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Geothermics 37 (2008) 400–428

The Tianjin geothermal field (north-eastern China):

Water chemistry and possible reservoir
permeability reduction phenomena
Angelo Minissale a,∗ , Daniele Borrini b , Giordano Montegrossi a ,
Andrea Orlando a , Franco Tassi b , Orlando Vaselli a,b ,
Antonio Delgado Huertas c , Jincheng Yang d , Wanquing Cheng d ,
Dario Tedesco e,f , Robert Poreda g
a Institute of Geosciences and Earth Resources, National Research Council of Italy (CNR),
Via G. La Pira 4, 50121 Florence, Italy
b Department of Earth Sciences, University of Florence, Via G. La Pira 4, 50121 Florence, Italy
c Estación Experimental de Zaidı́n (CSIC), Prof. Albareda 1, 18008 Granada, Spain
d Aode Renewable Energy Research Institute, 90 Weijin South Road, Nankai District, 300381 Tianjin, China
e Department of Environmental Sciences, Second University of Naples, Via Vivaldi 43, Caserta 81100, Italy
f Institute of Environmental Geology and Geo Engineering (CNR), Piazzale A. Moro 5, Roma 00100, Italy
g Department of Earth & Environmental Sciences, University of Rochester,

227 Hutchison Hall, Rochester, NY 14627, USA

Received 3 January 2007; accepted 6 March 2008
Available online 25 April 2008

Abstract
Injection of spent (cooled) thermal fluids began in the Tianjin geothermal district, north-eastern China,
at the end of the 1990s. Well injectivities declined after 3–4 years because of self-sealing processes that
reduced reservoir permeability. The study focuses on the factors that may have caused the observed decrease
in permeability, using chemical and isotopic data on fluids (water and gas) and mineral phases collected
from production and injection wells. The results of data processing and interpretation indicate that (1) it
is very unlikely that calcite and silica precipitation is taking place in the reservoir; (2) the Fe- and Zn-rich
mineral phases (e.g. sulfides, hydroxides and silicates) show positive saturation indexes; (3) SEM and XRD
analyses of filtered material reveal that the latter mineral phases are common; (4) visual observation of
casings and surface installations, and of corrosion products, suggests that a poor quality steel was used in
their manufacture; (5) significant quantities of solids (e.g. quartz and feldspar crystals) are carried by the

∗ Corresponding author. Tel.: +39 055 2757521; fax: +39 055 290312.
E-mail address: minissa@igg.cnr.it (A. Minissale).

0375-6505/$30.00 © 2008 Elsevier Ltd. All rights reserved.

doi:10.1016/j.geothermics.2008.03.001
 A. Minissale et al. / Geothermics 37 (2008) 400–428 401

geothermal fluid; (6) seasonal changes in fluid composition lead to a reduction in casing corrosion during
the summer.
It was concluded that the decrease in injectivity in the Tianjin wells is caused only in part by the oxidation
of casings, downhole pumps, and surface installations, triggered by free oxygen in the injected fluids; the
utilization of better quality steels should drastically reduce this type of corrosion. Self-sealing of pores and
fractures by reservoir formation solids and by the Fe-corrosion products suspended in the injected fluids
seems to be a more important phenomenon, whose effect could be greatly reduced by installing filtering
devices at all sites.
© 2008 Elsevier Ltd. All rights reserved.

Keywords: Water chemistry; Stable isotopes; Reservoir permeability reduction; Self-sealing; Tianjin; China

1. Introduction

The Tianjin geothermal district in north-eastern China, which includes the Tanggu, Wuqing,
Zhouliangzhuang, and Shanlingzhi producing areas, has more than 200 geothermal wells, 10–15
of which are used as injectors. The temperature of the waters produced varies from about 30 ◦ C
up to boiling (Brandi et al., 1986; Zheng et al., 1990; Liao and Chen, 1993; Axelsson and Dong,
1998; Kun et al., 2000; Li, 2003). These waters have been utilized since the late 1960s, mainly
for space heating but also in some industrial and agricultural applications (Aquater, 1984). Before
the recent rapid industrialization of China, the cooled geothermal waters were being discharged
into rivers and streams, which led to environmental problems related to proliferative vegetation
growth, the formation of stagnant marshy areas, etc.
By the end of the 1990s, the increased demand for air-conditioning in the summer, especially
in urban areas such as Tianjin, had led to the combined use of deep and shallow wells in heat pump
systems based on a closed production and injection loop (Kun, 2003). These systems were chosen
with the objective of recharging the deeper parts of the geothermal system in the summer while
maintaining steady fluid production in the winter, at the same time limiting, wherever possible, the
decline in the local water table and lessening the impact of these operations on the environment.
An overall drop in the water table has indeed been observed in all coastal regions of China (in
some places more than 90 m), which has led to significant ground surface subsidence phenomena
(Hu et al., 2004).
The design adopted for the dual-purpose geothermal wells at Tianjin, i.e. wells that can be
utilized for both fluid production and injection, but at different times, still needs to be improved.
Pumping problems have been reported in wells used for long-term injection tests (Kun, 2003),
especially in the ones producing from tertiary sedimentary formations. Fluid injection problems
of this type can be caused by a reduction in reservoir permeability at or near well bottom, as
a result of sealing of pores and/or fractures by particles suspended in the thermal fluid and/or
of rock–fluid chemical reactions and consequent mineral precipitation (scaling). The aim of the
present study was to investigate which of these processes was causing the reduction in reservoir
permeability, and to suggest solutions to the problem.

2. Geological background

The Tianjin geothermal resource (Fig. 1a) extends over about 11,000 km2 and is located
in the southern part of the Hua-Bei Plain (NE China), this being a Meso-Cenozoic basi-
402 A. Minissale et al. / Geothermics 37 (2008) 400–428

Fig. 1. Tianjin geothermal field. Geology of the substratum below the Tertiary formations and location of sampled
production and reinjection wells. (a) Thermal gradient (in ◦ C/100 m); (b): depth (in m) of pre-Tertiary substratum.

nal area, filled up by continental Tertiary and Quaternary sediments (Zheng et al., 1990).
The geothermal area can be regarded as being located in a large tectonic depression affected
by subsidence since the Neogene, and subjected to frequent strong earthquakes (Ding
and Lu, 1983; Han et al., 2003). Thickness of the Tertiary–Quaternary sedimentary series
varies from less than 1000 m in the structural high located around the area of Tianjin city
(known as the Cangxian Uplift), to more than 3000–8000 m, E-SE and W-NW of Tianjin
(Fig. 1b).
The Tertiary formations lie unconformably above a highly folded and tectonized Precambrian
to Mesozoic substratum (Fig. 1a). They can be divided into: (i) the Guan-Tao (Lower Tertiary) and
(ii) the Ming-Hua-Zhen (Middle-Upper Tertiary) groups, both represented mainly by mudstones
and sandy mudstones. The substratum consists, from the bottom up, of: (i) mica schists, gneisses
and granites (Pre-Sinian Basement), (ii) dolomitic and limestone formations and subordinate
conglomerates (Sinian to Permian), (iii) continental sandstones and conglomerates (Mesozoic).
It outcrops in the Taihangshan Range to the W-NW of Tianjin and in the area of Qinhuangdao to
the NE of the area in Fig. 1.
As a result of the intense tectonic activity in the Mesozoic and Cenozoic, the structural setting
of the Hua-Bei Plain is dominated by two main fault systems. The first one is a SSW-NNE
 A. Minissale et al. / Geothermics 37 (2008) 400–428 403

oriented alignment forming a horst-graben structure, which is transversely cut by the other tectonic
lineament (Xu et al., 1985). The horst, where the city of Tianjin is located, exhibits the highest
measured geothermal gradients (Fig. 1a), and it is the place where most of the more productive
geothermal wells have been drilled inside the pre-Tertiary producing horizons. There are shallower
producing wells (300–600-m deep) at lower temperature (<70 ◦ C) in the Tertiary formations, as
well as very deep wells (up to 2600 m) in the same Tertiary formations in the structural lows, east
and west of Tianjin (Fig. 1b).
The regional hydrogeology, from the top to the bottom, can be summarized as follows (Aquater,
1984): (i) the “Quaternary Aquifer”, consisting of continental sediments, at the base of which
impervious deposits isolate the most superficial aquifer from the hydrothermal reservoir; (ii)
the “Tertiary Aquifer” with a thickness of 600–1000 m, part of a continental depositional series
whose permeability is dominated by primary porosity; (iii) the “Lower Paleozoic-Sinian Aquifer”,
located mainly in karstic limestone and Ordovician-Sinian dolostone, up to 6000-m thick, with
fracture-dominated secondary permeability.
From a classification point of view, the Tianjin geothermal system in the Lower Paleozoic-
Sinian Aquifer is a typical liquid-dominated convective system (Brandi et al., 1986), where the
structural high allows water convection up to the top of the permeable pre-Tertiary limestone-rich
formations.

3. Sampling campaigns and analytical methods

In order to understand the nature of the reservoir plugging problem, two field campaigns
were organized in January and February 2005 to sample the thermal waters in production and
injection wells. Based on the evaluation of the data obtained in winter, one more field campaign
was organized in July 2005. In this third field survey, selected wells were re-sampled to evaluate
seasonal effects on the chemical composition of the deep fluids. In total, fluids from 35 wells
were collected, 7 of which were sampled repeatedly in winter (January–February) and summer
(July).
For each sampling site, seven water aliquots and a dissolved gas sample, stored in pre-evacuated
gas vials, were collected for chemical and isotopic analysis. Filtered material (>0.45 ␮m) was also
collected from each well. Some physical and chemical parameters were stabilized for measurement
in the lab (free CO2 and S(II) , Montegrossi et al., 2001), or were determined in situ (pH, Eh,
temperature, HCO3 , NH4 , SiO2 ). Four dissolved gas samples were analyzed at the Department
of Earth and Environmental Sciences at the University of Rochester (USA) for the determination
of 3 He/4 He isotopic ratios.
Data for all wells, including geographical coordinates, field data and main components, are
summarized in Table 1. Minor and trace elements (determined by inductively coupled plasma
mass spectrometry; ICP-MS) are shown in Table 2. The composition of dissolved gases is given
in Table 3. The 3 He/4 He ratios, together with all isotopic ratios measured in well waters (D/H,
18 O/16 O, 87 Sr/86 Sr and 13 C/12 C in dissolved inorganic carbon, DIC) and related gas (13 C/12 C in

CO2 ) are reported in Table 4.

In order to verify the presence of primary and/or secondary minerals carried in suspension by
the fluid(s), all filtered samples were analyzed by scanning electron microprobe (SEM) and/or
X-ray diffractometry (XRD). Measured elements and/or re-calculated mineral phases after energy
dispersive system (EDS) analysis are summarized in Table 5.
The analytical results of the seven water and six dissolved gas samples collected in July 2005
are reported in the tables by adding “s” after the ordered code number.
 404
Table 1
Main characteristics of Tianjin water wells and water samples
Sample no. Well name Well type Date Well depth (m) Lithotype Latitude Longitude T (◦ C) pH Eh (mV) pco2 TDS HCO3
1 DKJ Production 25 January 2005 200 Quaternary 39 06 39 117 10 57 16 7.61 −29.7 −2.12 2318 421
2 SH (Sport Hotel) Injection 25 January 2005 300 Quaternary 39 04 33 117 10 27 13 7.65 −13.0 −2.21 1932 367
3 HHL03 Production 24 February 2005 300 Quaternary 39 08 23 117 11 10 18 7.26 −18.4 −1.66 852 461
4 DFZZ01 Production 26 February 2005 400 Quaternary 39 05 49 117 08 27 23 8.58 −80.6 −3.09 867 392
5 DFZZ01-R (DFZZ02) Injection 26 February 2005 400 Quaternary 39 05 49 117 08 27 12 8.54 −75.9 −3.07 883 391
6 AS01 Production 24 February 2005 640 Tertiary 39 08 14 117 11 20 34 8.48 −74.1 −2.87 793 424
7 AS01-R (AS02) Injection 24 February 2005 400 Quaternary 39 08 14 117 11 20 19 8.12 −52.2 −2.54 817 434
8 HHL01 Production 25 January 2005 900 Tertiary 39 08 36 117 11 06 36 8.36 −78.3 −2.57 835 572
9 HHL01-R (HHL02) Injection 25 January 2005 400 Quaternary 39 08 36 117 11 06 16 8.61 −87.6 −2.97 833 552
−67.3 −2.31

A. Minissale et al. / Geothermics 37 (2008) 400–428

10 NK15 (Zoo) Production 25 January 2005 1300 Tertiary 39 04 46 117 09 33 41 8.13 1192 576
11 WQ10 Production 26 January 2005 1400 Tertiary 39 22 30 117 01 53 53 8.57 −67.9 −2.70 904 557
12 JH Production 26 February 2005 1500 Tertiary 38 50 24 117 12 46 48 7.53 −21.6 −1.71 2158 533
13 DG24 Production 27 January 2005 1744 Tertiary 38 50 56 117 26 36 57 8.13 −44.9 −2.21 1954 600
14 Tg19 (Tanggu) Production 24 January 2005 2200 Tertiary 39 02 22 117 39 15 66 7.80 −48.0 −1.82 1721 574
14s Tg19 (Tanggu) Production 12 July 2005 2200 Tertiary 40 02 22 118 39 15 65 7.65 −271.0 −1.69 1636 537
15 WQ5 Production 26 January 2005 2600 Tertiary 39 24 19 117 01 47 83 7.95 −35.6 −1.78 1103 656
15s WQ5 Production 12 July 2005 2601 Tertiary 40 24 19 118 01 47 81 7.72 −248.0 −1.56 1097 631
16 DL25 (Bio Park) Production 24 January 2005 1300 Tertiary 39 05 01 117 25 30 81 6.81 17.3 −0.84 1707 421
16s DL25 (Bio Park) Production 12 July 2005 1301 Tertiary 40 05 01 118 25 30 68 6.61 −280.0 −0.63 1885 522
17 DL25R (Bio Park) Injection 01 March 2005 1300 Tertiary 39 04 49 117 25 27 53 7.42 −15.3 −2.00 1760 439
18 WANG 3 Production 27 February 2005 1077 Ordovician 39 33 32 117 20 37 43 7.75 −34.1 0.01 1003 412
19 DL16 Production 24 January 2005 1312 Ordovician 39 04 32 117 22 05 66 7.78 −4.9 0.03 1803 510
20 NK14 Production 27 January 2005 2130 Ordovician 39 06 27 117 08 50 63 7.40 4.7 0.08 4744 230
21 JN02 Production 25 February 2005 2500 Ordovician 38 59 35 117 22 23 46 7.37 −9.4 0.03 1943 521
22 DL11 Production 24 January 2005 1490 Cambrian 39 08 04 117 22 05 74 7.35 −18.8 0.03 1755 444
23 WANG-4 Production 27 February 2005 2072 Cambrian 39 32 55 117 20 37 74 6.85 22.2 −0.99 952 355
23s WANG-4 Production 12 July 2005 2072 Cambrian 40 32 55 118 20 37 70 6.61 −325.0 −0.77 972 351
24 HD09 Production 23 January 2005 3450 Precambrian 39 08 56 117 15 39 83 7.01 4.2 −1.02 1813 425
25 HD09-R (HD02) Injection 24 February 2005 2800 Precambrian 39 08 56 117 15 39 82 7.40 −12.9 −1.46 1767 400
26 HD12 Production 23 January 2005 3190 Precambrian 39 08 04 117 13 07 80 6.95 8.8 −0.97 1910 442
27 HD12-R (HD13) Injection 01 March 2005 3068 Precambrian 39 08 04 117 13 06 36 7.04 10.5 −1.41 1913 403
28 HD14 Production 01 March 2005 3150 Precambrian 39 07 42 117 14 06 87 7.30 −9.4 −1.35 1807 380
28s HD14 Production 13 July 2005 3150 Precambrian 40 07 42 118 14 06 78 6.89 −160.0 −0.96 1847 398
29 HD14R Injection 01 March 2005 2750 Precambrian 39 04 49 117 25 27 40 6.86 15.2 −1.19 1834 412
30 JXW Production 26 February 2005 1000 Precambrian 38 53 56 117 08 58 69 7.14 2.8 −1.34 2151 362
31 XQ10 Production 25 February 2005 1800 Precambrian 39 00 33 117 12 09 80 7.10 4.1 −1.19 2139 378
32 DGZT Production 25 February 2005 2000 Precambrian 38 51 20 117 22 01 96 7.52 −24.3 −1.38 1995 502
32s DGZT Production 13 July 2005 2001 Precambrian 39 51 20 118 22 01 91 6.75 −213.0 −0.62 1950 515
33 XQ11 Production 25 February 2005 2500 Precambrian 39 00 44 117 13 10 95 7.13 2.1 −1.10 1959 394
34 ZL1 Production 27 February 2005 2700 Precambrian 39 32 09 117 21 43 66 7.60 −27.3 −1.83 937 331
34s ZL1 Production 12 July 2005 2701 Precambrian 40 32 09 118 21 43 80 7.12 −265.0 −1.18 1044 381
35 DL28 Production 24 January 2005 3450 Precambrian 39 04 37 117 20 59 77 7.09 −3.1 −1.07 1771 507
Table 1 (Continued )
Sample no. SO4 Cl Ca Mg Na K SiO2 NH4 NO3 F Br Li S-2 CO2 H3 BO3
1 450 725 105.0 89.0 510 2.1 15.8 0.30 0.25 1.55 1.25 0.02 1.48 51.68 1.7
2 406 550 52.0 49.0 495 2.2 11.0 0.08 1.75 3.25 1.95 0.03 3.76 nd 1.3
3 66 71 11.0 8.7 226 1.0 6.5 0.14 0.70 4.78 0.24 0.01 1.15 46.72 0.5
4 68 122 7.0 3.6 260 1.5 12.5 0.15 0.07 3.39 0.41 0.01 0.68 51.03 7.1
5 91 123 7.6 3.4 259 1.0 7.5 0.02 3.10 3.29 0.15 0.01 nd nd 7.1
6 37 81 5.2 1.5 220 1.1 23.0 <0,01 1.54 3.70 0.25 0.01 0.81 48.38 2.2
7 33 83 10.0 8.5 222 1.2 25.0 0.05 0.25 4.01 1.40 <0,01 nd nd 0.7
8 0.08 21 4.9 0.6 214 1.2 21.0 0.06 2.15 7.50 0.10 0.02 0.42 56.01 3.4
9 12.5 23 4.0 0.7 219 1.9 20.2 <0,01 0.05 5.50 0.12 0.02 nd nd 3.6
10 75 157 12.6 1.5 346 3.0 21.0 0.70 0.15 6.00 0.45 0.07 1.02 49.99 8.6

A. Minissale et al. / Geothermics 37 (2008) 400–428

11 30 34 5.2 0.5 247 1.2 29.5 0.73 0.05 3.60 0.15 0.01 0.63 73.32 4.3
12 316 593 35.3 8.3 628 30.8 13.5 0.61 0.78 6.95 1.40 2.00 2.15 nd 44
13 85 620 14.0 1.2 604 5.0 25.0 1.50 0.50 7.50 2.20 0.37 0.89 53.59 31
14 237 360 11.0 0.7 499 5.4 33.5 1.40 0.25 5.50 1.15 1.13 6.47 49.34 42
14s 225 330 10.0 6.0 490 5.2 32.5 1.00 0.60 7.70 0.95 1.05 nd nd nd
15 30 58 0.7 1.0 290 4.7 62.5 1.20 0.15 4.50 0.25 0.05 0.7 65.64 15
15s 32 61 0.8 1.2 310 4.8 56.5 0.56 0.07 3.20 0.35 0.06 nd nd nd
16 275 405 36.0 7.2 451 61.0 51.0 1.70 0.60 9.50 1.30 2.60 0.75 63.23 46
16s 325 400 42.0 7.8 475 66.0 47.5 1.09 0.80 10.50 1.05 2.50 nd nd nd
17 282 437 28.0 7.8 460 62.4 44.0 0.39 0.31 8.66 1.13 2.50 nd nd 44
18 136 99 34.2 9.0 216 44.2 52.0 0.19 0.82 7.11 0.34 1.20 6.12 52.25 33
19 310 390 45.0 8.5 458 60.0 21.5 0.90 0.25 8.15 1.30 2.60 1.02 45.37 47
20 2200 872 491.0 99.0 773 44.0 35.0 3.00 0.25 5.75 2.85 1.90 7.01 59.16 32
21 264 512 29.5 8.3 544 40.4 24.0 0.88 0.74 7.78 1.25 2.00 5.12 49.14 43
22 325 378 48.0 4.2 451 68.0 36.5 0.80 0.25 8.25 1.25 2.70 2.18 56.57 45
23 166 105 34.1 6.5 209 51.1 25.5 1.07 0.57 7.24 0.36 1.10 8.45 nd 36
23s 175 93 34.0 6.4 215 51.0 47.5 1.80 0.70 8.25 0.30 1.00 nd nd nd
24 325 442 27.0 12.0 458 75.0 48.5 2.60 1.00 10.50 0.55 2.80 01:15 54.08 46
25 325 423 30.3 14.3 438 77.4 59.0 0.64 1.21 9.23 1.15 2.70 nd nd 43
26 325 495 39.0 13.0 465 74.0 56.5 0.60 0.65 10.50 1.45 2.80 3.31 53.63 47
27 359 476 18.5 13.3 505 73.2 65.0 0.88 0.59 9.25 1.25 2.70 nd nd 45
28 327 474 30.0 13.8 460 72.6 49.5 1.08 1.44 10.03 1.27 2.70 1.78 50.44 45
28s 350 458 31.0 14.0 465 72.5 58.0 1.79 0.75 10.00 1.10 2.50 nd nd nd
29 305 475 29.5 13.5 466 71.2 61.5 0.95 1.87 9.25 12.79 2.60 nd nd 43
30 409 636 36.5 15.3 593 74.0 25.0 0.61 1.02 9.33 1.40 2.90 2.56 49.94 43
31 420 608 35.0 14.5 561 71.2 50.5 0.12 0.57 8.06 1.32 2.80 1.54 42.95 45
32 300 507 20.9 4.7 564 48.0 48.5 1.58 0.49 10.83 1.35 2.10 3.11 48.24 46
32s 300 430 21.5 4.8 565 48.2 65.0 2.62 0.57 9.50 1.15 1.75 nd nd nd
33 361 491 30.3 11.0 523 77.9 70.0 0.73 1.72 9.12 1.23 2.70 1.65 53.24 40
34 159 105 29.3 7.2 210 52.2 43.5 1.01 0.64 7.86 0.41 1.20 1.89 57.82 36
34s 200 90 30 7.5 215 53 67 0.72 0.96 8.5 0.3 1.1 nd nd nd
35 300 392 28.0 11.0 429 70.0 33.5 0.50 0.25 10.00 1.30 2.70 1.67 49.64 47
Chemical parameters given in mg/l. TDS, total dissolved solids; nd, not determined; “s” in the sample number (column 1) refers to the July 2005 sampling campaign.

405
 406
Table 2
Minor and trace elements (in ␮g/l) in water samples from Tianjin wells
Sample no. Well name Al As Ba Be Cd Co Cr Cs Cu Fe Hg Mn Mo Ni
1 DKJ 5 9.8 42 <0.05 0.33 0.03 0.7 0.01 5.2 21 1 213.9 66.7 <0.2
2 SH (Sport Hotel) 3 10.5 15 <0.05 3.04 0.02 <0.5 <.01 4.6 442 0.3 74.4 54.6 <0.2
3 HHL03 16 2.7 50 <0.05 0.97 0.04 2.2 0.14 3.5 88 0.7 29.6 76.2 0.4
4 DFZZ01 13 3.4 61 <0.05 7.41 <0.02 <0.5 <.01 15.6 70 0.4 8.0 15.4 0.2
5 DFZZ01-R (DFZZ02) 3 3.4 59 <0.05 0.69 <0.02 <0.5 <.01 7.1 50 <0.1 7.7 10.2 <0.2
6 AS01 20 5.5 60 <0.05 3.13 0.02 0.5 0.02 4.7 83 <0.1 9.9 13.7 0.6
7 AS01-R (AS02) 5 2.2 50 <0.05 <0.05 <0.02 17.6 <.01 2.3 <10 <0.1 2.7 68.9 <0.2
8 HHL01 14 1.2 42 <0.05 <0.05 <0.02 <0.5 <.01 2.1 72 <0.1 10.0 23.6 <0.2
9 HHL01-R (HHL02) 15 1.9 65 <0.05 0.37 0.06 <0.5 <.01 7.7 174 0.1 94.0 26.5 <0.2

A. Minissale et al. / Geothermics 37 (2008) 400–428

10 NK15 (Zoo) 14 1.1 18 <0.05 0.53 0.02 <0.5 0.02 3.7 40 <0.1 7.0 16.8 <0.2
11 WQ10 49 18.4 37 <0.05 <0.05 <0.02 <0.5 0.01 2.3 17 <0.1 4.3 32.3 <0.2
12 JH 20 1.9 56 0.12 226.6 0.1 0.6 3.58 5.7 1120 <0.1 42.9 63.9 <0.2
13 DG24 17 2.9 125 <0.05 <0.05 <0.02 <0.5 0.31 5.2 183 <0.1 19.6 4.4 <0.2
14 Tg19 (Tanggu) 20 1.9 82 0.07 0.22 <0.02 <0.5 0.26 4.5 75 0.1 30.1 1.5 <0.2
14s Tg19 (Tanggu) nd nd nd nd nd nd nd nd nd nd nd nd nd nd
15 WQ5 58 86.9 79 <0.05 3.56 <0.02 <0.5 0.18 2.8 38 <0.1 4.3 74.2 <0.2
15s WQ5 nd nd nd nd nd nd nd nd nd nd nd nd nd nd
16 DL25 (Bio Park) 17 5.1 89 0.17 0.73 <0.02 0.6 21.19 4.7 94 <0.1 87.5 0.4 <0.2
16s DL25 (Bio Park) nd nd nd nd nd nd nd nd nd nd nd nd nd nd
17 DL25R (Bio Park) 23 4.9 87 0.18 0.32 <0.02 <0.5 20.71 3.9 254 <0.1 89.5 0.6 <0.2
18 WANG 3 6 <0.5 119 0.12 1.35 <0.02 <0.5 8.11 1.9 <10 0.1 46.7 0.3 <0.2
19 DL16 12 13.8 86 0.08 0.07 <0.02 0.5 18.91 4.6 49 <0.1 15.4 31.9 0.2
20 NK14 14 2.9 29 <0.05 <0.05 <0.02 <0.5 4.87 8 6311 <0.1 62.8 0.7 <0.2
21 JN02 12 2.2 86 0.06 20.1 <0.02 0.5 11.97 4.6 861 0.3 12.1 4 <0.2
22 DL11 10 7.7 78 <0.05 0.4 <0.02 <0.5 19.76 4.2 44 0.1 8.7 1.4 2.5
23 WANG-4 20 0.6 125 0.11 0.24 <0.02 <0.5 10.73 2.2 92 <0.1 6.3 0.6 <0.2
23s WANG-4 nd nd nd nd nd nd nd nd nd nd nd nd nd nd
24 HD09 20 6.1 99 <0.05 2.87 <0.02 <0.5 21.65 4.8 133 <0.1 6.8 0.3 <0.2
25 HD09-R (HD02) 18 3.2 103 0.08 33.48 0.04 0.5 21.99 8.4 330 0.2 12.9 1 2.4
26 HD12 20 5.9 99 0.13 0.67 <0.02 <0.5 20.1 5.9 117 <0.1 3.2 0.3 0.5
27 HD12-R (HD13) 9 5.8 96 0.11 0.14 0.03 <0.5 19.52 4.6 698 <0.1 6.2 2 1.3
28 HD14 15 6.5 103 0.06 0.25 <0.02 0.5 19.86 4.7 97 0.3 5.7 0.7 0.2
28s HD14 nd nd nd nd nd nd nd nd nd nd nd nd nd nd
29 HD14R 16 7.9 101 <0.05 0.76 0.11 0.6 19.03 4.4 660 <0.1 9.0 9.7 2.6
30 JXW 8 2.8 65 0.06 2.68 <0.02 0.5 16.68 4.7 124 0.5 9.2 58.5 <0.2
31 XQ10 17 3.3 74 <0.05 4.3 <0.02 0.6 15.42 4.6 101 2.5 1.7 30.1 <0.2
32 DGZT 47 2.1 107 0.07 2.14 <0.02 <0.5 15.9 4.3 128 <0.1 4.6 9.5 <0.2
32s DGZT nd nd nd nd nd nd nd nd nd nd nd nd nd nd
33 XQ11 16 6.1 114 0.23 0.81 <0.02 0.5 23.42 4.6 100 <0.1 4.2 0.7 <0.2
34 ZL1 25 1.6 140 0.08 2.86 <0.02 <0.5 10.31 2 86 0.4 3.5 16.4 <0.2
34s ZL1 nd nd nd nd nd nd nd nd nd nd nd nd nd nd
35 DL28 20 5.8 115 0.09 0.39 <0.02 0.5 25.44 4.8 321 0.1 7.0 0.7 <0.2
Table 2 (Continued )
Sample no. P Pb Rb Sb Se Sn Sr Th Tl U V W Zn Zr
1 69 0.1 0.5 <0.05 4.5 <0.05 1749 <0.05 <0.01 4.76 5.0 0.1 16.6 <0.02
2 34 <0.1 0.4 <0.05 5.3 <0.05 1069 <0.05 <0.01 1.26 2.8 0.1 6.0 <0.02
3 64 0.5 0.5 <0.05 1 0.09 212 <0.05 <0.01 5.43 0.3 0.3 5.8 0.02
4 68 4.2 0.3 0.07 1.4 0.14 129 <0.05 <0.01 2.29 0.5 0.4 12.5 <0.02
5 65 0.9 0.3 <0.05 1.3 <0.05 126 <0.05 <0.01 2.23 0.5 0.4 4.9 <0.02
6 83 0.5 0.6 0.13 0.9 0.06 72 <0.05 <0.01 0.85 0.4 1.0 11.3 <0.02
7 <20 <0.1 0.3 0.17 1.4 <0.05 229 0.11 <0.01 5.09 0.4 2.0 0.7 <0.02
8 88 <0.1 0.7 <0.05 0.5 0.45 43 <0.05 <0.01 <0.02 0.3 6.7 2.3 <0.02
9 114 0.4 0.8 <0.05 0.5 <0.05 52 <0.05 <0.01 0.31 1.5 5.8 6.2 0.02
10 32 0.1 2.3 <0.05 2 <0.05 383 <0.05 <0.01 <0.02 1.1 4.4 2.2 <0.02

A. Minissale et al. / Geothermics 37 (2008) 400–428

11 46 0.2 1.0 <0.05 0.5 <0.05 44 <0.05 <0.01 0.05 0.3 6.6 0.8 <0.02
12 <20 0.5 57 <0.05 4.7 <0.05 3060 <0.05 <0.01 0.03 1.7 0.3 6.7 <0.02
13 <20 <0.1 8.2 <0.05 6.5 <0.05 380 <0.05 <0.01 <0.02 2.9 1.2 2.2 <0.02
14 21 0.1 11 <0.05 3.7 0.07 533 <0.05 <0.01 0.03 1.5 1.3 9.2 <0.02
14s nd nd nd nd nd nd nd nd nd nd nd nd nd nd
15 <20 0.1 7.8 0.25 1.5 0.09 109 <0.05 0.02 <0.02 0.3 10.2 5.8 <0.02
15s nd nd nd nd nd nd nd nd nd nd nd nd nd nd
16 <20 0.2 141 <0.05 4 0.1 2203 <0.05 0.69 <0.02 1.7 1.6 3.6 <0.02
16s nd nd nd nd nd nd nd nd nd nd nd nd nd nd
17 <20 0.1 141 <0.05 4.2 <0.05 2191 <0.05 0.63 <0.02 1.5 1.5 374.2 <0.02
18 <20 0.1 83 <0.05 1.6 <0.05 6605 <0.05 <0.01 <0.02 0.4 3.0 2.6 <0.02
19 <20 <0.1 139 <0.05 4.4 0.15 2840 <0.05 0.11 <0.02 1.7 1.2 2.9 <0.02
20 68 1.9 85 <0.05 5 0.11 13888 0.13 <0.01 0.02 2.2 0.5 13.8 0.02
21 <20 0.4 83 <0.05 4.2 <0.05 4209 <0.05 0.08 <0.02 1.5 0.6 4.1 <0.02
22 <20 0.1 150 <0.05 3.9 0.31 2056 <0.05 1.08 <0.02 1.6 2.1 2.3 <0.02
23 <20 <0.1 105 <0.05 1.4 <0.05 1554 <0.05 0.04 <0.02 0.4 3.5 1.2 <0.02
23s nd nd nd nd nd nd nd nd nd nd nd nd nd nd
24 <20 0.1 174 <0.05 4.3 0.18 2176 <0.05 0.79 <0.02 1.5 2.1 3.3 <0.02
25 <20 0.6 177 0.14 4.9 0.22 2153 <0.05 0.57 <0.02 1.0 2.2 10.3 <0.02
26 <20 0.3 170 <0.05 4.5 6.92 2220 <0.05 0.75 <0.02 1.8 1.6 14.7 <0.02
27 <20 0.1 167 <0.05 4.7 <0.05 2191 <0.05 0.32 <0.02 1.7 1.2 10.8 <0.02
28 <20 0.5 169 <0.05 4.4 <0.05 2247 <0.05 0.69 <0.02 1.7 1.9 20.6 <0.02
28s nd nd nd nd nd nd nd nd nd nd nd nd nd nd
29 <20 0.1 169 <0.05 4.3 <0.05 2280 <0.05 0.2 <0.02 1.8 2.0 7.8 <0.02
30 <20 0.3 150 <0.05 4.9 <0.05 2621 <0.05 0.25 <0.02 2.0 1.6 15.1 <0.02
31 <20 0.3 143 0.09 4.7 0.07 2448 <0.05 0.29 <0.02 1.9 1.6 4.6 <0.02
32 <20 0.2 105 <0.05 4.1 0.99 2025 <0.05 0.47 <0.02 1.6 1.2 3.0 <0.02
32s nd nd nd nd nd nd nd nd nd nd nd nd nd nd
33 <20 <0.1 180 0.06 4.6 <0.05 2292 <0.05 0.95 <0.02 1.5 0.9 4.2 <0.02
34 <20 0.1 108 <0.05 1.4 <0.05 1798 <0.05 0.2 <0.02 0.5 2.6 3.6 <0.02
34s nd nd nd nd nd nd nd nd nd nd nd nd nd nd
35 <20 0.2 165 <0.05 4.3 0.38 2239 <0.05 0.81 <0.02 1.6 1.8 6.2 <0.02
nd, not determined; “s” in the sample number (column 1) refers to the July 2005 sampling campaign.

407
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Table 3
Chemical composition of gas stripped from Tianjin water well samples
Sample no. Well name Well depth (m) Lithotype Date T (◦ C) Total CO2 N2 Ar CH4 O2 Ne H2 He

1 DKJ 200 Quaternary 25 January 2005 16 1.77 0.3940 1.1061 0.0264 0.0024 0.2383 0.000021 0.000030 0.000037
4 DFZZ01 400 Quaternary 26 February 2005 23 1.53 0.3234 1.1059 0.0263 0.0006 0.0754 0.000020 0.000015 0.001062
6 AS01 640 Tertiary 24 February 2005 34 6.79 0.5926 5.5011 0.1346 0.0037 0.5498 0.000104 0.000222 0.003128
8 HHL01 900 Tertiary 25 January 2005 36 1.22 0.3076 0.8411 0.0202 0.0471 0.0029 0.000016 0.000651 0.000188
10 NK15 (Zoo) 1300 Tertiary 25 January 2005 41 3.19 0.3918 2.3457 0.0564 0.1789 0.2139 0.000047 0.000044 0.001255
11 WQ10 1400 Tertiary 26 January 2005 53 1.91 0.1607 1.6893 0.0410 0.0046 0.0172 0.000031 0.000513 0.000045
12 JH 1500 Tertiary 26 February 2005 48 2.86 1.4935 1.3144 0.0310 0.0007 0.0140 0.000023 0.000029 0.008212

A. Minissale et al. / Geothermics 37 (2008) 400–428

13 DG24 1744 Tertiary 27 January 2005 57 2.09 0.8295 1.1924 0.0290 0.0340 0.0001 0.000023 0.000034 0.005526
14 Tg19 (Tanggu) 2200 Tertiary 24 January 2005 66 3.41 1.2048 2.1157 0.0506 0.0030 0.0347 0.000044 0.000390 0.005464
15 WQ5 2600 Tertiary 26 January 2005 83 3.90 2.3002 1.1672 0.0293 0.3272 0.0692 0.000023 0.002625 0.001917
15s WQ5 2601 Tertiary 12 July 2005 81 4.39 2.3072 1.6137 0.0398 0.3854 0.0437 0.000026 0.000516 0.002284
16 DL25 (Bio Park) 1300 Tertiary 24 January 2005 81 2.30 1.8954 0.3052 0.0074 0.0764 0.0171 0.000005 0.000034 0.000491
16s DL25 (Bio Park) 1301 Tertiary 12 July 2005 68 5.21 3.9705 0.9340 0.0222 0.2080 0.0738 0.000016 0.000063 0.005808
18 WANG 3 1077 Ordovician 27 February 2005 43 2.31 0.7323 1.3584 0.0323 0.0076 0.1789 0.000024 0.000059 0.000111
19 DL16 1312 Ordovician 24 January 2005 66 1.78 0.9069 0.6526 0.0161 0.0014 0.1983 0.000013 0.000033 0.000220
20 NK14 2130 Ordovician 27 January 2005 63 2.45 1.6158 0.7900 0.0195 0.0018 0.0157 0.000015 0.000156 0.003248
21 JN02 2500 Ordovician 25 February 2005 46 2.62 1.6683 0.8514 0.0207 0.0679 0.0094 0.000016 0.000041 0.000127
22 DL11 1490 Cambrian 24 January 2005 74 5.43 3.7593 1.1794 0.0284 0.2823 0.1766 0.000021 0.000104 0.001715
23 WANG-4 2072 Cambrian 27 February 2005 74 3.14 2.8297 0.1914 0.0047 0.1142 0.0029 0.000003 0.000072 0.000119
23s WANG-4 2072 Cambrian 12 July 2005 70 2.86 2.5047 0.2601 0.0061 0.0800 0.0058 0.000004 0.000448 0.000242
24 HD09 3450 Precambrian 23 January 2005 83 3.64 1.9182 1.2881 0.0306 0.2414 0.1609 0.000025 0.000585 0.000656
26 HD12 3190 Precambrian 23 January 2005 80 1.90 1.4575 0.3392 0.0080 0.0725 0.0117 0.000007 0.000320 0.008339
28 HD14 3150 Precambrian 01 March 2005 87 2.53 1.7609 0.6148 0.0149 0.0904 0.0434 0.000011 0.000981 0.001357
28s HD14 3150 Precambrian 13 July 2005 78 2.39 1.6146 0.5971 0.0155 0.1450 0.0189 0.000011 0.000403 0.002768
30 JXW 1000 Precambrian 26 February 2005 69 3.47 1.6432 1.5035 0.0365 0.0250 0.2627 0.000027 0.000038 0.002039
31 XQ10 1800 Precambrian 25 February 2005 80 2.11 1.3566 0.6749 0.0163 0.0490 0.0112 0.000013 0.000019 0.003830
32 DGZT 2000 Precambrian 25 February 2005 96 8.65 1.4502 5.6737 0.1381 0.0723 1.3141 0.000105 0.001211 0.001180
32s DGZT 2001 Precambrian 13 July 2005 91 5.45 3.6198 1.3901 0.0332 0.3414 0.0573 0.000024 0.006583 0.004727
33 XQ11 2500 Precambrian 25 February 2005 95 3.72 2.9072 0.6187 0.0147 0.1158 0.0632 0.000013 0.000219 0.001398
34 ZL1 2700 Precambrian 27 February 2005 66 4.02 1.9982 1.8307 0.0453 0.1261 0.0179 0.000035 0.001834 0.004038
34s ZL1 2701 Precambrian 12 July 2005 80 3.87 2.1862 1.1601 0.0285 0.0875 0.3975 0.000019 0.005200 0.000063
35 DL28 3450 Precambrian 24 January 2005 77 2.96 2.4155 0.4115 0.0098 0.0924 0.0333 0.000007 0.000150 0.000520

“s” in the sample number (column 1) refers to the July 2005 sampling campaign.
Table 4
Isotope data on fluids from Tianjin water wells
Sample no. Well name δ18 O-H2 O (‰ SMOW) δ2 H-H2 O (‰ SMOW) ␦13 C-DIC (‰ PDB) δ13 C-CO2 (‰ PDB) 3
He/4 He (R/Ra)
1 DKJ −9.80 −75.96 −10.68 nd nd
2 SH (Sport Hotel) −9.97 −76.32 −10.10 nd nd
3 HHL 3 −10.17 −74.77 −9.85 nd nd
4 DFZZ01 −9.94 −77.31 −11.64 nd nd
5 DFZZ01-R (DFZZ02) −9.85 −76.08 −11.71 nd nd
6 AS01 −9.92 −76.51 −11.50 nd 0.498
7 AS01-R (AS02) −9.92 −78.37 −10.15 nd nd

A. Minissale et al. / Geothermics 37 (2008) 400–428

8 HHL01 −10.09 −75.26 −10.71 nd nd
9 HHL01-R (HHL02) −8.55 −76.50 −11.05 nd nd
10 NK15 (Zoo) −9.60 −76.60 −12.78 −11.14 nd
11 WQ10 −10.17 −76.38 −6.44 nd nd
12 JH −9.09 −77.11 −5.51 nd nd
13 DG24 −9.04 −75.82 −17.49 −12.48 nd
14 TG19 (Tanggu) −8.93 −77.76 −7.24 −14.2 nd
15 WQ5 −8.79 −74.60 −4.59 nd nd
16 DL25 (Bio Park) −9.15 −75.74 −4.44 −11.9 nd
17 DL25R (Bio Park) −9.40 −76.89 −4.08 −11.63 nd
18 WANG 3 −9.91 −78.13 −3.44 nd 0.483
19 DL16 −9.46 −75.07 −4.79 nd nd
20 NK14 nd −75.73 −6.30 nd nd
21 JN02 −8.28 −76.15 −5.06 −5.62 nd
22 DL11 −9.65 −76.85 −4.41 nd nd
23 WANG 4 −10.16 −75.83 −3.33 −10.15 0.474
24 HD09 −9.59 −78.34 −4.74 nd nd
25 HD09-R (HD02) −8.98 −75.69 −4.83 nd nd
26 HD12 −9.39 −74.58 −5.29 −10.83 nd
27 HD12-R (HD13) −9.67 −76.27 −5.01 nd nd
28 HD14 −9.59 −75.85 −5.19 −10.97 nd
29 HD14R −9.76 −76.60 −5.25 nd nd
30 JXW −9.19 −76.07 −6.57 nd nd
31 XQ 10 −9.49 −75.43 −6.19 nd nd
32 DGZT −8.70 −76.18 −4.89 nd nd
33 XQ11 −8.93 −76.59 −5.01 nd 0.379
34 ZL1 −10.24 −75.65 −2.84 nd nd
35 DL28 −9.05 −75.64 −4.65 −9.34 nd
DIC, dissolved inorganic carbon; nd, not determined; SMOW, Standard Mean Ocean Water; PDB, Pee Dee Belemnite standard.

409
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Table 5
Recalculated and measured mineral phases based on Scanning Electron Microprobe (SEM) and/or X-Ray Diffraction (XRD) analyses of materials from Tianjin wells and surface
installations (samples collected in January, February and July 2005)
Sample no. Well name Quantity of solids Sample type SEM-ESD possible phasesa XRD analysis

1 DKJ No solids
2 SH (Sport Hotel) –
3 HHL03 –
4 DFZZ01 None
5 DFZZ01-R (DFZZ02) None
6 AS01 None

A. Minissale et al. / Geothermics 37 (2008) 400–428

7 AS01-R (AS02) High 0.45 ␮m filtered material qz, Kfeld, Fe, plag, MgFe
8 HHL01 None
9 HHL01-R (HHL02) None
10 NK15 (Zoo) None
11 WQ10 Not sampled
11 WQ10 Material in filtering device Quartz, feldspars
12 JH High 0.45 ␮m filtered material plag, NaCl, ZnS, FeS
13 DG24 Moderate 0.45 ␮m filtered material Fe, NaCl, plag
14 Tg19 (Tanggu) Moderate 0.45 ␮m filtered material NaCl, Fe, plag, Kfeld, NaS?
15 WQ5 Low 0.45 ␮m filtered material Kfeld, plag, Fe
16 DL25 (February) Low 0.45 ␮m filtered material MgFe, plag, FeS
16b DL25 (February) deposits inside exchager Quartz? + illite?; not Completely crystalline
16c DL25 (July) Wellhead steel Fe, Ni, Cr
16d DL25 (July) Wellhead incrustation CaCO3
16e DL25 (July) Steel pipe Fe
16f DL25 (July) Pipe incrustation CaCO3 , Fe
17a DL25R (February) High 0.45 ␮m filtered material ZnS, NaCl, FeS, Kfeld?
17b DL25R (October) Material in filtering device qz, Kfeld, FeS, plag, ZnS
18 WANG 3 None
19 DL16 Low 0.45 ␮m filtered material Kfeld, plag, Fe, phase P
20 NK14 Low 0.45 ␮m filtered material FeS, CaCO3 , ZnS, plag
21 JN02 Low 0.45 ␮m filtered material Fe, plag?, NaCl,FeS
22 DL11 Low 0.45 ␮m filtered material Kfeld, plag, Fe
23a WANG-4 Low 0.45 ␮m filtered material CaCO3 , NaCl, Hg, FeS?
23b WANG-4 Wellhead incrustation Calcite (with Mg)
24 HD09 Low 0.45 ␮m filtered material plag, FeS, Fe
25 HD09-R (HD02) Low 0.45 ␮m filtered material plag, Fe,CaCl?, FeS, Ba
Table 5 (Continued )
Sample no. Well name Quantity of solids Sample type SEM-ESD possible phasesa XRD analysis

A. Minissale et al. / Geothermics 37 (2008) 400–428

26a HD12 High 0.45 ␮m filtered material NaCl, ZnS, Kfeld?
26b HD12 Wellhead incrustation Halite, sylvite, aphthitalite (K3 Na(SO4 )2 )?
27 HD12-R (HD13) High 0.45 ␮m filtered material CuS, NaCl, ZnS,FeS, plag?
28 HD14 Low 0.45 ␮m filtered material Fe, NaCl, ZnS, MgFe
29 HD14R High 0.45 ␮m filtered material FeS, plag, ZnS, NaCl?, Hg,Fe
29 HD14R Deposits on the floor FeO, magnetite, Zn?
30 JXW None
31 XQ10 Low 0.45 ␮m filtered material Hg, CuS, qz, Fe, CaCO3
32 DGZT Low 0.45 ␮m filtered material NaCl, CaCO3 , Kfeld
33 XQ11 Moderate 0.45 ␮m filtered material qz, NaCl, Fe, MgFe,CaCO3 ?
34 ZL1 Low 0.45 ␮m filtered material qz, CaCO3 , Kfeld
35 DL28 High 0.45 ␮m filtered material plag, Fe,FeS, NaCl, Kfeld
36 New well Tianjin Deposits inside exchanger plag, Kfeld, Fe, Cu
36 New well Tianjin Steel pipe Fe
36 New well Tianjin Pipe incrustation CaCO3 , Fe
a Ba, Ba containing phase; CaC, Ca and Cl? containing phase; CuS, Cu and S containing phase; phase P, phosphate?; FeS, Fe & S containing phase; Hg, sulfur(?) containing
Hg; Kfeld, K-feldspar; MgFe, Mg and Fe silicate; NaS, Na and S? containing phase; plag, plagioclase; qz, quartz; ZnS, Zn and S containing phase.

411
412 A. Minissale et al. / Geothermics 37 (2008) 400–428

Fig. 2. Chemical characteristics of water samples collected in January and February 2005 (see Table 2). Numbers
correspond to sample numbers (see tables).

4. Chemistry of well waters: water types

All water samples collected in January and February 2005 (Table 2) have been plotted in
Fig. 2. The diagram shown in Fig. 2a is the classic Langelier and Ludwig (1942) classification
diagram for waters. Most samples from the Tertiary and the Quaternary sedimentary formations
have salinity lower than 1000 mg/l and are of Na–HCO3 type. Samples from the underlying pre-
Tertiary formations have higher salinity (some above 2000 mg/l) and a Na–Cl composition, with
a marked Na–HCO3 component. Two shallow water samples [<200-m deep: # 1 (well DKJ) and
# 2 (well SH)] from the Quaternary sediments, have Na–Cl composition, with higher salinity
(up to 2000 mg/l). One sample from the Ordovician unit (# 20; well NK14) has a Ca–Cl(SO4 )
composition, with a relatively high salinity (4700 mg/l).
 A. Minissale et al. / Geothermics 37 (2008) 400–428 413

The Na–Cl diagram in Fig. 2b shows that all samples, including the anomalous Ca–Cl(SO4 )
sample 20 (well NK14), have similar Cl/Na ratios (about 0.6) and differ strongly from those
of seawater (Cl/Na = 1.2) and the dissolution of halite (Cl/Na = 1). They are clustered into two
main groups with different salinities: one including samples from the Tertiary and the Quaternary
formations, the second including samples from the underlying producing pre-Tertiary horizons.
The similarity of the Cl/Na ratio of all the samples would suggest possible dilution and/or mixing
between the two groups (or end-members).
In terms of water–rock interaction, the log(Na/K)-temperature diagram of Fig. 2c (after
Fournier, 1991) indicates that these two important elements do not derive simply from any common
primary (albite and K-feldspar) or alteration (Na- and K-montmorillonites) mineral assemblages,
and that their concentrations are not controlled by mixing with ocean-type waters. This diagram
shows how different are the waters hosted in the Tertiary and the Quaternary formations with
respect to those from the underlying formations.
Finally, the Na/K ratio versus depth diagram of Fig. 2d shows that the aquifer in the
Tertiary–Quaternary formations is present at depths down to 2500 m, whereas the one produc-
ing from the underlying pre-Tertiary (Lower Paleozoic-Sinian) formations rises to 1000 m in the
Tianjin structural high. There seems to be only a slight tendency of waters hosted in the Tertiary
Aquifer to mix with those from older geologic units.

5. Isotopic composition of waters: their origin

The 18 O/16 O and D/H isotopic ratios (Table 4) of the investigated water samples have been
plotted in the classic δ18 O–δD diagram (Craig, 1961) of Fig. 3; also shown are the Global Meteoric
Water (GMWL) and the Local Meteoric Water Lines (Pang, 2000).
The δD values of all well-water samples fall within a narrow range, i.e. between −74
and −79‰ (SMOW1 ), whereas δ18 O values span a wider range, from −10.5 to −8.3‰
(SMOW). It is noteworthy that the samples all plot to the right of the GMWL, with rela-
tively uniform δD values and no differentiation between the two main groups defined in Section
4.
By considering an average isotopic gradient of precipitation for China (data from IAEA/WMO,
2001), the δD values of the two aquifers suggest a similar origin, deriving from precipitation at
elevations roughly between 1500 and 1800 m above sea level, perhaps in the Taihangshan Range
and Yan Shan Range NW of Tianjin.
Although the position of the local meteoric line with respect to the GMWL can be used to
define the average recharge elevation for the waters, the δ18 O values of well-water samples are
scattered, probably the result of 18 O exchange processes between the fluid and the confined
aquifer rocks. Such oxygen shifts are typical of fluids in active high-enthalpy geothermal systems
(Craig, 1963), where the long-residence time of the fluid contacting primary minerals leads to
the formation of secondary minerals with lighter oxygen in their lattices because of rock–fluid
18 O–16 O fractionation (Giggenbach, 1991). Although deep temperatures in Tianjin are not typical

of high-enthalpy systems, this is the more reasonable explanation for the position of the 18 O data
in Fig. 3. The figure also suggests that the confined fluid in both aquifers has not been affected by
steam losses.

1 SMOW, Standard Mean Ocean Water.

414 A. Minissale et al. / Geothermics 37 (2008) 400–428

Fig. 3. Isotopic composition of waters from Tianjin wells. The grey areas refer to the isotopic elevation of the recharge
according to the Global Meteoric Water Line (light grey) or the Local Meteoric Line (light grey plus dark grey). Elevations
are given in meters above sea level. Numbers correspond to sample numbers (see tables).

6. Gas samples: origin of components

Dissolved gas samples from the well waters (Table 3) have been plotted in the CH4 –CO2 –N2
diagram of Fig. 4a. They spread in composition from almost pure CO2 to almost pure N2 , with
relatively low concentrations of CH4 . The low CH4 content is somewhat surprising because we
expected it to be higher in the Hua-Bei Plain, a continental Tertiary–Quaternary sedimentary
basin.
Waters samples from the pre-Tertiary formations are more enriched in CO2 , whereas those
from Tertiary and Quaternary strata have higher N2 . This suggests a deep high-temperature origin
for the CO2 as a product of decarbonation, and a more N2 -rich atmospheric “recharge” component
in samples from the Tertiary and the Quaternary formations.
The He–Ar–N2 diagram (Giggenbach et al., 1983) shown in Fig. 4b displays the end-member
compositions of: (i) a gas deriving from dissolved air (air), (ii) a gas resulting from the exsolution
from air-saturated waters (ASW), (iii) a gas deriving from an andesitic magmatic source (magma)
having a N2 /Ar ratio = 800, and (iv) a gas formed mainly inside the Earth’s crust (crust), with
progressively higher concentrations of radiogenic 4 He. All Tianjin samples plot close to the line
 A. Minissale et al. / Geothermics 37 (2008) 400–428 415

Fig. 4. (a) CH4 –CO2 –N2 diagram, and (b) He–Ar–N2 diagram (Giggenbach et al., 1983) for gas phases stripped from
Tianjin water wells. ASW is the position of a gas derived from air-saturated water. Numbers correspond to sample numbers
(see tables).

connecting the position of ASW and a gas formed in the crust (high radiogenic 4 He), although
slightly enriched in N2 . This suggests that the dissolved gas in the Tianjin water samples derives
from exsolution of air-saturated waters and that air is the only source of N2 .
To understand the origin of CO2 , its partial pressure in the well waters has been calculated
using the PHREEQC-2.11 simulation program (Parkhurst and Appelo, 1999). Calculated values
of −log PCO2 (PCO2 ) are listed in Table 1 and shown in Fig. 5. The maximum values of pCO2
occur in the well waters located in the structural high of the pre-Mesozoic formations around
the city of Tianjin (Fig. 5). This suggests a deep origin for the CO2 in or below the pre-Tertiary
formations that show structural highs in this area. The permeable limestones of the pre-Tertiary
formations support both the elevated PCO2 and the convective flow of the dissolved gas towards
those highs.
The presence of hydrogen in all the analyzed wells (up to 0.0067 mmol/l in sample 32 (well
DGZT)), especially in N2 -rich samples, is not compatible with a natural origin but can probably
be related to oxidation reactions involving the iron casings during injection, as will be explained
below.

7. 3 He/4 He ratios in gas samples

The 3 He/4 He ratio (R) in the gas samples can be used to detect deep mantle fluids that penetrate
the crust (Craig and Lupton, 1976). The ratio in mantle gas, which can be more than 35 times than
416 A. Minissale et al. / Geothermics 37 (2008) 400–428

Fig. 5. Distribution −log PCO2 (in atm) calculated based on Tianjin water sample data (pCO2 given in Table 1). The
area with maximum values (up to −0.8) coincides with the structural top of the pre-Mesozoic formations (see Fig. 1b).
Symbols for production and injection well as in Fig. 1.
 A. Minissale et al. / Geothermics 37 (2008) 400–428 417

the ratio in air (Ra = 1.39 × 10−6 ), is indicative of the time when the Earth was formed. Mantle
gases penetrating the crust become enriched in radiogenic 4 He, which tends to reduce the 3 He/4 He
ratio to as little as 0.001 times the ratio in air. It has been estimated that, for R/Ra higher than
0.2, there is some mantle gas affecting the crust (O’Nions and Oxburgh, 1988). The values we
measured in four Tianjin wells (AS01, WANG3, WANG-4, XQ11; Table 4) are all around 0.4,
reflecting only small fractions of mantle 3 He, probably rising from depth through deep fractures
and/or through the Tianjin metamorphic structural high.

8. 13 C/12 C isotopic ratios in CO2 and HCO3

The 13 C/12 C carbon isotopic ratio of HCO3 ions (reported as DIC; Table 4) has been analyzed
in all fluid samples. There is a marked difference in this ratio in fluids from wells bottoming in the
Quaternary and Tertiary formations with respect to those producing from the pre-Tertiary forma-
tions. In relatively shallow wells (samples #1–10), δ13 C-DIC is lower than −10.0‰ (PDB2 );
in deeper wells (samples #11–35), bottoming predominantly in pre-Tertiary formations, the
δ13 C-DIC value is more positive, ranging −3.0 to −7.0‰. This difference can be explained
by considering that HCO3 in the shallower samples probably derives its relatively light isotopic
composition partly from the oxidation of organic matter in soils (typically less than −20‰).
The 13 C/12 C ratio in the second deeper group probably represents a mixture between shallow
organic-derived and inorganic HCO3 , the latter deriving from the dissolution of limestone that
yields HCO3 with δ13 C values close to 0‰ (Rollinson, 1993).
All (or most of) the pre-Tertiary formations have limestone as an important part of the lithology
and these more positive δ13 C values are stratigraphically lower and, at the same time, hotter. This
indirectly points to mixing, at depth, between the isotopically heavy hot deep CO2 present in the
reservoir(s) and isotopically light descending soil-recharge-related CO2 .
The 13 C/12 C isotopic composition of the stripped CO2 from the liquid phase was analyzed
in those wells bottoming below the Tertiary, where there was enough CO2 (samples 10, 13, 14,
16, 17, 21, 23, 26, 28, and 35; Table 4). Apart from sample 21, where δ13 C of DIC and CO2
are similar, all δ13 C values are less than −10‰, quite different (lighter) than the corresponding
δ13 C-DIC. As the lowering of the δ13 C caused by the stripping fractionation at 50–100 ◦ C is about
1‰, in samples where the difference is greater than 1‰ an organic source of CO2 can be invoked.
It seems likely, therefore, that there are both inorganic and organic origins for carbon of HCO3
in solution (as DIC) and in the free CO2 .

9. Seasonal effects on the fluid composition of well waters

In July 2005 seven samples (# 14s, 15s, 16s, 23s, 28s, 32s and 34s) were collected and analyzed
to highlight possible seasonal effects. Due to the production depths in the sampled wells and the
likely long-circulation pathways between the shallow and the deep aquifers, we were not expecting
relevant differences caused by changes in the recharge waters between winter (January–February)
and summer (July). Comparison of chemical data for both gas and waters in Tables 1–3 confirms
that there is no significant difference; both cation and anion contents vary within their relative
analytical errors.

2 PDB, Pee Dee Belemnite standard.

418 A. Minissale et al. / Geothermics 37 (2008) 400–428

Fig. 6. Temperature vs. depth diagram for Tianjin wells; thermal gradients vary from less than 2 ◦ C/100 m up to 6 ◦ C/100 m.
Numbers correspond to sample numbers (see tables).

On the contrary, unexpected differences, important for understanding the probable cause of
reservoir plugging during injection, have been found in the redox potential (Eh ) and pH of the
fluids. The Eh and pH are more negative (about 200 mV) and lower (about 0.2 units), respectively,
in summer. As the main composition of the fluids is unchanged, there seems to be only one
possible explanation in terms of seasonal effects, which is the reduced discharge rate of hot
water in summer and consequently longer residence time of the fluid in the well casings. It seems
reasonable to postulate that oxidation of the casings is lower in summer, with more reduced Fe2+ in
solution. Because of longer iron–fluid interaction times in summer, it is easier to reach saturation
with respect to several possible oxidized iron phases, such as Fe2 O3 , Fe3 O4 , Fe3 O(OH). The
simultaneously lower pH is probably related to higher PCO2 (Table 1), due to the accumulation
of the gas phase at the top of the wells.

10. Conceptual model of the field based on the chemical–physical data

The Tianjin geothermal field is a typical low-enthalpy liquid-dominated convective system

(Brandi et al., 1986) hosted in sedimentary formations, where maximum temperature gradients
are found in the Cangxian Uplift, a structural high in the pre-Tertiary formations in the area of
Tianjin city.
According to the temperature profiles at depth shown in Fig. 6, it is evident that there are
only a few wells where the thermal gradient is higher (up to 7 ◦ C/100 m; wells DL25 and JXW)
than the average Earth crustal gradient (about 3.3 ◦ C/100 m), and that most wells have even lower
 A. Minissale et al. / Geothermics 37 (2008) 400–428 419

Fig. 7. Graph of −log PCO2 (in atm) versus depth (in m) for waters in Tianjin wells; the oblique dashed line represents
the PCO2 at the production depth according to Henry’s Law. Numbers correspond to sample numbers (see tables).

thermal gradients. Based on the temperatures measured in wells bottoming in the Tertiary and
the Quaternary formations (wells DKJ, DFZZ01, HHL01, NK15, JH, DG24, Tg19 and WQ5),
the average shallow thermal gradient in the coastal area investigated (and probably in all eastern
China) seems to be less than 3.3 ◦ C/100 m.
According to several authors (Axelsson and Dong, 1998; Kun et al., 2000; Li, 2003) the
exploitation of the Tianjin geothermal resource has caused drawdown of the water table locally
(up to about 100 m), due to the increased pumping (at present up to 21 million m3 /year) caused
by the fast industrialization of the area in the last 10 years. In spite of this generalized drawdown,
the aquifer continues to be confined in some restricted parts, such as in the Tanggu area (about
5 bar wellhead pressure in Tg19). This clearly points to the fact that the two aquifers recognized
so far and previously described are effectively isolated from each other.
As suggested by the map showing the distribution of calculated pCO2 in the thermal waters
(Fig. 5), there seems to be a higher flux of CO2 in the wells located in the structural top of the
pre-Tertiary formations with log PCO2 higher than −1. However, this anomalous flux is actually
only apparent. By plotting the partial pressure of CO2 existing at well bottoms, and comparing
with theoretical values assuming increased solubility of CO2 due to higher hydrostatic pressures
(dashed line in Fig. 7), the fluid hosted in the Tianjin geothermal system can be considered, on
the average, equilibrated for the temperature at the production depth. Only a few wells (DKJ,
HHL03, JH, DL25, WANG3, DL16, JXW, XQ10, DGZT, XQ11) have a PCO2 higher than the
one expected by Henry’s Law. However, they are low with respect to many geothermal areas in
the world, where pCO2 in water wells is frequently greater than zero.
420 A. Minissale et al. / Geothermics 37 (2008) 400–428

Fig. 8. Graph of silica vs. temperature for waters in Tianjin wells; the dashed line represents the best fit. Numbers
correspond to sample numbers (see tables).

The deep-equilibration of the fluid at depth has also been verified by the concentration of
silica as a function of temperature (Fig. 8). In spite of the intense exploitation of the field over
several decades, and the different lithologies of the Tertiary and Quaternary poorly consolidated
sediments and pre-Tertiary (mostly limestone-rich) metamorphic formations, the amount of silica
in solution is a function of formation temperature.

11. Water–rock interaction, chemical speciation and mineral equilibria

The chemical activity of the calculated dissolved species in the geothermal solutions, as well
as the saturation indices (SI)3 for the most significant minerals in the Tianjin geothermal wells
(Table 6) have been computed using the PHREEQC-2.11 simulation code (Parkhurst and Appelo,
1999). The indices for relevant oversaturated mineral phases (SI > 0) in the well fluid are shown
in bold in that table.
The data presented in Table 6 suggest that almost all water wells are saturated with respect to
a carbonate phase, either calcite and/or aragonite and/or dolomite, as well as quartz.
Saturation with respect to carbonates is not surprising, because the loss of CO2 from solution at
atmospheric pressure during production increases the pH of the solutions, thereby favouring calcite
precipitation according to the Ca2+ + CO3 2− = CaCO3 reaction, the concentration of CO3 2− ions
in solution being strongly dependent on pH.

3 SI = log(I /K), where I is the ionic activity product for the described mineral phase and K is the theoretical equilibrium
ap ap
constant of formation for the same mineral phase.
Table 6
Saturation Index (SI) for relevant minerals in Tianjin geothermal waters (calculated at reservoir temperatures)
Sample Well name Dolomite Calcite Aragonite Fluorapat. Chalcedony Quartz Goethite Greenalite Pyrite Magnetite Hematite Maghemite ZnSiO3 Willemite FCO3 Apatite Dolomite Fe3 (OH)8
no.
Ca(Mg)CO3 CaCO3 CaCO3 Ca5 (PO4 )3 F SiO2 SiO2 Fe3 O(OH) Fe2 3Si2 O5 (OH)4 FeS2 Fe3 O4 Fe2 O3 Fe2 O3 Zn2 SiO4 CaMg(CO3 )2
1 DKJ 0.347 0.389 0.238 2.148 0.083 0.541 2.813 −3.087 10.777 7.691 7.591 −2.099 3.914 2.006 16.379 0.935 −7.644
2 SH (Sport Hotel) −0.315 0.066 −0.087 0.432 −0.038 0.438 4.380 0.887 14.048 12.086 10.711 1.265 2.921 0.204 13.878 0.286 −2.850
3 HHL03 −1.754 −0.663 −0.812 −1.982 −0.331 0.121 2.816 −3.778 11.364 7.837 7.607 −2.243 2.587 −0.275 8.217 −1.175 −7.759
4 DFZZ01 0.223 0.368 0.222 1.584 −0.130 0.305 5.687 3.635 12.029 16.149 13.373 3.131 4.863 3.976 14.200 0.781 −0.087
5 DFZZ01−R −0.309 0.240 0.087 1.086 −0.208 0.264 4.823 2.711 nd 13.642 11.591 2.228 3.862 2.276 14.871 0.297 −1.158
(DFZZ02)
6 AS01 0.076 0.338 0.200 1.538 0.006 0.408 6.205 3.628 12.046 17.576 14.458 3.401 5.311 4.527 12.483 0.591 0.007

A. Minissale et al. / Geothermics 37 (2008) 400–428

7 AS01-R (AS02) −0.082 0.145 −0.003 nd 0.236 0.684 nd nd nd nd nd nd 3.450 0.863 nd 0.493 nd
8 HHL01 −0.179 0.381 0.245 1.530 −0.050 0.346 5.804 2.564 12.091 16.541 13.664 2.466 4.281 2.486 12.454 0.328 −1.261
9 HHL01-R −0.601 0.253 0.102 1.235 0.167 0.625 5.507 5.191 nd 15.782 12.979 3.289 4.296 2.686 14.524 −0.014 0.447
(HHL02)
10 NK15 (Zoo) 0.242 0.581 0.448 1.234 −0.095 0.287 5.391 0.628 11.981 15.308 12.861 1.316 4.149 2.180 11.690 0.731 −3.062
11 WQ10 0.500 0.688 0.563 1.251 −0.110 0.239 5.996 −0.614 12.475 16.582 14.118 1.783 4.148 1.991 9.880 0.946 −3.079
12 JH 0.157 0.383 0.255 nd −0.345 0.018 6.230 1.265 12.643 17.642 14.567 2.554 4.342 2.695 nd 0.620 −1.493
13 DG24 0.509 0.737 0.614 nd −0.186 0.154 6.887 1.626 12.705 19.311 15.917 3.331 4.744 3.194 nd 0.942 −0.760
14 Tg19 (Tanggu) −0.350 0.395 0.278 −0.302 −0.131 0.185 6.134 −0.557 11.695 17.364 14.444 1.317 5.347 4.207 5.811 0.053 −3.593
15 WQ5 −0.482 −0.356 −0.464 nd −0.020 0.258 5.923 −3.986 9.543 16.289 14.079 0.003 6.404 5.967 nd −0.130 −6.221
16 DL25 (Bio Park) −0.760 −0.003 −0.113 nd −0.065 0.217 5.137 −5.046 10.068 14.330 12.500 −1.469 4.735 2.701 nd −0.401 −8.005
17 DL25R (Bio −0.838 −0.160 −0.285 nd 0.119 0.468 5.725 0.044 nd 16.108 13.577 1.242 7.061 7.588 nd −0.393 −3.553
Park)
18 WANG 3 0.500 0.541 0.409 nd 0.287 0.663 nd nd nd nd nd nd −0.829 −8.192 nd 0.981 nd
19 DL16 1.153 0.918 0.800 nd −0.323 −0.006 6.272 −2.392 11.790 17.156 14.719 1.592 5.015 3.734 nd 1.556 −3.802
20 NK14 1.132 0.932 0.813 5.450 −0.069 0.255 7.565 3.070 13.681 21.288 17.294 4.345 5.352 4.200 16.692 1.545 0.619
21 JN02 −0.250 0.146 0.016 nd −0.074 0.294 5.733 0.493 17.384 16.131 13.564 1.683 −0.227 −6.679 nd 0.220 −2.789
22 DL11 0.086 0.577 0.463 nd −0.156 0.142 5.509 −3.388 11.595 15.459 13.222 −0.363 4.128 1.677 nd 0.465 -6.248
23 WANG-4 −0.826 −0.056 −0.169 nd −0.309 −0.011 4.352 −7.453 16.835 11.892 10.907 −2.678 −2.567 −11.560 nd −0.447 −9.815
24 HD09 −0.278 0.077 −0.032 nd −0.104 0.171 5.718 −3.641 10.514 16.049 13.668 −0.408 4.986 3.216 nd 0.074 −6.460
25 HD09-R (HD02) 0.527 0.459 0.350 nd −0.016 0.264 6.728 −0.766 nd 18.937 15.686 1.663 6.328 5.825 nd 0.882 −3.485
26 HD12 −0.224 0.152 0.042 nd −0.013 0.272 5.454 −3.938 10.286 15.267 13.132 −0.784 5.576 4.344 nd 0.137 −6.980
27 HD12-R (HD13) −1.482 −0.631 −0.767 nd 0.466 0.862 4.512 −0.661 nd 12.541 11.082 −0.116 4.272 1.954 nd −0.975 −5.262
28 HD14 0.316 0.384 0.277 nd −0.131 0.138 6.133 −3.174 9.578 17.180 14.513 0.227 6.517 6.251 nd 0.657 −5.674
29 HD14R −1.441 −0.531 −0.665 nd 0.399 0.784 4.248 −1.838 nd 11.828 10.570 −0.907 3.943 1.291 nd −0.950 −6.430
30 JXW −0.230 0.071 −0.046 nd −0.273 0.037 5.499 −3.386 10.622 15.349 13.184 −0.117 5.267 4.143 nd 0.164 −5.894
31 XQ10 −0.130 0.158 0.048 nd −0.062 0.222 5.715 −3.503 10.606 15.966 13.653 −0.262 5.216 3.674 nd 0.232 −6.281
32 DGZT 0.437 0.643 0.541 nd −0.216 0.035 6.281 −3.893 11.732 17.562 14.835 0.093 4.497 2.178 nd 0.754 −6.038
33 XQ11 −0.006 0.325 0.222 nd −0.041 0.211 6.052 −4.039 10.162 16.910 14.375 −0.318 5.734 4.490 nd 0.313 −6.609
34 ZL1 0.431 0.498 0.380 nd −0.014 0.303 6.108 −0.726 11.391 17.176 14.391 1.263 5.313 4.022 nd 0.834 −3.781
35 DL28 −0.062 0.185 0.073 nd −0.216 0.075 6.000 −2.282 10.866 16.948 14.213 0.461 5.074 3.586 nd 0.308 −5.031
nd, not determined; data in bold correspond to saturated samples.

421
422 A. Minissale et al. / Geothermics 37 (2008) 400–428

Almost all the water wells in Table 6 are supersaturated with respect to quartz, indicating that
more soluble phases, such as chalcedony, control silica solubility. Since the solubility of silica is
strongly dependent on temperature (Fournier, 1991), any conductive, convective or mixing cooling
during production may result in quartz over-saturation in the injected fluids. Although theoretically
possible, injectate oversaturated in quartz may not precipitate any silica phase because of kinetic
effects (Icopini et al., 2005).
Data in Table 6 suggest that there are several unexpected Fe- and Zn-mineral phases (e.g.
goethite, magnetite, hematite, pyrite) whose SI is positive. Solutions saturated with respect to these
minerals are associated typically with alteration areas of sulfide ore deposits (e.g. Bigham et al.,
1996) but not very common in geothermal systems. We would have expected fluids oversaturated
in such mineral phases from the high-temperature, lower redox wells producing from the pre-
Tertiary crystalline formations (pre-Sinian basement), but these mineral phases have been found
supersaturated even in fluids produced from wells bottoming in the low-temperature Tertiary and
Quaternary formations. This suggests that Fe–Zn mineral precipitates may be produced by the
oxidation of the low-quality steel used in well casings and submerged pumps.

12. SEM-EDS and XRD analysis of filtered material from well waters sampled in 2005

The >0.45-␮m filtered particles carried in suspension by the fluid in most of the Tianjin water
wells have been analyzed by scanning electron microscopy equipped with energy dispersive
system (SEM-EDS) and, where possible, by X-ray diffraction (XRD). The first set of samples
was collected in January–February 2005. Results have been summarized in Table 5, where the
most likely minerals able to fit the SEM-EDS analysis are shown in the column labelled “possible
phases”. Where no common minerals fit the elements analyzed, the single elements found have
been reported in the same column (e.g. Hg, Fe, Mg–Fe).
In several wells (AS01, JH, DL25-R, HD12, HD14 and DL28), the quantity of material accu-
mulated in the filters is relatively high in relation to the quantity of the filtered water (50 ml).
Plagioglase, quartz, K-feldspar, Fe–S and Zn–S seem to be the most common solids, with lesser
amounts of CaCO3 and NaCl mineral phases. The presence of entrained solids suggest that they
could be an important factor in plugging the reservoirs during injection, probably even more
important than the precipitation of Fe–Zn mineral phases described in Section 11. The presence
of solids containing Fe, S and Zn in the retained/filtered particles is in good agreement with the
SI of the fluids corresponding to the Fe–Zn minerals.
Additional samples of material were gathered at the surface in July 2005. The purpose of the
sampling was to determine if the filtered material could have been released by the iron-made
surface installations located between the wellheads of the production and the injection wells (e.g.
pipes and heat-exchangers). The additional samples include (see Table 5):

(1) filtered material at the heat-exchanger from a new well drilled in the center of Tianjin city;
(2) fragment of iron pipe from the same well as 1);
(3) incrustation material in the iron pipe in 2);
(4) fragment of iron from the wellhead of DL25 at Bio Park;
(5) iron pipe at Bio Park between wellhead of DL25 and heat-exchanger;
(6) incrustation in wellhead of DL25 at Bio Park;
(7) incrustation in pipe between wellhead of DL25 and heat-exchanger;
(8) particles collected from the filtering system in injection well DL25R at Bio Park.
 A. Minissale et al. / Geothermics 37 (2008) 400–428 423

Apart from the first three samples, which are from the new well drilled in the center of Tianjin
city, the other five samples are from well DL25. This Bio Park well is of particular economic
importance, because it supplies heat to an important greenhouse complex producing multiple
agricultural products (orchids, tomatoes, etc.).
With the exception of the iron at the Bio Park wellhead, which is made of high-quality chrome-
rich steel (Cr = 17% and Ni = 7%), all the remaining iron samples are of low-quality iron and
present extensive iron-oxidation products (mostly goethite).
The three incrustations from the Bio Park production well DL25 (samples 16b, 16d, and 16f;
Table 5), and those collected from the wellheads of WANG-4 and HD12 [samples 23(b) and
26(b); Table 5] in February 2005, are similarly composed of detrital material, such as silicates
and Fe-oxides and Fe-hydroxides, embedded or cemented in a carbonate matrix.
The filtered material sampled at the filtering device installed in front of the wellhead of injection
well DL25R at the Bio Park (sample 17a; Table 5), has been analyzed by SEM-EDS, with one
raster analysis and 10 single-spot analyses. The raster analysis by back-scattered electrons has
allowed a rough estimation of detrital silicates, mainly quartz (about 10%) and iron-mineral
phases (about 90%). One of the 10 spot analyses detected detrital material (quartz and silicates);
the remaining nine identified Fe-oxides, Fe-hydroxides, Fe-silicates, plus similar Zn-compounds,
with minor sulfur (sulfates) and carbonate material.
The results obtained at the DL25R well, the only one with an efficient filtering system, can be
extended to all the other wells, the iron structures being very similar, as is the SI of minerals and
the Fe(Zn)-rich phases recognized in all production wells, largely independent of the geology of
the producing formation.

13. Evaluation of potential reservoir plugging during injection

The main objective of this study was to evaluate the chemical and physical processes causing
the difficulties encountered at the Tianjin geothermal field during the injection of waste (cooled)
fluids back into the reservoir(s).
Neither the produced nor the injected Tainjin fluids seem to be particularly chemically reactive.
According to geochemical modelling calculations, there seem to be three types of minerals that
may precipitate during the injection process: (1) chalcedony, (2) calcite, and (3) Fe–Zn oxides
(hydroxides) and sulfides.
Precipitation of calcite seems to be unlikely since the quantity of CO2 in the geothermal
fluid is that expected on the basis of the hydrostatic pressure and temperature of production
wells, without any CO2 oversaturation (see Fig. 7). Moreover, the solubility of CO2 is higher
at low temperatures and therefore, even if produced fluids are saturated with respect to calcite,
the injectate will be undersaturated because of the lower temperature of the fluid once it passes
through the heat exchanger. To support this interpretation, the SIcalcite values have been plotted
versus temperature in Fig. 9. It is evident that for investigated pairs of deep production/injection
wells (e.g. HD12-HD13; HD9-HD02; DL25-DL25R), the injected fluid is clearly undersaturated
in calcite. The situation is less clear for the shallower wells open in the Tertiary (e.g. AS01-AS02)
and in the Quaternary (e.g. DFZZ01-DFZZ02) formations. Fluids in the shallow production and
injection wells are oversaturated, and calcite precipitation during injection cannot be excluded.
The existence of a metastable state of supersaturation in production wells suggests that calcite
will not precipitate from injected fluids having such SI values.
A silica polymorph, such as chalcedony, is considered the most likely potential cause of chem-
ical sealing and plugging agent in the injected fluids, especially for the higher temperature fluids
424 A. Minissale et al. / Geothermics 37 (2008) 400–428

Fig. 9. Diagram of saturation index (SI) of calcite versus temperature for waters from Tianjin wells, including injected
fluids. The arrows indicate that the saturation index decreases with injection (see text). Numbers correspond to sample
numbers (see tables).

and in wells where the fluid temperature drop, after utilization, is significant. The solubility of
chalcedony or other silica polymorphs drops as the fluid temperature decreases, and the kinetics
of precipitation probably preclude immediate chalcedony precipitation within the heat exchanger.
With the exception of sample 3 (from well HHL03), which has a very low SiO2 concentration
(Table 1), it is evident that the cooling of the injected fluids (along the direction of arrows in
Fig. 10), makes the precipitation of chalcedony in the reservoir theoretically possible, though
unlikely. In fact, the kinetics of silica precipitation are extremely slow at the relatively low SiO2
concentrations (always <60 mg/l) and temperatures found in the Tianjin wells, and explains why
silica scaling was never found inside the heat exchangers. Moreover, we did not find particles
of silica polymorphs in the filtered injectate. The subsequent heating of the injected fluids in the
reservoir further reduces the tendency of silica to precipitate.

14. Discussion and conclusions

The thermal fluids produced by the Tianjin geothermal wells seem to derive from two main
aquifers. The shallower one, located in the Tertiary–Quaternary formations, is characterized by
temperatures below 70–80 ◦ C, and is predominantly of Na–HCO3 composition with salinities
lower than 1000 mg/l and high Na/K ratios (up to 300; Fig. 2c). The deeper aquifer, located in
the pre-Tertiary formations, has temperatures up to 100 ◦ C, of predominant Na–Cl type, total
dissolved solid contents larger than 1000 mg/l (up to 4000 mg/l) and low Na/K ratio (below 20).
 A. Minissale et al. / Geothermics 37 (2008) 400–428 425

Fig. 10. Temperature vs. silica for waters from Tianjin wells, including injected fluids. The diagram also shows the
saturation lines for some silica mineral phases as a function of temperature (solid lines). The dashed lines illustrate the
effects of injection. Numbers correspond to sample numbers (see tables).

The two aquifers are physically separated (in distinct geologic formations and at depths differing
by more than 1500 m) without any evident fluid mixing trends (Fig. 2d).
The average thermal gradient in the Tertiary and Quaternary formations is about 3 ◦ C/100 m,
slightly lower that the average crustal gradient in stable cratonic areas (Fig. 6). The Tianjin field is
a good example of geothermal energy exploitation in an area where the anomalous thermal flow
is localized in a structural high, in this case in the pre-Tertiary formations near the city of Tainjin.
The surrounding regions, WNW and ESE of the city, present normal thermal gradients.
The pH of the two thermal aquifers is neutral-to-slightly basic (Table 1), which suggests that
acid gases, such as H2 S and CO2 , typical of active hydrothermal systems, do not affect the pH
of the discharging fluids. Although several wells have CO2 as the main gas in solution (Fig. 4),
its concentration seems to be compatible with increased solubility of CO2 caused by higher
hydrostatic pressures in accordance with Henry’s Law (Fig. 7). Moreover, the isotopic carbon
composition of both DIC and CO2 (Table 4) suggests that this CO2 is not only hydrothermal
(through decarbonation reactions), but partly formed inside the reservoir formations through
oxidation of organic matter. Crustal 3 He/4 He ratios determined in fluid samples from four wells
(Table 4) also suggest that a limited fraction of CO2 -rich mantle gas rises through the sedimentary
formations in the Tianjin area.
The chemical and isotopic data and the geochemical calculations for the Tianijin geothermal
wells do suggest that plugging is not occurring in the reservoir due to chemical processes and
will not affect the long-term injection strategy for the field. On the contrary, we found that
426 A. Minissale et al. / Geothermics 37 (2008) 400–428

the produced waters transport solids to the surface, consisting mainly of Fe(Zn)-minerals and
subordinate silicate-detrital minerals. It is therefore likely that these solids may cause plugging
when waste (cooled) fluids are injection back into the reservoir.
Plugging by Fe-bearing solids is not very common in geothermal exploitation when good-
quality steels are used in well casings, pumps, heat exchangers and pipes. The few examples
reported in the literature where this type of mineral plugging has occurred (e.g. Akar et al., 1995;
Amalhay et al., 1995) refer to fluids particularly rich in H2 S in the gas phase (but this is not the
case of Tianjin), where the increased acidity of solutions caused by the oxidation of H2 S to H2 SO4
and of Fe to Fe2+ , with production of free H2 according to the reaction:

Fe + H2 S + 4H2 O  Fe2+ + 5H2 + SO4 2−

Such a reaction (or similar ones) may of course also be triggered by (i) free oxygen, (ii)
particularly low redox potentials (redox pairs) or, even worse, (iii) free oxygen associated with
the presence of thiobacteria.
Unless the production/injection loop is tightly sealed, atmospheric fresh air (and therefore
free oxygen) can be introduced into the system. After the air has dissolved, oxygen and nitrogen
will tend to exsolve when deep-formation temperatures achieve values higher than those of the
injected fluids, since the solubility of gases is reduced at higher temperatures. The released gas
may flow toward the surface along the well casings that represent the preferential flow channels.
Oxidation of casings could be enhanced by the presence of thiobacteria, which process iron in
their metabolism and are very active in geothermal environments, especially where free oxygen
is available (Brock et al., 1976).
If the iron casings are being oxidized, we expect to find some H2 in the gas phase stripped
from the produced waters. As shown in Table 3, hydrogen concentrations in wells vary from
0.015 ␮mol/l in well DFZZ01 (sample 4) up to 6.6 ␮mol/l in well DGZT (sample 32s). Such
high concentrations of H2 are not common in low-temperature geothermal systems, especially
those rich in N2 such as are often found in Tianjin. In nature, high concentrations of H2 in
low-temperature environments are often associated with Fe2+ -rich rocks such as ophiolites (e.g.
Abrajano et al., 1988).
Based on the data presented above, we suggest that the decrease in the injectivity of Tianjin
geothermal wells over time is due to physical plugging of the reservoir by Fe–Zn-rich and minor
detrital particles suspended in the injectate. Remediation in all wells used for injection should
consist of the installation of mechanical filters, such as the one presently used at the Bio Park
facilities (well DR25R). Filtering of the fluids before their injection should be able to remove
most of the materials causing reservoir plugging.
When the injection problem began in Tianjin, some field operators responded by installing
filtering devices, although there were no data at that time to suggest that plugging by suspended
particles was the problem. The “a posteriori” analysis of chemical data presented here suggests
that mechanical filtering of suspended solids is the main effort required in the future to prevent
reservoir plugging. We determined that the filtering device installed at the Bio Park Farm (well
DL25R) “cleans” the injected fluid, with a solid particle residual as low as 0.002 mg/l.
In a long-term injection strategy for the Tianjing geothermal field, the replacement of old
material with new, high-quality stainless steel in well and surface installations would lower the
potential for corrosion and the presence of reservoir plugging particles in the fluid that is injected
back into the geothermal reservoir.
 A. Minissale et al. / Geothermics 37 (2008) 400–428 427

Acknowledgements

The Institute of Geosciences and Earth Resources (IGG) of the National Research Council of
Italy (CNR) and the Aode Geothermal Institute (AODE) of the Tianjin Municipality, carried out
this investigation under an agreement between the Italian Ministry for the Environment (through
the Sino-Italian Cooperation Program–PMO) and the Chinese Ministry of Science and Technology
(MOST), signed in Beijing in November 2004.
Nevio Capodagli (PMO) is warmly thanked for his assistance throughout the project. Mario
Paolieri is kindly acknowledged for helping with the SEM-EDS analysis. The contributions of
Carol Bruton (Lawrence Livermore Laboratory) and S. Simmons (University of Auckland, New
Zealand) during the revision process, improved considerably the first version of the manuscript.

References

Abrajano, T.A., Sturchio, N.C., Bohlke, J.K., Lyon, G.L., Poreda, R.J., Stevens, C.M., 1988. Methane-hydrogen gas seeps,
Zambales Ophiolite, Philippines: deep or shallow origin. Chem. Geol. 71, 211–222.
Akar, A.A., Ignatiadis, I., Lecuseur, H., 1995. Methods for detecting perforation of wells exploiting geothermal fluids.
In: Proceedings of the 1995 World Geothermal Congress, 18–31 May, Florence, Italy, pp. 2397–2402.
Amalhay, M., Cotiche, C., Ignatiadis, I., 1995. Study of the electrochemical behaviour of a carbon steel in a real and
treated geothermal environment. In: Proceedings of the 1995 World Geothermal Congress, 18–31 May, Florence,
Italy, pp. 2369–2374.
Aquater, 1984. Mathematical model of the Tianjin hydrothermal field (final report). United Nations D.T.C.D., Contract
TCD-CON 21/83, S. Lorenzo in Campo, Italy, 213 pp.
Axelsson, G., Dong, Z., 1998. The Tanggu geothermal reservoir (Tianjin, China). Geothermics 27, 271–294.
Bigham, J.M., Schwertmann, U., Traina, S.J., Winland, R.L., Wolff, M., 1996. Schwertmannite and the chemical modelling
of iron in acid sulfate waters. Geochim. Cosmochim. Acta 60, 2111–2121.
Brandi, G.P., Ceccarelli, A., Di Paola, G.M., Fengzhong, L., Pizzi, G., 1986. Model approach to the management of the
Tianjin hydrothermal field, China. Geothermics 15, 639–655.
Brock, T.D., Cook, S., Petersen, S., Mosser, J.L., 1976. Biogeochemistry and bacteriology of ferrous iron oxidation in
geothermal habitats. Geochim. Cosmochim. Acta 40, 493–500.
Craig, H., 1961. Isotopic variations in meteoric waters. Science 133, 1702–1703.
Craig, H., 1963. The isotopic geochemistry of water and carbon in geothermal area. In: Tongiorgi, E. (Ed.), Nuclear
Geology on Geothermal Areas. C.N.R., Pisa, Italy, pp. 17–53.
Craig, H., Lupton, J.E., 1976. Primordial neon, helium and hydrogen in oceanic basalts. Earth Planet Sci. Lett. 31, 369–385.
Ding, G., Lu, Y., 1983. Discussion of the basic features about neotectonic appearance in North China platform. Earthquake
Sci. North China 1, 1–9.
Fournier, R.O., 1991. Water geothermometers applied to geothermal energy. In: D’Amore, F. (Ed.), Application of
Geochemistry in Geothermal Reservoir Development. UNITAR-U.N.DP, Rome, Italy, pp. 37–65.
Giggenbach, W.F., 1991. Isotopic composition of geothermal water and steam discharges. In: D’Amore, F. (Ed.), Appli-
cation of Geochemistry in Geothermal Reservoir Development. UNITAR-U.N.DP, Rome, Italy, pp. 253–273.
Giggenbach, W.F., Gonfiantini, R., Jangi, B.L., Truesdell, A.H., 1983. Isotopic and chemical composition of Parbaty
Valley geothermal discharges, NW-Himalaya. Geothermics 12, 199–222.
Han, Z., Wu, L., Ran, Y., Ye, Y., 2003. The concealed active tectonics and theor characteristics as revealed by drainage
density in the North China Plain (NCP). J. Asian Earth Sci. 21, 989–998.
Hu, R.L., Yue, Z.Q., Wang, L.C., Wang, S.J., 2004. Review on current status and challenging issues of land subsidence
in China. Eng. Geol. 76, 65–77.
IAEA/WMO, 2001. Global Network of isotopes in precipitation. The GNIP Database, http://isohis.iaea.org.
Icopini, G.A., Brantley, S.L., Heaney, P.J., 2005. Kinetics of silica oligomerization and nanocolloidal formation as a
function of pH and ionic strength at 25 ◦ C. Geochim. Cosmochim. Acta 69, 293–303.
Kun, W., 2003. Reinjection experiments in the basement geothermal reservoir, Tianjin, China. In: Proceedings of the
International Geothermal Conference (IGC-2003), 14–17 September, Reykjavik, Island, pp. 21–26.
Kun, W., Chunhua, L., Jialing, Z., 2000. Reservoir evaluation for the Wuqing geothermal field, Tianjin, China. In:
Proceedings of the 2000 World Geothermal Congress, May 28–June 10, Kyushu-Tohoku, Japan, pp. 3103–3108.
428 A. Minissale et al. / Geothermics 37 (2008) 400–428

Langelier, W., Ludwig, H., 1942. Graphical methods for indicating the mineral character of natural waters. J. Am. Water
Assoc. 34, 335–352.
Li, J., 2003. Reservoir evaluation of the Zhouliangzhuang geothermal field, Tianjin, China. The United Nations University,
Geothermal Training Programme, Reykjavik, Island, Report 2003/15, pp. 361–384.
Liao, Z., Chen, Z., 1993. Thermal waters of Shanlingzhi geothermal field, Tianjin. Acta Scientiarum Naturalium Univer-
sitatis Pekinensis 29 (2), 224–232.
Montegrossi, G., Tassi, F., Vaselli, O., Buccianti, A., Garofalo, K., 2001. Sulphur species in volcanic gases. Anal. Chem.
73, 3709–3715.
O’Nions, R.K., Oxburgh, E.R., 1988. Helium, volatile fluxes and the development of continental crust. Earth Planet. Sci.
Lett. 90, 331–347.
Pang, Z., 2000. Isotope geochemistry of geothermal waters in northern China basin: implications on deep fluid migration.
In: Proceedings of the 2000 World Geothermal Congress, Kyushu-Tohoku, Japan, May 28–June 10, pp. 1559–1564.
Parkhurst, D.L., Appelo, C.A.J., 1999. User’s guide to PHREEQC (Version 2): a computer program for speciation, batch-
reaction, one-dimensional transport, and inverse geochemical calculations. U.S. Geological Survey, Water-Resources
Investigations, Report 99-4259, 312 pp.
Rollinson, H., 1993. Using Geochemical Data. Longman, London, U.K, p. 352.
Xu, J., Hong, H., Zhao, G., 1985. Evolution and mechanic features of the Cenozoic rift basin in North China plain. Res.
Mod. Crust Movement 1, 26–40.
Zheng, Z., Yin, H., Zeng, X., 1990. Thermal reservoir models and heat flow characteristics of geothermal field in Tianjin.
Bull. Inst. Hydrogeol. Eng. Geol. 6, 25–42.