Geothermics, Vol. 20, No. 5/6, pp. 343--353, 1991.

Printed in Great Britain.

0375-6505/91 $3.00 + 0.00 Pergamon Press plc 1991 CNR.

SULFIDE

SCALE FORMATION CASE OF LEAD

AND CONTROL: SULFIDE

THE

N. ANDRITSOS and A. J. KARABELAS

Chemical Process Engineering Research Institute, and Department of Chemical Engineering, University of Thessaloniki, P.O. Box 1517, GR 540 06 Thessaloniki, Greece (Received March 1991; acceptedfor publication September 1991)
Abstract--The main characteristics of scale encountered in a typical high enthalpy/high salinity geothermal field (Milos island) are summarized. The results of scale sample analysis, coupled with the results of laboratory experiments with model fluids, point in the direction of design and operating conditions, which may significantly mitigate the scaling problems. Carefully controlled brine acidification appears to be a valid option, worth testing in the field. Encouraging results are also obtained in this study on the use of organic scale inhibitors. Their effectiveness, however, must be assessed under field conditions of high temperature and salinity.

INTRODUCTION The formation of scale on equipment surfaces exposed to geothermal fluids can have serious economic consequences, arising out of energy losses, increased cost of cleaning and maintenance, loss of production, or even abandoning a producing well. With intensified efforts to use geothermal resources for energy production and for other industrial applications, there is an increased interest in understanding the scaling process. An improved understanding may lead to measures for mitigating this problem. The great complexity of the scale formation process results from the large number of species found in a geothermal fluid and from the plethora of possible physical mechanisms involved. The latter may include mass, momentum and heat transfer, as well as chemical reactions at the equipment surfaces. Furthermore, the diversity of fluid composition from site to site and the variation of processes along the flow path make the generalization of both the mechanisms responsible for the scale formation and the preventive measures difficult. The composition of the scale in geothermal plants is commonly very complex and depends on many parameters, such as the temperature and pressure of the fluid, the history of water-rock interactions and the operating conditions. Low and moderate temperature brines (T < 150C) yield, as a rule, scale consisting of calcium carbonate (Owen and Michels, 1984; Corsi, 1986). There are a few exceptions to this rule, such as the geothermal wells in the Paris Basin, where relatively large concentrations of chloride and dissolved sulfide result in iron sulfide scale deposits (Criaud and Fouillac, 1989). High enthalpy and low salinity fluids usually form silica scale (e.g. certain wells in Iceland). On the other hand, high temperature liquids with high TDS content yield both siliceous and sulfide scale, with lead sulfide being one of the major constituents. A typical example of the latter case is the scale deposited in the Milos geothermal plant. Karabelas et al. (1989) present analyses of the brine and of several scale samples from this plant. The objective of the work presented here is twofold; i,e. to document the nature and the composition of the scale encountered in a fairly typical high salinity/high enthalpy field, such as the Milos geothermal field, and to understand the mechanism of scale formation through 343

344

N. Andritsos and A. J. Karabelas

Table 1. High enthalpy geothermal areas with sulfide scaling problems and scale characteristics

Geothermal area Salton Sea, California (1) Niland, Salton Sea, California (2) Asal Wells, Djibouti (3) Milos plant, Greece (4) Certain wells at Cerro Prieto, Mexico (5) Reykjanes, Iceland (6, 7) Krafla, Iceland (7) Dogger, France* (8)

TDS (g dm 3) 250 170-250 128 110 30-40 30 1 6-35

Pb (mg dm -3) 80 20-100 n.r. 2 n.r. n.r. ---

Fe (mg dm 3) 2000 200-1900 10 2(I n.r. i 0.02 0.1-3

S (mg dm -3) 15-30 10--30 ~2 2-4 n.r. 1 9 0.1-80

Sulfide crystalline phases Cu9S5, CusFeS4, Cu2S , FeS 2 PbS, ZnS, CuFeS 2, Cu2S PbS, ZnS, Ag2S PbS, Fe0.95S , ZnS FeS, FeS 2, PbS FeS, CuS, ZnS (3-4% Pb in scale) FeS, FeS2, CuFeS 2 Fe9Ss, FeS, FeS 2

* Low Enthalpy Area; n.r. not reported; (1) Skinner et al. (1967); (2) Austin et al. (1977); (3) as reported by Criaud and Fouillac (1989); (4) Karabelas et al. (1989); (5) Mercado et al. (1989); (6) Lfndal (1989); (7) Kristmannsd6ttir (1989); and (8) Criaud and Fouillac (1989).

laboratory experiments. In this paper, sulfide scale formation in high enthalpy geothermal plants is reviewed first. A discussion follows on the mechanism of lead sulfide deposition in pipes, elucidated by conducting once-through experiments in a 13 mm i.d. pipeline under corrtrolled conditions, which resemble those prevailing in a geothermal plant. The experimental findings serve as the basis for commenting on certain methods of mitigating the sulfide scaling problem and for assessing the most important one, i.e. the pH modification of the brine. Finally, some results are reported on the use of our experimental set-up for testing potential inhibitors of sulfide scaling. SULFIDE DEPOSITION IN GEOTHERMAL PLANTS Regarding the mechanism of sulfide scale formation, two opposing phenomena take place as the brine flashes (Owen and Michels, 1984). For mildly acidic fluids, such as that of Milos, most of the sulfide species enter the vapor phase in the form of H2S, causing a desirable decrease of those species in the residual brine. However, the pH rise due to the simultaneous release of carbon dioxide and the hydrolysis of carbonate ions favors the precipitation of heavy metals as sulfides. The heavy metals at the high temperatures of the brines are mainly transported as chloride complexes. Additionally, the precipitation of metal sulfides is promoted by two other factors, i.e. the temperature decrease, since the solubility of most sulfides significantly increases with temperature, and the "enrichment" of the residual brine in heavy metals because of steam separation. As an example, in the case of Milos plant the solubility of galena in the residual brine is estimated to decrease approximately 50 times, by using Helgeson's (1969) data or 600 times by following Seward (1984). These estimates are based on the assumptions that after flashing 50% of the fluid is separated as steam and that the pH of the residual brine increases by one unit, whereas the temperature declines by 20C. Table 1 presents the major crystalline sulfide phases identified in certain geothermal fields, along with the concentration of lead, iron and sulfide ions in the respective brines. The low enthalpy field of Dogger, France, with severe iron sulfide scaling, is also included. However, in the latter case the origin of the scale forming ions is distinctly different from that in high enthalpy/high salinity fields. The corrosion of mild steel casing due to high chloride content is considered responsible for the large concentration of iron in the fluid, while the sulfide ions are possibly products of bacterial reduction of sulfates (Criaud and Fouillac, 1989).

Sulfide Scale Formation and Control

Table 2. Characteristics and analysis of scale samples from the Milos geothermal plant Sample A Location Flashing valve Sample B Pipe between hot water collecting tank and reinjection pumps 6--8 mm fl-ZnS, a-ZnS, PbS, Fe0.95S 0.8 0.3 0.2 0.1 0.6 3.7 30.0 13.5 0.6 0.0 0.0 6.4 1.2 0.3 Sample C Pipe section - 3 0 m downstream from reinjection pumps 4-6 mm Feo.95S, a-ZnS, fl-ZnS, PbS 1.1 0.4 0.2 0.1 0.5 3.0 39.6 7.8 0.3 0.0 0.0 4.6 2.2 1.0 Sample D

345

Pipe section -100 m downstream from reinjection pumps 2-3 mm Fe0.95S, a-ZnS, fl-ZnS, PbS 2.3 0.6 0.3 0.1 0.8 3.0 27.1 13.0 0.1 0.0 0.0 7.2 3.6 0.5

Thickness Crystalline phases Element Na K Mg Ca Mn

Pb

-PbS, Fe0.95S

Composition(wt%) 0.3 0.1 0.1 0.1 0.1 40.7 15.4 0.8 0.3 0.1 0.5 2.9 0.5 0.3

Fe Zn Cu Ni Ag Si C1 SO~-

Despite the low concentration of heavy metals (particularly of lead) and the limited availability of sulfide species in the Milos brine (as well as in other brines), a significant amount of sulfides is deposited. Sulfide deposition is most pronounced close to the flashing valve and occurs at lower rates further along the flow path. In particular, PbS comprises almost 60% of the scale at the flashing valve, becoming much less abundant further downstream. The same trend was also observed at Salton Sea (Austin et al., 1977); PbS was by far the main sulfide deposited just downstream of the first stage control valve, while at the third and fourth stage only traces of PbS could be detected. Table 2 presents characteristics and analyses of a representative part of scale samples from various positions in the Milos geothermal plant. A schematic illustration of this plant and some scale analyses from the initial operation of the plant can be found in Karabelas et al. (1989). Atomic absorption and induced coupled plasma spectroscopy were employed for the analysis of anions, while chlorides were determined by titration with silver nitrate and sulfates by liquid chromatography. The color, hardness, thickness and composition of the deposits vary considerably in the various locations of the Milos plant. The scale samples correspond to plant operation with primary flashing at 24 bar, thus suppressing silica supersaturation and formation of silica deposits, Certainly, several interruptions occurred during the 11-month period of plant operation, resulting in bands of deposits, displayed by all samples with the exception of sample A. An interesting feature of some deposits is the presence of a silica-rich initial thin layer, between the pipe metal and the main sulfide band, as concluded by X-ray microanalysis and SEM observations. It is quite possible that the sulfides do not deposit directly onto the pipe wall and that a silica substrate facilitates their deposition, as first suggested by Austin et al. (1977). Furthermore, the solubility of the heavy metal sulfides (and to a lesser extent the kinetics of precipitation of each sulfide) possibly determines the sequence of their deposition. It is, indeed, observed that galena (PbS) is the first out of three major sulfides to precipitate near the flashing point, as one would expect on the basis of their solubility.

346
0.20

N. Andritsos and A. J. Karabelas

13 C=26.0 1 C=3.5
O

0.15 [] []

=_.
0,10
ee
m e.o

cO

Q.

0,05

/
o
0 1

[] []

\
2 3 4 5

pH
Fig. ]. PbS deposition rate as a function of pH and concentration (PbS concentration, C, in mg dm ~)

LEAD SULFIDE DEPOSITION IN THE LABORATORY The influence of various parameters on lead sulfide deposition in pipes was studied under controlled conditions, in order to elucidate the mechanism of sulfide scaling in geothermal plants (Andritsos and Karabelas, 1991a,b). In brief, solutions of lead and sulfide ions at a fixed pH were mixed to form a solution supersaturated in PbS, which flowed in a 13 mm i.d. pipeline with two test sections. Initial deposition rates were obtained by weighing the mass of PbS deposited on special stainless steel or teflon coupons. The effect of pH, PbS concentration, temperature and liquid salinity on the deposition rate and the deposit morphology were investigated. Additional experiments on deposit removal were carried out recently. The main points of that work, which are relevant to this discussion, are summarized as follows: (a) Appreciable lead sulfide deposition occurs in a narrow pH range, associated with the solubility of lead sulfide. The deposition curve exhibits a bell shape (as illustrated in Fig. 1 for two lead sulfide concentrations), with the maximum at the so-called "threshold pH"; i.e. the pH for spontaneous nucleation in the bulk. The threshold pH can be easily determined from light absorbance measurements. Above that range, bulk precipitation occurs immediately upon mixing of the reagent solutions and only some loose PbS flocs can be seen on the pipe walls. These flocs consist of numerous tiny PbS crystals (dp < 100 nm). (b) The diffusion of lead and sulfide ions onto the pipe surface appears to be the controlling mechanism of sulfide deposition, for the conditions investigated (Re = 3000-12,000, T = 2050C). At high temperatures, though, it is quite possible that surface reaction may also play a role, because of the high diffusivity values. (c) Detachment of the deposited particles (particle erosion) does occur, but the rate is generally small, as has been demonstrated by independent experiments. Dissolution of the deposited particles is also observed for pH values lower than 3, where the solubility of lead sulfide is not negligible. The fraction removed by erosion does not seem to depend on the flow rate in the range of Reynolds numbers between 6000 and 12,000. On the other hand, the nature of the deposits (single particles, aggregates) appears to influence markedly the detachment rate. (d) The morphology of the deposits is influenced by liquid salinity and, to a lesser extent, by temperature. Larger particles are formed at relatively low supersaturation ratios and in the pipe section next to the entry point. It is interesting to recall here that the same trend is observed in

Sulfide Scale Formation and Control

347

the PbS crystals found in the Milos scale samples. The largest particles (>10/~m) are encountered in the sample from the flashing valve. PbS particles from zero-salinity liquids have a cubic shape, while octahedron or truncated octahedron-shaped crystals are obtained from saline liquids. Another characteristic of the deposited crystal from saline liquids is that they "fuse" with each other as the deposition progresses, resulting in a strong adherence to the substrate. The micrographs of Fig. 2 depict the similarity of shapes between PbS particles deposited in the lab from saline liquids and those in scale samples. PREVENTION AND CONTROL OF SULFIDE SCALE FORMATION Total prevention of sulfide scale formation seems almost impossible at present. However, certain convenient measures may suppress the amount of scale forming in geothermal plants. The main approaches in this direction are the chemical modification of the brine (e.g. pH reduction), the careful design of the plant, the selection of appropriate operating conditions, and the use of additives (mainly crystal growth inhibitors). The least preferable approach to control scale formation is the removal of scale by chemical or mechanical means during periodic plant interruptions, unless this cleaning is carried out on a limited scale during regular plant maintenance. Some typical measures to be taken in the selection of design and operating conditions, are outlined below: It was clearly demonstrated in the Milos plant that the careful adjustment of primary flashing pressure, at a sufficiently high level, drastically reduced scale formation by keeping solids saturation relatively low. This pressure adjustment was quite effective on silica deposition, but apparently did not influence sulfide scaling. Large pipe diameters may offer some advantages in reducing sulfide scaling, provided that a diffusion controlled mechanism is responsible for the sulfide crystallization onto the pipe walls, as has been indicated in the tests with PbS. The prevention of shut-downs and of operating condition changes may be of help in certain cases, by avoiding the formation of bands of deposits of different strength. Such deposits can sometimes be shattered and dislodged from the pipe walls, transferred by the flow, and finally accumulated and cemented at certain places, such as the elbows of vertical expansion risers. Finally, flashing in the wellbore should be avoided by maintaining higher pressure in the well. Reaming of the well is the most effective way to remove the deposits in the casing (Thomas and Gudmundsson, 1989), but it is rather difficult to remove scale from the slotted liner. Surface equipment plugged by scale can be cleaned easier and more economically than the wellbore. Understanding the mechanism of PbS deposition in pipelines may help assess the pH reduction technique, with special attention to the Milos plant. This method is further discussed below, along with a first attempt to evaluate chemical additives as potential sulfide scale inhibitors. p H Reduction The method of sulfide scale control by reducing the pH of a geothermal brine is based on the well known fact that the solubility of sulfides increases markedly in acidic solutions. In the range of pH values that are typical of high salinity and high enthalpy brines (pH < 6), a ten-fold increase of the sulfide solubility is obtained by reducing the pH by one unit. Provided that the deposition behavior of PbS from a real brine is similar to that from a synthetic one (Fig. 1), even a small reduction of pH may sometimes reduce drastically the amount of deposits. It is noteworthy that at pH values less than 5, the rates of nucleation and growth of silica particles decrease considerably (Macrides et al., 1980). Consequently, a reduction of pH will also have a

N. Andritsos and A. J. Karabelas

Zig. 2. Micrographs depicting PbS crystals in (a) scale sample A, (b) scale sample C and (c) experimental deposits wi saline water (0.2 M in NaCI).

Sulfide Scale Formation and Control

Table 3. Comparison between solubilities of heavy metal sulfides (from Helgeson, 1969) and the concentration of the corresponding heavy metals in the Milos brine (T = 230C, Salinity = 2 M NaC1) Concentration in brine (mg dm-3) 1.8 3.3 20.0 0.2 Solubility, mg dm-3 M 2+ pH = 4.3 pH = 5.3 7.3 39.0 17.5 0.2 0.75 4.10 1.80 2.00

349

Metal Pb Zn Fe Cu

beneficial effect on the formation of silica deposits. However, two negative factors must also be considered i.e. the possible corrosion of pipes at low pH values and the cost of acid. The method of brine acidification has been successfully applied in several cases. It has been shown in a number of experiments (Grens and Owen, 1977) that lowering the pH of the Salton Sea geothermal brine has been effective in reducing or eliminating the formation of sulfide and siliceous scale. Gallup (1989) reports that inhibition of iron-silicate scale is achieved by lowering the pH by only 0.1 to 0.3 units. Also, Harrar (1981) notices that the pH reduction in laboratory experiments inhibits the deposition of both silica and sulfides. However, for complete scale prevention the brine p H should be reduced to about 3, which tends to increase significantly the corrosion rate of steel. In another example, brine acidification reduced the rate of silica scale formation a hundred times (Rothbaum et al., 1979). Table 3 shows that the concentrations of certain scale forming heavy metal ions exceed the solubilities of the corresponding sulfides for the conditions of the Milos brine. These solubilities are calculated according to Helgeson (1969), for a fluid with a 2 M salinity at 230C and must be considered approximate. Thus, the reduction of brine pH by one unit (e.g. by injection of hydrochloric acid) may prevent scale formation, even if a mild supersaturation in certain sulfides still exists, as indicated in Table 3.

Crystal growth inhibitors and inhibitor evaluation

The inhibitors are moderately large molecules that are readily adsorbed on the growth-active sites of the crystal surfaces, thus blocking the growth process (Nancollas and Zawacki, 1984). The main families of chemicals used as inhibitors are organic phosphonates, polyacrylates, and maleic acid derivatives. Crystal growth inhibition is considered the cheapest and most efficient method of controlling carbonate scale formation in geothermal installations (Vetter and Campell, 1979). Scale control can sometimes be achieved by the injection of a commercial inhibitor in concentrations as low as 1 mg dm -3. Despite the success in preventing carbonate scaling, no inhibitor is known to efficiently suppress the formation of sulfide and silica scales from high enthalpy and high TDS brines (Harrar etal., 1980; Corsi, 1986). One reason for this is that organic inhibitors are in general unstable at temperatures higher than -180C. The main target of this part of the work is not to uncover the active groups of the inhibitor or how it affects crystal growth, but rather to demonstrate that the experimental system employed for the deposition studies can be effectively used to determine the efficiency of a potential additive. For a preliminary investigation a commercial product (Belchem 206 G of WaterChem) was tested for effectiveness in scale inhibition. This additive is a mixture of several chemicals including phosphonates and polycarboxylates. However, its exact identity was not revealed. Light absorbance measurements of a PbS sol can be used to determine the p H range of

350
1.2 1.0
0.8 0.6 R El 0

N. Andritsos and A. J. Karabelas

C=O C=1 C=5 C=25

'~'~ 0.4 0.2

o.oi

0.0

0.5

1.0

1.5

2.0

2.5

3.0

pH
Fig. 3. Effect of additive concentration on the absorbance of PbS sols. Additive concentration, C, in mg dm 3.

appreciable deposition and the pH of the maximum deposition rate, as pointed out in Andritsos and Karabelas (1991a). Consequently, the absorbance measurements of sols, in which the potential inhibitor is added at a certain concentration, comprise the initial stage of the experimental procedure, before carrying out laboratory or pilot plant experiments. Equimolar solutions of Pb 2+ and S2-, filtered through a 0.10/am membrane, were mixed under mild magnetic stirring in a beaker containing 100 cm 3 of distilled and filtered water at the appropriate pH and additive concentration. Immediately after mixing, a sample from the beaker was transferred into a spectrophotometric cuvette and its absorbance was monitored for 10 min. Figure 3 presents the initial absorbance curves as a function of pH for four additive concentrations at 25C. The PbS concentration in each sol was 26 mg dm -3, computed by assuming that a complete reaction takes place. For the zero additive concentration the distinct sharp rise of the absorbance curve at the threshold pH is well reproduced. However, with increasing additive concentration, the sharp rise gradually declines and the absorbances are markedly lower than those for the zero additive concentration. The higher the additive concentration, the lower the absorbance values. The temporal variation of the sol absorbance, for several fixed additive concentrations, is depicted in Fig. 4. The pH of these measurements is 1.45, at which bulk precipitation is observed almost instantaneously for the zero additive concentration sol. It is clearly evident in these measurements that the additive retards significantly the precipitation of lead sulfide. However, even for the highest additive concentration used, 25 mg dm-3, the precipitation is not completely inhibited. The absorbance curve for the 25 mg dm -3 additive concentration implies that deposition in the pipeline may not occur along a considerable initial pipe length. Each pipeline run to study the effectiveness of the additive lasted four hours. For all runs the pH was 1.45, the Reynolds number 6000, and the temperature 25C, except for the zero salinity run, where the temperature was 20C. The experimental procedure is described in Andritsos and Karabelas (1991a). The additive was dissolved under stirring in a 1.5 m 3 water tank. Figure 5 shows deposition curves for three additive concentrations, all other parameters being constant. In all cases with appreciable deposits, deposition is seen to be linear with time. However, a short induction period is observed with all non-zero additive concentrations, even for a concentration of i mg dm-3. The deposition rates at the two test sections are presented in

Sulfide Scale Formation and Control

1.0
! | | !

351

0.8

0.6 o
oo

[]

t,I-'=
0 0 0 0 0 0 C=0 0

0.4

o 0.2 o
0.0

o o o

13 C=1 C=5 o C=25

, , ,

4 6 Time (min)

10

Fig. 4. Temporal variation of sol absorbance with additive concentration at pH = 1.45. Additive concentration, C, in mg dm -3.

&6
=1

I i C= 0, T=20eC [] C= 6, T=25~C C=25, T=25C

o o

,d'

=.,

3
m o

J+./ -J
I"1 0 m1 . ,~ 2 Tinl~ (h) 3 * ~ 4 * 5

1.

Fig. 5. Effect of additive concentration on PbS deposition in the first test section. Additive concentration, C, in mg dm -3.

Fig. 6. The deposition rate is defined as the slope of the linear deposition curve, which may not pass through zero. The deposition rate for zero concentration is corrected for the temperature difference. Although some inhibition of deposit formation is detectable even for the 1 mg dm -3 concentration, appreciable inhibition takes place for concentrations above 12 mg dm -3. Microscopically, the additive causes a small decrease in the equivalent length of PbS crystals deposited on the metal substrate. Furthermore, a greater degree of aggregation is observed with increasing additive concentration. For concentrations above 20 mg dm -3 the deposits are only in the form of aggregates, something that can be observed even macroscopically. A character-

352

N. Andritsos and A . J. Karabelas

20

o
U

1st T.S.
2nd T.S.

\
~

8 10 I" o
IIC

,4

e ~
, , ,

10 15 20 Additive Conc. (rag dm "3)

25

30

Fig. 6. Effect

of additive concentration on the initial deposition rate of PbS in both test sections (PbS conc. = 26 mg dm-3, T = 20C, Re = 6000, pH = 1.45).

istic of the deposits for concentrations greater than 10 mg dm -3 is that they are not uniformly distributed on the substrate. The aforementioned laboratory experiments demonstrate that there is an additive that inhibits the formation of PbS deposits, when its concentration in the liquid roughly matches that of lead ions. These preliminary results are generally encouraging, although it is questionable whether this additive can function at the high t e m p e r a t u r e of the Milos brine (>200C). Additional work is obviously required to examine whether such additives can have a beneficial effect under field conditions. CONCLUDING REMARKS H e a v y metal sulfides comprise a significant part of scales forming in geothermal installations, especially in those handling high salinity brines. Sulfides are deposited in significant quantities downstream of the geothermal fluid flashing point, where a sudden supersaturation in certain minerals occurs. The deposition rate of sulfides tends to decrease with distance from that point. A p a r t from the acidification of the brine, no effective measures to mitigate silica and sulfide scaling problems have been reported in the literature. Acidification to reduce somewhat the p H of the Milos geothermal fluid seems to be a technically feasible method to control sulfide scaling. However, additional work is required to estimate the cost of treatment and in particular to assess the corrosion potential of the treated brine. The injection of crystal growth inhibitors has not so far yielded encouraging results in the field as a preventive measure and should be further investigated. A commercial inhibitor tested under laboratory conditions in the present study shows a significant inhibition capability at concentrations similar to those of the depositing species (PbS). However, no definite conclusion can be drawn on the effectiveness of this or other inhibitors, unless they are tested at high t e m p e r a t u r e and high salinity conditions such as those characterizing the Milos brine. Acknowledgements--This work has been supported by the Commissionof European Communities under contracts No. EN3G-0040-GR and No. JOUG-0005-C, and by the Greek Secretariat for Research and Technology.

Sulfide Scale Formation and Control

REFERENCES

353

Andritsos, N. and Karabelas, A. J. (1989) Laboratory studies of PbS scale formation in steel pipes. Geothermics 18, 17-24. Andritsos, N. and Karabelas, A. J. (1991a) Crystallization and deposit formation of lead sulfide from aqueous solutions. I. Deposition rates. J. Colloid Interface Sci. 145, 158-169. Andritsos, N. and Karabelas, A. J. (1991b) Crystallization and deposit formation of lead sulfide from aqueous solutions. II. Morphology of the deposits. J. Colloid Interface Sci. 145, 170-181. Austin, A. L., Lundberg, A. W., Owen, L. B. and Tardiff, G. E. (1977) The LLL Geothermal Status Report, January 1976-January 1977. Lawrence Livermore Laboratory, Livermore, CA, UCRL-50046-76. Corsi, R. (1986) Scaling and corrosion in geothermal equipment: problems and preventive measures. Geothermics 15, 839-856. Criaud, A. and Fouillac, C. (1989) Sulfide scaling in low enthalpy geothermal environment: a survey. Geothermics 18, 73-82. Gallup, D. L. (1989) Iron silicate scale formation and inhibition at the Salton Sea geothermal field. Geothermics 18, 97104. Grens, J. Z. and Owen, L. B. (1977) Field evaluation of scale control methods: acidification. Geotherm. Resour. Counc. Trans., 119-121. Harrar, J. E. (1981) Final Report of Brine Chemistry and Scaling at the Salton Sea geothermal field, 197%1979. Lawrence Livermore Laboratory, Livermore, CA, UCID-18917. Harrar, J. E., Locke, F. E., Otto, C. H., Lorensen, L. E., Frey, W. P. and Snell, E. O. (1980) On-line Tests of Organic Additives for the Inhibition of the Precipitation of Silica from Hypersaline Geothermal Brine. IV. Final Tests of Candidate Additives. Lawrence Livermore Laboratory, Livermore, CA, UCID-18536. Helgeson, H. G. (1969) Thermodynamics of hydrothermal systems at elevated temperatures and pressures. Am. J. Sci. 267, 72%804. Karabelas, A. J., Andritsos, N., Mouza, A., Mitrakas, M., Vrouzi, F. and Christanis, K. (1989) Characteristics of scales from the Milos Geothermal Plant. Geothermics 18, 169-174. Kristmannsd6ttir, H. (1989) Types of scaling occurring by geothermal utilization in Iceland. Geothermics 18,183-190. Lfndal, B. (1989) Solids deposition in view of geothermal applications in Reykjanes and Svartsengi, south western Iceland. Geothermics 18,207-216. Makrides, A. C., Turner, M. and Slaughter, J. (1980) Condensation of silica from supersaturated silicic acid solutions. J. Colloid Interface Sci. 73, 345-367. Mercado, S., Bermejo, F., Hurtado, R., Terrazas, B. and Hernandez, L. (1989) Scale incidence on production pipes of Cerro Prieto geothermal wells. Geothermics 18, 17-24. Nancollas, G. H. and Zawacki, S. J. (1984) Inhibitors of crystallization and dissolution. In Industrial Crystallization (edited by Jancic, S. J. and de Jong, E. J.), pp. 51-59. Elsevier, Amsterdam. Owen, L. B. and Michels, D. E. (1984) Geochemical Engineering Reference Manual. Dept. of Energy, Rep. No DOE/ SF/11520/T1. Rothbaum, H. P., Anderton, B. H., Harrison, R. F., Rohde, A. G. and Slattcr, A. (1979) Effect of silica polymerization and pH on geothermal scaling. Geothermics 8, 1-20. Seward, T. M. (1984) The formation of lead(II) chloride complexes to 300C: a spectrophotometric study. Geochim. Cosmochim. Acta 48,121-134. Skinner, B. J., White, D. E., Rose, H. J. and Mays, R. E. (1967) Sulfide associated with Salton Sea geothermal brine. Econ. Geol. 62, 316-330. Thomas, D. M. and Gudmundsson, J. S. (1989) Advances in the study of solids deposition in geothermal systems. Geothermics 18, 5-15. Vetter, O. J. and Campell, D. A. (1979) Carbonate scale control inhibition in Republic's East Mesa geothermal operations. Geotherm. Resour. Counc. Trans. 3, 757-760.