slightly acidic to n et al. neutral with values between 5.5 and 7.4 (Barraga 2005). Reservoir temperatures of more than 300C occur at the north zone, while slightly lower values, between 270 and 290C, have been estimated for the south (Nieva et al. 1987). The well-discharges from Los Azufres contain a relatively high content of non-condensable gases compared with other geothermal elds. Typically, the main constituent in dry gas is CO2 (average 94% by volume), with signicant H2S (average 2.5%) while H2, CH4, N2 and NH3 concentrations are low. 222 Rn data from few wells at Los Azufres were recorded during the stage of development of the eld (19831986; Santoyo et al. 1991).

METHODOLOGY AND DATA

Production characteristics of wells Production data are routinely gathered from wells under specic conditions at wellheads. Depending on the purposes of well-assessment, different tests can be performed, these include: production rates from wells, interference between wells, connectivity of wells, etc. Production characteristic curves, also called output curves, are routinely determined for most geothermal wells. These curves relate mass ow rate at the wellhead to the corresponding wellhead pressure and enthalpy (Iglesias et al. 1983). In order to perform such tests in wells, pressure at the wellhead is regulated by known diameter discharge orices. Thus, the enthalpy of uids produced at wellhead can be estimated and a characteristic curve for the well is obtained. Obviously, it is not recommended to sample uids for geochemical characterization from wells when pressure or other tests are being developed, due to the occurrence of transient conditions induced by tests that will affect the composition of uids. Table 1 provides production data of studied wells AZ-17 in the south zone and AZ-5 in the north zone,

Table 1

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Rn data, steam fractions at sampling, wellhead pressures, mass ow rates of steam and liquid and wellhead enthalpy of wells AZ-17 and AZ-5. y (steam fraction) 1 1 1 1 1 1 1 1 1 1 0.66 0.66 0.66 0.66 0.66 0.71 0.71 0.71 0.71 0.71 Wellhead pressure (bar) 21.1 19.3 19.2 18.3 19.5 20.5 25.4 39.4 18.3 20.4 28.8 28.3 25.5 29.4 29.5 25.3 24.0 50.3 24.6 22.9 Mass ow rate of steam (kg sec)1) 19.4 15.8 15.8 15.8 16.1 16.9 13.0 0 16.1 15.1 16.4 17.1 16.7 17.1 16.0 17.2 18.0 0 18.9 16.7 Mass ow rate of liquid (kg sec)1) 0 0 0 0 0 0 0 0 0 0 7.1 9.9 10.8 10.3 9.7 11.3 11.7 0 11.4 11.4 Wellhead enthalpy (kJ kg)1) 2755 2755 2753 2753 2754 2761 2662 2779 2781 2168.7 2033.0 1976.0 2022.5 1999.8 1980.3 1985.4 2017.7 1950.4

Well AZ-17

Date (dd mm yy) 26 08 1983 11 11 1983 28 03 1984 26 04 1984 06 06 1984 10 08 1984 11 09 1985 09 10 1985 27 02 1986 14 05 1986 27 01 1983 26 04 1983 08 09 1983 27 03 1984 26 04 1984 08 08 1984 12 09 1985 10 10 1985 25 02 1986 13 05 1986

Rn (Bq kg)1) 1924 1924 1517 1887 1480 1591 3145 1036 962 888 370 518 370 233.1 277.5 321.9 136.9 103.6 255.3 218.3

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AZ-5

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Effects of changes in reservoir thermodynamic conditions on for dates close to SeptemberOctober 1985 222Rn sampling, when major anomalies occurred. Time series for production data of the studied wells are given in Figs 2 and 3. Figure 2A shows the wellhead enthalpy, Fig. 2B the wellhead pressure and Fig. 2C the mass ow rates produced by the well AZ-17. Figure 3AC shows the same parameters for well AZ-5. In the gures, the nominal production orice diameters of the wells are also given. Enthalpy measurements The enthalpy measurements in geothermal wells are routinely performed by using the lip pressure method (Grant et al. 1982). This method consists of the separation of water and steam discharged by the well, at atmospheric pressure. The steamwater mixture (also called total discharge) is discharged through a pipe into a silencer to

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Rn composition of discharged uids 255

separate steam and water phases. The lip pressure is measured at the extreme end of the pipe using a liquid-lled gauge to damp out pressure uctuations. Water ow from the silencer is measured using a sharp-edged weir near the silencer outlet. The James formula that relates mass ow, discharge pipe area, enthalpy and lip pressure is applied: G Ht1:102 1680; Plip0:96 1

where Plip is the lip pressure in MPa, G is the mass ow per unit area in kg cm)2 sec and Ht is the enthalpy in kJ kg)1. Simulation of wells The thermodynamic well-bottom conditions of uids were obtained by using the WELFLO program (Goyal et al.

Fig. 2. Time series of: (A) wellhead and wellbottom enthalpies, (B) wellhead and well-bottom pressures, (C) mass ow rates of uids produced and (D) 222Rn composition of well AZ-17. Nominal orice diameter (NOD) in inches is also shown. The vertical line indicates the 19 September 1985 earthquake.

2008 The Authors Journal compilation 2008 Blackwell Publishing Ltd, Geouids, 8, 252262

 N et al. 256 R. M. BARRAGA

Fig. 3. Time series of (A) wellhead and well-bottom enthalpies, (B) wellhead and well-bottom pressures, (C) mass ow rates of uids produced and (D) 222Rn composition of well AZ-5. Nominal orice diameter (NOD) in inches is also shown. The vertical line indicates the 19 September 1985 earthquake.

1980), a simulator of heat and mass ows in geothermal wells using the history of production data as input. The results include: well-bottom pressure, enthalpy, temperature and steam water ratio. Well-bottom enthalpies and pressures from simulation for wells AZ-17 and AZ-5 are given in Figs 2A,B and 3A,B respectively. Gas equilibria In order to estimate reservoir temperatures and steam fractions from gas data of geothermal wells, the following n et al. 2005) on the basis of the method was used (Barraga equilibrium of the FischerTropch reaction at the reservoir: CH4 2H2 O 4H2 CO2 2

5 3 3 7 H2 FeS2 Fe2 O3 H2 O 3H2 S Fe3 O4 ; 4 2 4 4

assuming that equation (3) controls the composition of H2S in the uids. The chemical parameters, FT and HSH2, are dened in terms of the concentration of gas species involved for equilibrium of reactions (2) and (3) as follows:

FT 4 logH2 =H2 O logCO2 =H2 O logCH4 =H2 O 5 HSH2 3 logH2 S=H2 O logH2 =H2 O 4

4 5

togetherwith the combined pyritehematite mineral equilibrium reactions:

FT and HSH2 can also be stated in terms of theoretical equilibrium constants for the reactions (2) and (3),
2008 The Authors

Journal compilation 2008 Blackwell Publishing Ltd, Geouids, 8, 252262

Effects of changes in reservoir thermodynamic conditions on vapourliquid distribution coefcients of the chemical species involved as a function of temperature and vapour fraction at reservoir (Salonga et al. 2004). A theoretical grid diagram solved for selected values of temperatures (C) and vapour fractions (y) is usually generated as a reference to localize the FTHSH2 chemical parameters obtained from the measured gas composition. From the theoretical grid, values for temperature and vapour fraction of the sample can be obtained. Salonga et al. (2004) provided all the details of the method and also provided a blank theoretical FTHSH2 grid.
222

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Rn composition of discharged uids 257

given in Table 2. According to production data (Table 1), well AZ-17 was undergoing testing by changing production orices from 4 to 12 September, until it was closed on 13 September. 222Rn samples from well AZ-17 were collected on 11 September (production orice in the well of 3 in.) and October 10 (well closed, owing by a purge line). 222Rn samples for well AZ-5 were collected on 12 September when the well was under stable conditions (orice diameter of 4 in.) and 10 October when the well was closed (owing by a purge line). Figures 2D and 3D show the time series of 222Rn data for wells AZ-17 and AZ-5 respectively. Other data used Results from dD, N2 and CO2 already published (Nieva et al. 1987; Santoyo et al. 1991) were also used for the discussion of the results. Reinjection data for well AZ-15 were also used (Arellano et al. 2003, 2005).

Rn collection and data

Rn was sampled using evacuated stainless steel bottles equipped with two vacuum pressure valves at its ends. The procedure consists of connecting the bottle to the steam line of the geothermal well. The vapour was condensed by means of a double coil immersed in two waterice baths cooled to 4C. The 222Rn was cleaned up in a purication and extraction line operated at high vacuum conditions. The system has two silica traps and one activated carbon trap to remove water vapour and gases, such as CO2, H2S, NH3 and CH4, which are the major gas content in the vapour phase. The puried radon was transferred into a Lucas tube scintillation ask by means of a Toepler pump. The 222Rn concentration was measured by means of an alpha particle counting system. Calibration was performed with a 226Ra standard. The results are given in Bq kg)1 (Santoyo et al. 1991). 222 Rn data for wells AZ-17 (627-m deep producing from the upper steam layer of the reservoir) and AZ-5 (1493-m deep producing from the two-phase layer) are

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RESULTS AND DISCUSSION

Well AZ-17 September 1985 222Rn values increase before the 19 September 1985 earthquake in the steam well AZ-17. The increase observed was temporary, because the 222Rn values for October 1985 decreased to lower values compared with background 19831984 values. In order to understand this behaviour, well-bottom parameters for well AZ-17 were examined. From Fig. 4, a temperature of approximately 290C and a reservoir steam fraction of approximately 0.4 are revealed for September 1985 data for the well AZ-17. Figure 5
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Table 2 Production data of wells AZ-17 and AZ-5 for dates close to the SeptemberOctober 1985

Rn anomalies in uids. Mass ow rate of liquid (kg sec)1) 0 0 0 0 0 0 0 11.7 11.7 12.8 12.0 11.1 7.1 3.9 2.8 0 Wellhead enthalpy (kJ kg)1) 2661.8 2661.8 2661.8 2661.8 2661.8 2661.8 1988.9 1985.4 1920.8 1941.4 1947.9 2084.5 2286.9 2202.4

Well AZ-17 AZ-17 AZ-17 AZ-17 AZ-17 AZ-17 AZ-17 AZ-5 AZ-5 AZ-5 AZ-5 AZ-5 AZ-5 AZ-5 AZ-5 AZ-5

Date (dd mm yy) 04 09 1985 06 09 1985 07 09 1985 08 09 1985 10 09 1985 12 09 1985 13 09 1985 29 08 1985 14 09 1985 17 09 1985 17 09 1985 17 09 1985 17 09 1985 17 09 1985 18 09 1985 10 10 1985

Nominal orice diameter (in.) 9 7 6 4.5 3 2 0 4 4 10 6 5 4 3 2 0

Wellhead pressure (bar) 5.6 7.4 8.9 14.8 25.4 33.2 38.6 24.1 23.8 9.2 11.3 16.9 23.9 26.7 42.2 50.3

Mass ow rate of steam (kg sec)1) 19.8 19.2 18.3 17.4 13.0 7.9 0 18.1 18.0 26.6 26.0 24.3 20.8 19.1 11.1 0

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 N et al. 258 R. M. BARRAGA steam from steam tables. In the gure, the dates for the well AZ-17 data are also given. Arrows indicate the direction of the trends. This diagram is a useful way to illustrate the behaviour of the thermodynamic well-bottom parameters (pressure and enthalpy) obtained for September 1985 data in well AZ-17. Simulation results indicate the transient (induced by test and seismic-related) effects on thermodynamic deep well parameters, (pressure, enthalpy and steam water ratio) as discussed below. Production history data from well AZ-17 indicate that saturated steam occurs at the bottom of the well (Fig. 5, May and November 1985 data), where the well-bottom pressure and the enthalpy are located on the saturation curve. However, well-bottom data for 46 September 1985 indicate a small pressure decrease and enthalpy increase regarding the baseline points, this was due to the changes related to the test. These changes moved the location of well-bottom conditions to the superheated steam region. Subsequently, the point for 12 September 1985 shows a compressive process (pressure increase and enthalpy decrease) with the development of a liquid phase at the well-bottom. The 222Rn sample was taken on 11 September 1985, when this compressive process was dominant in the well. An average of 1720.5 Bq kg)1 for 222Rn was recorded for 19831984 data. The large increase in 222 Rn concentration (to 3145 Bq kg)1) found for September 1985 must have been due to the change in the wellbottom steam to water ratio, which occurred as a result of the compressive process. During this process, a phase change occurred in the reservoir, part of the steam became liquid but leaving 222Rn and other volatile species in the steam phase. The 222Rn content in the original steam, before it changed phase (y = 1), remained in a relatively minor fraction of steam (y $ 0.9) at the well-bottom. This could have caused the increase in 222Rn and other volatile species concentrations in the September 1985 sample compared to baseline values. Considering the compressive process suggested in Fig. 5, the temperature results from Fig. 4 suggest a higher temperature than that corresponding to the 12 September 1985 data of well AZ-17 on the pressure-enthalpy plot (Fig. 5), in which a temperature of 238C is estimated. The 290C reservoir temperature obtained from Fig. 4 for well AZ-17 was located at the corresponding isotherm in Fig. 5. The steam fraction of this particular point (X) was obtained through the intersection of the 290C isotherm and the line relaying data from May, September and November 1985. This value (0.65) for the steam fraction was used to estimate the 222Rn concentration of the reservoir (RES) before the liquid was formed, considering the negligible 222Rn concentration of the liquid (222RnRES = 222RnSTEAM y; Semprini & Kruger 1984) in order to explain the 222Rn anomalously high value found. Phase segregation and preferential ow of steam to the wellhead occurred as the steam fraction at the
2008 The Authors Journal compilation 2008 Blackwell Publishing Ltd, Geouids, 8, 252262

Fig. 4. Grid diagram of the FT versus HSH2 chemical parameters (Salonga et al. 2004). The ordinate of the gure corresponds to FT = 4 log(H2 H2O) + log (CO2 H2O) ) log(CH4 H2O) and the abscissa HSH2 = 3 log(H2S H2O) ) (5 4)log(H2 H2O) for 19841985 gas data of well AZ n et al. 2005). The star indicates the results for 11 September 17 (Barraga 1985.

Fig. 5. Well-bottom pressure versus well-bottom enthalpy for well AZ-17. The solid line corresponds to saturated water-steam data from steam tables. Isotherms (200C and 290C) are also indicated. x is the fraction of steam in the watersteam mixture, examples for x = 0, 0.2, 0.4, 0.6, 0.8 and 1 are given. The stars correspond to the evolution of the well in time. The cross (X) corresponds to the reservoir temperature under the compression process.

shows the well-bottom pressure versus the well-bottom enthalpy in a semi-log plot, where the solid curve corresponds to pressure-enthalpy data for saturated water and

Effects of changes in reservoir thermodynamic conditions on wellhead for this sample (11 09 1985) was 1 (Table 1). By doing this, a value for 222Rn of 2042.4 Bq kg)1 for well AZ-17 can be obtained, which compares well with values taken in 1983. The well was sampled for 222Rn in October 1985, and the result was 1036 Bq kg)1, which was lower than the 19831984 data. According to production data, at this date, the well was closed and was sampled through a purge line. Two 222Rn measurements in well AZ-17 taken in 1986 showed even lower values than that recorded in October 1985, which suggests that the well received a relatively 222Rn depleted uid, which could be a mixture of the 222Rn enriched reservoir uid and 222Rn depleted returned from reinjection. The interpretation given for the 222Rn increase in well AZ-17 can be used to help understand similar behaviour in other steam wells, including those in which no tests were performed. Although a careful study of every case should be analysed, it can be stated that the compressive stresses that produced the phase change at the bottom of the wells were seismically induced, as they occurred just before the September 1985 earthquake. Two-phase well AZ-5 In the two-phase well AZ-5, a decrease in total discharge 222 Rn was found in September 1985 relative to measurements in 19831984 (average of 347.8 Bq kg)1). An anomalously low value of 129.5 Bq kg)1 for 222Rn was found in 12 September 1985 while the lowest 222Rn value of 103.6 Bq kg)1 was recorded in 10 October 1985. As stable conditions were maintained in this well, 222Rn data collected over time were correlated to the mass ow rates discharged (Table 1). The anomalously low 222Rn value obtained in September 1985 occurred when the maximum total mass ow rate (29.64 kg sec)1) of uid was discharged by the well. Figure 6 shows the 222Rn content of discharged uids versus the mass ow rates produced by the well. The locations of the points in the gure suggest two linear, end-member trends of behaviour (A and B in Fig. 6) with different slopes but with convergence at a point with a negligible 222Rn content, which was considered to be the reservoir parent uid (liquid) feeding well AZ-5. The linear trends observed in Fig. 6 imply composite steamliquid mixtures produced by the well that can be related to different production zones of the well, as there is evidence that this well is fed by more than one production stratum (Nieva & Quijano 1991). Thus there are two different 222Rn-enriched end-members. The 222Rn content of the two different end-member uids occurring at reservoir and feeding well AZ-5 were estimated by extrapolating the mass ow rates versus 222Rn linear ts at the origin ordinates (to mass ow rate = 0) from trends A and B of Fig. 6. Extrapolation to the origin on the x-axis assumes that the linear 222Rn versus mass ow rate trend will be
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Rn composition of discharged uids 259

Fig. 6. 222Rn composition versus total mass ow rates produced by the well AZ-5. The dates are given as dd mm yy. The star indicates the hypothetical composition of the reservoir liquid entering well AZ-5 while the lines A and B are the linear ts of the data points, as explained in the text.

followed for all total mass ow rates in the well but no data are available to verify this. However, an attempt was made to obtain the 222Rn values for both end-members, which, despite uncertainties, are useful to approximately characterize the reservoir uids and then try to use more effectively 222Rn data to identify sources of uids and ow patterns in production wells (Gerardo-Abaya et al. 2000). The values were 1207 14 Bq kg)1 and 2283 280 Bq kg)1 for A and B end-member steam phases respectively. The large uncertainty obtained for the B endmember is due to data dispersion from the linear t in which a correlation coefcient of 0.88 was found. For comparison, the correlation coefcient for the linear t of curve A was 0.99. The 222Rn concentration of the uid type B can be taken to be the representative of the reservoir steam at Los Azufres. For reference, the 222Rn concentration for the steam well AZ-6 (9 September 1983) was 2405 Bq kg)1 (Santoyo et al. 1991), which is slightly higher than the value obtained for the t but is within the uncertainty interval. The type A end-member uid has a relatively low 222Rn concentration (1207 14 Bq kg)1), which suggests a two-phase uid that was probably produced by a mixture of reinjection and reservoir uids. A 222 Rn composition of well AZ-16AD (26 April 1984), which is known to produce a mixture of reservoir and rein n et al. 2005), was 925 Bq kg)1 jection uids (Barraga (Santoyo et al. 1991). This value compares reasonably favourably with the results given for the A end-member. Reinjection of produced uid in well AZ-15 (located in the northern zone, Fig. 1) started in 1982 (Fig. 7), but

 N et al. 260 R. M. BARRAGA corresponding to February (trend B in Fig. 6) is isotopically more depleted than the point corresponding to May (trend A in Fig. 6). The isotopic enrichment of the sample taken in May 1986 is probably due to the presence of reinjection returns, which are isotopically enriched regarding dD, due to an evaporation processes at surface conditions, before injection. At the same time, dD at well AZ-5, corresponding to September 1985, represents the most isotopically depleted point ()65.8 &), indicating a value close to the reservoir liquid composition that was reported to be )64.6 & 1.8 (Nieva & Quijano 1991). In order to reinforce these conclusions, in Fig. 8, the behaviours of N2 in steam and CO2 in total discharge and in the reservoir liquid for well AZ-5 for 1985 and 1986 are presented. The minimum N2 concentration occurred in September 1985 showing that reinjection returns were negligible at such time, as the reinjection uid contains air (rich in N2) and water. The maximum N2 concentration is found for May 1986, which lies on curve A that corresponds to a mixture of reservoir and reinjection uids on Fig. 6 evidencing a close relationship with reinjection uids; nevertheless, the sample from February 1986 that lies on curve B, which is related to reservoir uids (Fig. 6), shows a lower amount of N2 in Fig. 8 (no relationship with reinjection). In contrast, the maximum CO2 in reservoir liquid also occurred in September 1985. The same pattern for CO2 in total discharge has been observed, reinforcing the presence of the anomaly that was discussed previously by Santoyo et al. (1991). These observations show that uids from curve type A could be the result of a mixture of reservoir and reinjection uids and that reinjection returns have probably fed through to production wells in the north zone effectively since reinjection started.

Fig. 7. Time series of the mass ow rates injected in well AZ-15 and dD composition of well AZ-5. The dates are given as dd mm yy.

there was no denitive proof of the presence of returns (reinjected liquid and vapour) in the uids discharged by the north zone wells. When comparing A and B 222Rn trends in well AZ-5 (Fig. 6) with the reinjection history in well AZ-15 (Fig. 7), most of the A trend data correspond to maximum reinjection rates. In a complex system such as the geothermal production eld, it is difcult to precisely determine the cause of geochemical and phase variations; however, it is very likely that the trends A and B can be inferred as stated. As mentioned, the presence of two uids with slightly different isotopic composition occurring at the north zone was proposed as part of the reservoir geochemical model (Nieva et al. 1987). The presence of returns in well AZ-5 and other north zone wells was found by Arellano et al. (2003, 2005) by the analysis of production data and was conrmed recently by a tracer test (Iglesias et al. 2006). Thus, the results obtained in this work using 222Rn data could conrm that reinjection uids arrived at production zones of wells in the north zone, more or less since reinjection started. After the anomalously low values found for September and October 1985, total discharge 222Rn concentrations in well AZ-5 (two values taken in 1986) showed a decreasing tendency, to an average value of 237 Bq kg)1 but no more 222 Rn data were collected. In Fig. 6, the point corresponding to February 1986 ts the trend B while the point corresponding to May 1986 ts the trend A. This pattern indicates that the reinjected uids reached the production zone of the well in a sporadic fashion, such as reported for wells in the south zone (Arellano et al. 2003), depending on reinjection mass ow rates. To illustrate this phenomena, the ow rates of material injected into well AZ-15 versus dD at well AZ-5 were plotted in Fig. 7. The point

Fig. 8. CO2 in total discharge and in reservoir liquid and N2 in steam for 1985 and 1986 in well AZ-5. The dates are given as dd mm yy.

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Effects of changes in reservoir thermodynamic conditions on The 222Rn results obtained for well AZ-5 suggest that shortly before the 19 September 1985 earthquake, seismicity increased the reservoir permeability creating new paths allowing the reservoir liquid to reach the production zone of some two-phase wells. Other geochemical studies developed in the seismic areas have shown that the geochemistry of uids reect the faulting behaviour and have been closely related to tectonic, geological and hydrological settings (Favara et al. 2001; Balderer et al. 2002; Caracausi et al. 2005).

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Rn composition of discharged uids 261

CONCLUSIONS
A comprehensive interpretations of the 222Rn anomalies observed in uids from two wells of the Los Azufres geothermal eld, precursors of the (Ms = 8.1) 19 September 1985, earthquake was provided. The results indicate that transient variation in well-bottom pressure and commensurate phase changes occurred in some wells during SeptemberOctober 1985, when signicant 222Rn anomalies were seen. At least in one of the steam wells that showed an anomalously high 222Rn content, a production test was being undertaken, to study the variations in the mass ow rates produced for different wellhead pressures. This new evidence suggests that the variations in well-bottom conditions were, in part, induced by the test in which changes in the diameter of the production orice occurred but were also seismically related. In contrast, in a two-phase well, under stable production conditions, anomalously low 222Rn content observed in September 1985 was correlated with the mass ow rates produced, giving information on the ow regimes of the well and an approximate composition of reservoir uids (liquid and steam). The approach used revealed the dominant processes that occurred at the Los Azufres reservoir previous to the September 1985 earthquake. It is recommended that 222Rn and geochemical data together with production data are analysed for all wells.

ACKNOWLEDGEMENTS
Authors acknowledge Prof. T. F. Yang and two anonymous reviewers for useful comments and suggestions that helped to improve this work. Important discussions, comments and careful edition made by Editor Prof. Richard Worden are also acknowledged.

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