GO E ~ A E D RM

ELSEVIER Geoderma 68 (1995) 193-210

Mineralogical, chemical and morphological features of salt accumulations in the Flumen-Monegros district, NE Spain
C. Vizcayno a, M.T. Garcia-Gonzalez a, M. Gutierrez a, R. Rodriguez b
" Cemro de Ciencias Medioambientales, CSIC, Serrano 115 dup, 28006 Madrid, Spain b Univ. Lleida, ETSIA, R, Route 144, Lleida, Spain

Received 6 September 1994; accepted 13 April 1995

Abstract
Relationships among the mineralogy, morphology and the formation processes of salt accumulations were studied in three sampling areas in the Flumen-Monegros district, which represent three geochemical environments [Na-SO4-CI, Na-(Mg)-SO4-C1 and Na-CO3-SO4-C1], according to chemical and mineralogical results. The samples included both natural ones and others that were obtained in the laboratory by the crystallization of brines with and without substrate. A climatic chamber was used to reproduce the environmental conditions. Laboratory crystallization of brines without soil substrate does not always reproduce the natural mineral associations. Such associations were reproduced, however, when the crystallization was carried out with the epipedon. New morphologies are described for bloedite (radiating prismatic, and foliated rosette-like) and burkeite ( book plates and spheroidal association of plates), the latter formed through capillary evaporation. X-ray diffraction, scanning electron microscopy (SE and BSE modes), energy dispersive X-ray spectrometry and polarized light microscopy were some of the techniques used, supplemented by chemical data.

1. Introduction
Up to now the majority of papers on soil salt accumulations have reported the mineralogy and morphology of saline species. The least number of publications have been those which reproduced the crystallization of the minerals in the laboratory, in order to model the mineralogy of salt efflorescences, and to improve the knowledge of the formation conditions, 0016-7061/95/$09.50 1995 Elsevier ScienceB.V. All rights reserved S S D I O O 1 6 - 7 0 6 1 (95)00032-1

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morphologies and stability of the phases ( Vergouwen, 1981 a; De la Pefia et al., 1982; Keller et al., 1986). With the aim of understanding the relationships between the mineralogy, morphology and formation processes of salt accumulations in the Flumen-Monegros district, both natural samples and others that were obtained in the laboratory by the crystallization of brines, were studied. A climatic chamber was used in the laboratory to reproduce the natural conditions. Considering that the substrate could have an important role in the formed mineral assemblages, and in their morphology, the laboratory experiments were done both with and without substrate of soil.

2. Materials and methods

The Flumen-Monegros irrigation district is situated in the Province of Huesca (northeastern Spain) in the Ebro Valley Basin (Fig. 1). Geologically, the surface materials are Miocene marls and sandstones, and different types of Quaternary deposits (Quirantes, 1978). The parent materials of the studied areas are finely laminated Holocene sediments rich in silt, with a high calcium carbonate content and a high level of salinity-sodicity (Porta and Rodriguez-Ochoa, 1991 ). The major macromorphological and chemical characteristics of the soil profiles where the salt accumulations were collected are shown in Tables 1 and 2. The chemical characteristics of the groundwaters are related to the salinity of the Tertiary and Quaternary materials, and irrigation water characteristics. The district has been under irrigation management since the 60's; this fact has caused water seepage, leaching and redistribution of salts, as well as uprising of the water table. The sampled areas are in the bottom positions in the landscape and due to the fact that they are actually abandoned, without irrigation and cultivation, they are acting as zones of local evaporation. The climate during the period 1969-1992 is characterized by a winter mean precipitation, maximum temperature and mean relative humidity of 88.4 mm, 12.4C and 64%, respectively; winter reference evapotranspiration (ETo, Blaney-Criddle method, Doorenbos and Pruitt, 1977) is 75 mm. The summer mean precipitation, maximum temperature and mean relative humidity are 98.8 mm, 34.6C and 42%, respectively; summer and annual ETo is 600 and 1270 mm, respectively. In the Thornwaite classification the climate is DB2' db3'. Worth noting are NW and SE dry winds which favor evaporation, and the influence of the rain-shadow effect produced by the mountains which surround the Ebro Basin, resulting in a scarcity of precipitation. The soil moisture regime, is aridic for soils that retain less than 70 mm of water and xeric for soils with larger reserves (Jarauta, 1989). At the localities of Marcrn (MA), Almuniente (AL) and Callrn (CA) in the FlumenMonegros irrigation district (Fig. 1), 48 surface salt accumulations, 9 winter groundwaters and 6 winter brines of ephemeral ponds, were sampled. Sampling was carried out during 1992 and 1993. Laboratory efflorescences were obtained from the brines, filtered previously, in three ways: ( 1) evaporation pan experiment; (2) capillary evaporation experiment using a column of a natural epipedon (5 cm high; 6 cm diameter) wrapped in parafilm to prevent lateral evaporation; brine was added at the base till efflorescence appeared on the surface;

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195

~f~O~

20~Km

{" - ", Ftumcn - Momp~ros . . - / irrigation d;strlct (~ Study oreo

Ca/t~n

"

Marcdn

'

'

Glacis slopes with fine detritic materials. CalcixeroUic Xerochrepts. Fluventic Xerochrepts. Typic Xerofluvents. Valleys and depressions with fine detritic materials, Typic Xerofluvents. Oxyaquic Xerofluvents. Slopes with Tertiary materials and local deposits, Typic Xerorthents. Xeric Torriorthents. Residual platforms (terraces and glacis) with coarse detritic materials. Calcixerollic Xerochrepts. Petrocalcic Xerochrepts. XerolUc Paleorthids.

Structural platforms with Miocenic sandstones and marls. Typic Xerorthents, Xeric Torriorthents. Xeric-Lithic Torriorthents.

Fig. 1. Location of the studied area. Geomorphology,parent materials and most frequent soils. and (3) evaporation o f a portion of filtered brine administered over a column of natural epipedon prepared as in (2). A Heraeus Votsch HPS-500 chamber was used for simulation of environmental conditions. Evaporation sequences of 20C at 60% RH and of 35C at 40% RH modelled winter and summer conditions, respectively. The length of each experiment was about a week.

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Table 1 Major macromorphological features of the soil profiles Profile

MA

Horizon
Apl Ap2 C 2C 3C 4C 5C Ap~ Ap2 Ci 2Bw~nay

Depth (cm)
0-10 10-25 25--42 42-60 67-84 90-140 140-160 0-9 9-20 20-60 60-100 100-150 0-7 7-20 20--44 44-75 75-90 90-120

Colour (moist) 2.5Y5/4 2.5Y5/4 2.5Y6/5 2.5Y5/6 2.5Y5/4 10YR5/6 7.5YR5/6 10YR6/4 10YR6/4 7.5YR6/5 7.5YR5/5 10YR4/3 10YR6/8 10YR6/8 10YR4/6 10YR5/6 7.5YR5/6 10YR6/8

Textural class USDA

S-L S-L S-L L-Sa Sa-L Sa-L S-L S-C-L S-C-L S-C-L S-C-L S-C C-L C-L S-C-L S-C-L

Structure
sb,c,vw sb,c,vw ma gr pl,vf, vw pl,m,vw ma sb,c,w pl,m,w ma pr,m,w pr,m,s sb,c,w sb,m,w

Consistence
friable friable friable v. friable v. friable

np, ns
pl, ns friable

AL

firm
pl, ss pl, st pl, st

2Bw2nay
CA

Ap~
Ap2 Bw Bw/C 2C 3C

pr,c,w
pr,m,vw

soft firm firm

friable friable friable

nd nd

ma ma

MA = Marcrn, A L = Almuniente, C A = Callrn, nd = not determined. Texture: S-L = silty loam, L-Sa = loamy sand, Sa-L = sandy loam, C-L = Clay loam, S-C-L = silty clay loam, SC = silty clay.

form: sb = subangular blocky, ma = massive, gr = granular, pl = platy, pr = prismatic; size: c = coarse, m = medium, f = fine, v f = very fine; grade: vw = very weak, w = weak, s = strong. Consistence: v = very, pl = plastic, np = nonplastic, st = sticky, ns = nonstick, ss = slightly sticky.
Structure:

The mineralogical identification was performed using X-ray diffraction (XRD). Patterns were obtained with a Philips PW 1130 diffractometer (graphite monochromated Cu-Kc~ radiation). An operating voltage of 40 kV and a current of 20 mA were utilized. Specimens were lightly ground in an agate mortar to reduce the effects on intensity of preferred orientation in the random powder preparations. The mineral phases were identified with the aid of the Powder Diffraction File. The micromorphological studies were performed on salt accumulations in the corresponding epipedon (about 5 cm depth). The samples were impregnated with polystyrene resin. The thin sections were prepared according to Gillor6 (1980) and described using the standard terminology of Bullock et al. (1985). Submicromorphological study was done with a Zeiss DSM 960 scanning electron microscope (SEM) equipped with a backscattered electron detector (BSE) and an Oxford Link 5118 energy dispersive X-ray spectrometer (EDS). Samples were coated with carbon for SEM study. In some cases, small pieces of the samples were embedded in LR White resin and sectioned transversely. Chemical analyses of groundwaters, brines and dissolved efflorescences were done by flame photometry (Na ), atomic absorption (Mg 2 +, Ca 2 ), ionic chromatography (CI-, S O l - ), titration (CO3H-, CO~- ), conductimetry (EC) and potentiometry (pH).

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197

Table 2 Chemical characteristics of the soil profiles Profile Horizon Depth M.O. CaCOs CE pH Soluble ions (cmol 1-]) SAR (cm) (%) equiv. (dS paste (%) m i) Ca 2+ Mg -'+ Na + CI SO4- CO~- HCOC MA Apl Ap2 C 2C 3C 4C 5C 0-10 10-25 25-42 42-60 67-84 90-140 140160 0.8 0.9 0.4 0.2 0.3 0.0 0.4 1.0 1.4 0.6 nd 0.8 1.2 1.3 (1.9 0.8 0.3 0.4 26.2 25.7 13.4 23.2 15.6 21.7 23.8 30.6 29.4 29.7 nd 24.6 42.5 43.1 23.0 22.9 24.8 26.5 39.1 17.8 14.2 4.5 10.0 4.4 8.9 30.1 37.3 34.2 28.7 13.1 26.9 8.9 6.1 4.4 2.9 nd 8.1 7.8 7.9 8.4 8.2 8.3 8.3 8.3 8.3 8.1 8.4 8.0 54.5 41.4 25.5 5.2 13.2 3.8 nd 37.3 542.3 378.9 275.4 12.7 154.1 142.3 66.9 5.8 133.0 92.9 68.7 2.3 40.6 40.0 35.3 9.3 95.7 52.0 58.8 1.7 48.1 22.1 31.4 nd nd nd nd nd 2.6 2.3 2.4 2.2 2.2 3.2 nd 1.8 2.8 0.6 1.2 1,4 12.7 28.3 11.3 15.1 11.3 nd 80.0 27.5 33.6 20.9 28.9 24.7 nd 51.5 42.2 47.7 53.2 26.8 134.2 48.7 33.4 33.9 19.8 nd

AL

Apl 1-9 Ap2 9-20 Ci 20--60 2Bwlnay 60-100 2Bw2nay 100150 Apl Ap2 Bw Bw/c 2C 3C (1-7 7-20 20-44 44-75 75-90 90-120

27.5 80.1 377.5 186.7228.0 32.0 119.4 367.0 291.5 276.0 31.0 73.0 344.0 255.5 244.0 28.5 56.3 346.5 202.1 222.0 27.5 21.8 133.3 63.5 118.0

CA

1(I.2 6.1 10.1 4.8 10.1 4.5 10.4 4.6 10.4 3.8 nd nd

4.3 305.9 106.5 148.3 34.(I 3.7 100.4 19.3 41.9 17.2 3.0 64.7 14,5 31.9 17.3 1.5 59.2 18.8 10.9 23.3 1.6 32.6 6.7 2.4 19.7 nd nd nd nd nd

MA = Marcdn, AL = Almuniente, CA = Call6n, nd = not determined, - = not detected.

3. Results
T h e c a t i o n i c c o m p o s i t i o n o f the g r o u n d w a t e r s ( T a b l e 3, Fig. 2) is d o m i n a t e d b y N a a n d the a n i o n i c c o m p o s i t i o n b y CI a n d SO4, in all cases. In the A l m u n i e n t e area, the M g c o n t e n t is r e l e v a n t in the g r o u n d w a t e r a n d in the s u m m e r efflorescence. T h e l o w e r v a l u e o f M g in the w i n t e r e f f l o r e s c e n c e is a s s o c i a t e d w i t h a r e l a t i v e e n r i c h m e n t in the N a S O 4 species, the solubility o f w h i c h d e c r e a s e greatly w i t h the l o w e r i n g o f the t e m p e r a t u r e ( T i m p s o n et al., 1986). In the Call6n area the p r e s e n c e o f H C O 3 a n d C O 3 - is i m p o r t a n t . T h e s e facts lead us to c o n c l u d e that the areas r e p r e s e n t three g e o c h e m i c a l e n v i r o n m e n t s : N a - S O 4 - C I , N a (Mg)-SO4-CI, and Na-CO3-SO4-C1.
3.1. M a r c ~ n a r e a

G e o m o r p h o l o g i c a l l y this area (Fig. 1 ) o c c u p i e s the l o w e s t level o f valley p o s i t i o n s a n d the soils were classified as O x y a q u i c X e r o f l u v e n t s , fine silty o v e r sandy, m i x e d ( c a l c a r e o u s ) , t h e r m i c . V e r y h i g h saline a n d sodic phase. T h e g r o u n d w a t e r is located in the Q u a t e r n a r y m a t e r i a l s a n d in t w o o b s e r v a t i o n s the w a t e r table d e p t h s were 9 0 a n d 130 cm. M a c r o m o r p h o l o g i c a l l y , in the w i n t e r e f f l o r e s c e n c e s t r a n s p a r e n t m i r a b i l l i t e crystals ( c o n firmed b y X R D ) o f e l o n g a t e p r i s m a t i c f o r m up to 15 c m in l e n g t h were o b s e r v e d in

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Table 3 Chemical data of groundwaters, brines, dissolved efflorescences and irrigation water ( Figures are averages of the different samples within each area) Sample Na + (%) GW Br Ew Es GW Br Ew Es GW Br Ew Es 43.3 47.4 47.7 47.4 41.2 45.7 46.7 31).0 43.6 47.1 49~5 49.4 11.9 Ca2+ %) 3.7 1.0 1.1 1.4 1.7 0.9 1. l 0.4 3.6 2.8 0.3 0.3 24.1 Mg2* (%) 3.0 1.6 1.2 1.2 7. I 3.5 2.2 19.6 2.8 0.1 0.2 0.3 14.0 CI (%) 21.8 34.3 12.8 1.6 22.3 34.1 3.6 8.3 26.2 23.8 0.9 3.3 4.7 SO] (%) 23.1 14.9 36.7 48.2 26.5 15.5 46.11 41.6 17.9 8.5 18.8 12.0 17.1 HCO-~ (%) 5.1 11.8 0.5 1/.2 1.2 /).3 11.4 0.1 5.9 8.8 13.4 18.1 28.2 CO~ I%) 8.9 16.9 16.6 pH EC (dSm ~ 7.11 44.3 nd nd 28,11 154.0 ud nd I11.0 24.5 nd nd 11.4

MA

9.2 8.1/ nd nd 8.4 7.9 nd nd 8.5 10.8 nd nd 8.3

AL

CA

lrrwa

MA: Marc6n, AL: Almuniente, CA: Call6n, GW: Groundwater, Br: Winter Brines, Ew: Winter efflorescence, Es: Summer efflorescence, -: not detectable, In wa: irrigation water, nd: not determined. microdepressions ( 5 - 2 0 c m ) associated with ephemeral ponds. On other parts of the surface of soil, p o w d e r y salt minerals are present. Within the upper part of the soil, serrated edged rods of mirabillite have been identified, which under atmospheric conditions dehydrate rapidly to form thenardite. In the s u m m e r efflorescences, thenardite and halite mixtures have a puffed type behavior. This area (Fig. 21 is of the N a - S O 4 - C 1 type. X R D results show that halite and thenardite are the predominant c o m p o n e n t s in the s u m m e r efflorescences and mirabillite and halite in the winter ones ( T a b l e 4). The presence o f g y p s u m was also detected; g y p s u m was added to the soil for structure i m p r o v e m e n t in about 1975. Thin layers of winter saline accumulations indicate that they are porous and the organization of groundmass is c h a n g e d mainly by halitic impregnative overgrowths. Also notable are impregnative halite crystals, which in places show fibrous-prismatic growth patterns. Thenardite occurs as small prismatic crystals, which form aggregates with the shape of mirabillite prisms, and as a powdery surface c o v e r i n g the basal material. In both cases there is halitic c e m e n t in the vertical growth directions, which confers consistency. Lenticular thenardite crystals are present in the upper part of the groundmass and also on the surface of the efflorescences. At the latter location, they show dissolution p h e n o m e n a and precipitation aureoles (Fig. 3a). Porphyroblastic g y p s u m fragments of coarse sand size are present, as well as lenticular and small needle-shaped crystals. M i c r o m o r p h o l o g i c a l study of s u m m e r salt accumulations indicates very pronounced disturbance and mix of the groundmass and salt material, forming a strongly d e v e l o p e d structure. Thenardite appears in anhedral crystalline to microcrystalline form, and as rounded and elongate nodules of acicular crystals. Halite is mainly a superimposed cementing agent, but locally fibrous crystals occur in planar pores.

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195

Irrigation waters

1 I~larc~n a r e a 2 Almuniente area 3 Eolian area G r oundwatL~" x Brines

o Winter

fflorescences

Summer efflorescences

\
/\\\, \ "3

Z&

~, Ca'* CI Fig. 2. Ionic compositions (Piper diagram) of the groundwaters, brines, dissolved efflorescences and irrigation waters.

In the SEM study of winter salt accumulations, the morphology of mirabillite could not be observed, due to its transformation into thenardite by dehydration upon placing the samples under vacuum for electron microscopic observation. Thus, in these samples drusylike thenardite crystals were observed (Fig. 4a), which had pseudomorphically replaced mirabillite by dehydration. Crystallization of brines in the environmental chamber, simulating summer and winter conditions and using both pan and capillary evaporation experiments, produced the same mineral species found in the natural samples (Table 4). Only the crystal morphology varied. In the SEM study of the efflorescences obtained by pan evaporation of brines under summer conditions, thenardite growths with a rosette-like morphology have been observed (Fig. 4b). The crystals have a clearly prismatic habit, with a tendency toward lath-shaped individuals. Under winter conditions, prismatic macrocrystals of mirabillite are produced. If capillary evaporation occurs, the mirabillite forms microcrystals with a powdery aspect.

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C. Vizcayno et al. / Geoderma 68 (1995) 193 210

Table 4 Mineralogical composition ( X R D ) of the natural and laboratory salt accumulations of F l u m e n - M o n e g r o s district Mb MA Nat Lab A
B

Tn * *** ***

H * * *** ** *** ***

***

Gy tr Ir tr tr

BI

Ky

Ep

Hx

Bu

Tr

Na

W S W S
W
S

* * * * * * ***

***

AL

Nat Lab A
B

W S W
S

* * tr

* *** * * *
***

**

***

***

Ir

W
S

**
***

CA

Nat Lab A
B

W
S

* *
**

*
**

* *

tr

W
S

* * *
***

W
S

*
**

***
**~

MA: Marc~n, AL: Almuniente, CA: Calldn, Mb: Mirabillite, Tn: Thenardite, H: Halite. Gy: G y p s u m , BI: Bloedite, Ky: Konyaite, Ep: Epsomite, Hx: Hexahydrite, Bu: Burkeite, Tr: Trona, Na: Natr6n, Nat: Natural, Lab: Laboratory, A: without substrate, B: with substrate, W: winter, S: summer. Asterisks indicate relative abundances; tr: traces.

3.2. A l m u n i e n t e a r e a

Geomorphologically this area occupies a depression with a very limited drainage. The soils were classified as Oxyaquic Xerofluvents, fine silty, mixed (calcareous), thermic. Very high saline and sodic phase. The groundwater is located in the Quaternary materials and in two observations the water table depths were 60 and 180 cm. Macromorphologically two types of surface evaporitic accumulations are distinguished independent of the time of year the samples were collected. The first type consists of brittle, white, coherent, microcrystalline efflorescences that are not associated with centimetrical microdepressions. The second type is saline crusts, associated with microdepressions, which are nearly colorless to whitish stratiform masses with a thickness of approximately 1 cm; these coherent masses consist of layers of different consistencies; the layer in contact with the soil substrate is the hardest, and it may seal the soil; the layers are frequently interconnected by radiate growths; hopper- and chevron-type halite crystals are present.
Fig. 3. Thin sections of different salt accumulations. Marcdn area: (a) ( X 4 0 , P P L ) : 1 = T h e n a r d i t e crystals, 2 = Thenardite lenticular, 3 = Haloturbation processes. Abnuniente area: (b) ( 4(), P P X ) . L o w e r layer of the saline crust: Bloedite prismatic radiating with dusty line; contact with the soil substrate in the bottom. (c) ( 40, PPX 115). Saline crust: 1 = Surface layer: Halite hoppers. 2 = Middle layer: Bloedite microcrystalline in foliated aggregates. Almuniente area: ( d ) ( 25, P P L ) . Salt efflorescence: Bloedite. CaliPh area: ( e l ( 100, P P L ) . S u b r o u n d e d crystal of halite showing cleavage. (f) ( 40, P P X ) . I = Book plates of burkeite, 2 = Needle-shaped crystals of trona, 3 = Burkeite and trona.

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201

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C. Vizcayno et al. / Geoderma 68 (1995) 193-210

Fig. 4. Marc~n area: (a) Pseudomorphic thenardite crystals after mirabillite (SE image). (b) Rosette-like thenardite and prismatic gypsum crystals ( SE image). Almuniente area: (c) Cross-section of a saline crust (BSE image). (d) Saline crust (BSE image). (e) Lower ( 1) and middle (2) layers of the saline crust. Cement and needle-shaped of halite and prismatic bloedite (BSE image). (f) Middle (2) and surface (3) layers of the saline crust. Cubic and cement halite and cement and prismatic bloedite crystals (BSE image).

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203

This area (Fig. 2) is of the Na-(Mg)-SO4--CI type. The winter mineralogical association of the efflorescences and the saline crusts includes bloedite, konyaite, and minor amounts ofthenarditeand halite (Table 4). In summer, the proportion ofkonyaiterelafivetobloedite is lower, due to dehydration; a decrease in thenardite content and an increase in the amount of halite is also observable. The micromorphological study of the salt efflorescences (Fig. 3d), indicates that on the surface there are porous, globular, intertwined overgrowths with a layered structure made of alternating layers of crystalline and microcrystalline bloedite; also present are bloedite and halite as cement and as overgrowths which combine massive zones with porous ones. Massive halite is present at the surface forming an irregular seal and locally the bloedite is forming radiate growths with dissolution features. Within the epipedon, bloedite is present as diffuse radiate impregnative nodules and continuous impregnative hypocoatings with serrated edges; there are nodules of microcrystalline gypsum and also individual lenticles. The micromorphological study of the saline crusts allows distinction of three layers; the lower one shows radiate intergrowths of prismatic bloedite crystals, impregnative and displacive in contact with the soil substrate; the successive stages of crystalline growth of bloedite produced internal dusty lines (Fig. 3b, bottom). In the middle layer (Fig. 3c.2), bloedite appears as radiate growths, and/or individualized with microcrystalline characteristics, as well as transitions between macro- and microcrystalline. Also noted are hypidiotopic equigranular intergrowths of halite and bloedite. Halite is present as cubes, in anhedral form, and as arched structures. The surface layer (Fig. 3c. 1) shows halite in anhedral form, as cubes, and at the top as hopper crystals. Bloedite appears as subidiomorphic prismatic and foliated aggregates of microcrystalline character with pseudoparallel arrangement. The middle layer is connected to the surface layer by bloedite in foliated aggregates and prismatic crystals with a semispherical rosette-like morphology. At the submicroscopic scale, the minerals present in the crusts show a variation in morphology and distribution. This is demonstrated by BSE images of vertical cross sections. The crusts consist of the following layers (Fig. 4c): Lower layer: (Fig. 4c. 1, 4d.i, 4e): Formed by idiomorphic prismatic bloedite crystals joined by halitic cement. Some halite overgrowths in the form of needle-shaped crystals were observed. Middle layer: (Fig. 4c.2, 4d.2, 4f): Euhedral cubic halite crystals coexist with idiomorphic and rounded bloedite crystals. Bloedite is occasionally present as cement. Surface layer (Fig. 4c.3, 4d.3): Composed of massive halite, and rosette-like intergrowths of thenardite crystals (Fig. 5a), with minor occurrences of microcrystalline foliated rosette-like aggregates of bloedite (Fig. 5b) and radiate aggregates of prismatic bloedite crystals (Fig. 5c). These surface and middle layers are interconnected by foliated rosette-like bloedite formations (Fig. 5d). The crystallization of brines in the evaporation pan experiment gives rise to associations different from those in natural samples. Halite, epsomite, and hexahydrite are forming under winter conditions, while epsomite is absent from the summer samples; sodium-magnesium sulfates are not present (Table 4). The crystallization of brines, in both capillary and surface water evaporation on a natural epipedon, led to the identification of halite and bloedite/konyaite, in agreement with the mineralogy of natural efflorescences (Table 4).

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Fig. 5. Almuniente area: (a) Halite massive, rosette-like thenardite and rounded btoedite crystals (SE image~. (b) Foliated microaggregatesof bloedite (cross section, BSE image). (c) Prismatic radiating bloedite crystal ( BSE image). (d) Foliated rosette-like bloedite crystals ( SE image).
3.3. Calldn area

Geomorphologically this area occupies a depression with a very limited drainage. The soils were classified as Typic Xerofluvents, fine silty, mixed (calcareous), thermic. Very high saline and alkaline phase. The groundwater is located in the Quaternary materials and the depth of one observation was 230 cm. Macromorphologically, this area is characterized by the presence in summer and winter of dark eff~orescences (black alkali) forming very thin layers which frequently develop a puffed type structure. Whitish accumulations (white alkali) also occur in association with the black ones. This area is of the Na-SOa-CO3-C1 type (Fig. 2). XRD results show that in the winter effiorescences, the main mineralogical components are trona and thenardite. Natron, mirabillite and halite are present in lesser proportions (Table 4). In the summer samples the principal component is thenardite, with halite, burkeite and trona in lower amounts. The

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presence of burkeite in the winter efflorescences cannot be excluded, since its identification (peaks at 0.264, 0.280 and 0.277 nm) is complicated by the presence of the minerals trona and thenardite (0.264 and 0.278 nm, respectively) in considerable quantities. Thin section observations of the summer efflorescence (more developed than that of winter), reveal a mixture of salt minerals and silicatic--carbonatic material presenting a disturbed structure, strongly impregnated with organic material in the first mm (black alkali). Halite (Fig. 3e) appears as corroded subrounded crystals, as locally octahedral and as anhedral cement; book plate aggregates were afterwards assigned, considering the XRD and SEM results of the laboratory samples, to burkeite. These show strong allochromatism due to the presence of organic material (Fig. 3f). Trona occurs as needle-shaped crystals grouped in subrounded nodules, with a coalescent tendency. Thenardite appears as microcrystalline nodules, as well as rosette-like aggregates. In the less developed black alkali efflorescences, only a more or less continuous surface covering the soil was observed. The whitish salt accumulations have the same mineral associations as the black ones. The study with SEM revealed trona crystallized as bars without a markedly radial arrangement (Fig. 6a); lath-shaped thenardite crystals occasionally forming incipient rosette-like structures were also seen. Also present were some crystals as plates arranged in books (Fig. 6b); analysis by EDS showed they are a sulfur- and sodium-containing mineral. With this composition, only burkeite and thenardite were identified by XRD. This morphology (books of plates) has not previously been reported for thenardite. The analyses did not give any information pertaining to carbon content since the samples were covered with C for SEM observation; thus it was impossible to determine whether the compound in question was Na2SO4 or Na2SO4Na2CO3. In the samples that were obtained in the evaporation pan experiment (winter conditions), the main component is halite, with burkeite and trona in lower proportions (Table 4). Under summer conditions, the composition is the same (Table 4) with only a slightly lower amount of trona. With capillary evaporation using a column of soil under simulated winter conditions, thenardite and mirabillite formed in addition to halite, burkeite and trona (Table 4). In the SEM study of minerals obtained in the evaporation pan experiment, needle-shaped thenardite crystals were identified (Fig. 6c), contrasting with the rosette-like morphology seen in samples from the other sites. Halite appears as cubic crystals showing clear signs of corrosion. Trona crystallized as lath-shaped crystals in random arrangements and as radiating fans (also described by Vergouwen, 1981b) (Fig. 6d). In the central zone of Fig. 6d a spheroidal morphology is present, the colour of this feature indicates a chemical composition different from that of trona and halite. The results of semiquantitative analyses (EDS) led us to conclude that, as in the natural samples, it is impossible to distinguish between thenardite and burkeite. In an attempt to clarify this problem, the same brine was crystallized in a strongly alkaline medium (pH = 12) under summer conditions. XRD identifies thermonatrite Na2CO3" H20 (Stoops, 1987), trona, halite, and burkeite, with thenardite absent. This association, identified with microanalysis, is illustrated in Fig. 6e; zones 1 and 2 show different relative content of Na, which together with XRD data indicate that zone 1 corresponds to radiating fans of lath-shaped trona crystals, while zone 2 corresponds to microcrystalline thermonatrite which had pseudomorphically substituted natron by dehydration. Zone 3 corresponds to halite crystals. In zone B spherical intergrowths of parallel plates are

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Fig. 6. Call~n area. Natural salts: (a) Trona in bars (SE image). (b) Book plates of burkeite (SE image). Laboratory salts: (c) Needle-shaped crystals of thenardite (SE image). (d) Spheroidal burkeite and bars of trona (BSE image). (e) 1 = trona; 2 = thermonatrite; 3 = halite; B = burkeite (BSE image). (f) Detail of zone B in (e) Spheroidal burkeite ( BSE image).

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observable (in greatest detail in Fig. 6f), and were identified as burkeite with microanalytical confirmation of their sulfur content. It may be stated now, that in both natural and laboratory efflorescences, the mineral burkeite is present as book plates (Fig. 6b) and/or spheroidal association of plates (Fig. 6a, d, e, and f).

4. Discussion and conclusions

4.1. Mineralogical and morphological aspects

The occurrence of natron, exclusively in the natural winter efflorescences, is due to the stability of this mineral at low temperatures (Milton and Eugster, 1959). The presence of thenardite with rosette-like morphology (Stoops, 1973; Stoops et al., 1978; Tursina and Yamnova, 1986) in summer efflorescences (natural and laboratory), appears to indicate that this morphology is associated with rapid crystallization. This is according to the observations, in respect to gypsum, of Jafarzadeh and Burnham (1992). Thenardite lenticular morphologies are associated with slow processes of crystallization; small-sized crystals of thenardite with drusy-like morphology pseudomorphize to mirabillite prisms in a rapid process of dehydration. Rosette-like morphologies of thenardite are associated with surface layer evaporation, and also with pan evaporation experiments. Bloedite may occur with various morphologies (Table 5) including individual prisms and prismatic radial aggregates; both are produced through a slow crystallization associated with surface layer evaporation. Bloedite also occurs as prismatic subidiomorphic crystals and as foliated rosette-like microcrystalline aggregates with pseudoparallel dispositions; these growths seem to be associated with rapid processes of crystallization from a supersaturated solution. Burkeite has already been described by other authors (Vergouwen, 1981a; Mees and Stoops, 1991 ); in the present work, two new morphologies are attributed to this mineral, those of plates forming books and/or subspheres (Table 5). The anhedral and book plate morphologies, found in the natural samples are formed through capillary evaporation. Trona has been observed with different morphologies, as bars in radiating fans, as prismatic acicu!ar crystals and as penetrative overgrowths in halite crystals, all of them are associated with capillary processes.
4.2. Regional aspects

Results obtained in the Marcrn area, for the natural and laboratory samples, suggest two processes of formation of salt accumulations. The first is through capillary evaporation (Bertrand and Jelisejeff, 1974) related to uprising groundwater and seepage caused primarily by irrigation; surface halitic-mirabillitic efflorescences with a powdery aspect are formed. The second is related to the leaching and differential dissolution of surface salts which accumulate in microdepressions, with subsequent precipitation of prismatic crystals of mirabillite. Within the epipedon, the mirabillite appears as serrated edged rods and its dehydration leads to loss of structure (Tursina et al., 1980).

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Table 5 Minerals occurring in natural (N) and laboratory (L) salt accumulationsof Flumen-Monegros district Name Bloedite Formula
Na2Mg(SO4)2 4 H 2 0

Morphology Prismatic and subidiomorphic idioFoliated rosette-like Rounded. Prismatic radiating Cementing agent Spheroidal. plates Book Prismatic Lenticular Needle-shaped Prismatic Cubic Needle-shaped Cementing agent Fibrous prismatic Prismatic. Acicular Prismatic Serrated edged rods Prismatic subidiomorphic Pseudomorphic after mirabillite with drusylike Rosette-like Needle-shaped Lenticular. Anhedral Nodular Pseudomorphic natron after Bars in radiating fans Needle-shaped

Locality AL AL AL AL CA AL MA-AL MA-AL MA AL~CA AL MA-AL-CA MA AL AL MA MA CA MA MA-AL-CA CA MA MA-CA CA CA CA

Type N N N N N,L L N N L N,L N N N L N,L N,L N N N N,L L N N L N,L N

Burkeite Epsomite Gypsum

2Na2SO4. Na2CO3 MgSO4.7H20 CaSO4.2H20

Halite

NaC1

Hexahydrite MgSO4"6H20 Konyaite Na2MgSO4) 2"5H20 ( Mirabillite Na2SO4" 10H20 Natron Thenardite Na2CO3 10H20 Na2SO4

Thermonatrite Na2CO3 1 H 2 0 Trona Na2CO3-NaHCOa.2H20

Marcrn (MA), Almuniente (AL) and Callrn (CA) areas. In the Almuniente area, two types of saline accumulations are distinguished: surface efflorescences and saline crusts. They are formed through capillary evaporation and surface water evaporation, respectively. The formation of the saline crust can be described by the following: 1. Precipitation of bloedite as prismatic idiomorphic crystals, occasionally with anhedral thenardite inclusions. 2. Alternating crystallization of bloedite and halite, the latter forming euhedral cubic crystals and a cementing agent for the first bloedite crystals. 3. Crystallizations with characteristic morphologies of rapid processes, massive halite, microcrystalline foliated rosette-like aggregates of bloedite, and rosette-like crystals of thenardite. In the Callrn area, the alkaline efflorescences are formed through capillary evaporation; only the results of the natural samples are similar to those obtained through capillary evaporation experiments.
4.3. Laboratory efflorescences

The pan and the capillary laboratory crystallizations in the Marcrn and Callrn areas produced the same minerals as found in natural samples. In the Callrn area the relationships

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between the morphology, mineralogy and formation process of burkeite could be established through the laboratory crystallization. In the Almuniente area, mineralogical differences between pan evaporation (formation of halite, epsomite, and hexahydrite) and capillary and surface water evaporation (formation of halite and bloedite) is probably due to the non-equilibrium conditions existing in the pan (Vergouwen, 1981a), which lead to the fractional crystallization of epsomite/hexahydrite. When evaporation is carried out with substrate, the equilibrium conditions lead to the crystallization of bloedite, exactly as occurs in the natural efflorescences. Laboratory crystallization of brines without substrate does not reproduce, in all cases, the natural mineral associations, as was also found by Vergouwen (1981a). However, the present work has shown that such associations can be reproduced when crystallization is carried out with the epipedon.

Acknowledgements
We thank Dr. Wierzchos for his help in relation with the SEM study and Mrs. Lazaro and Mr. Pinto for technical assistance. Our particular gratitude goes out to Prof. Stoops and Dr. Mees for helpful discussions on an earlier draft of this paper. This research was supported by DGICYT (Spain) under Project PB 90/90.

References
Bertrand, J.P. and Jelisejeff, A., 1974. Formati6n d'evaporites par des processus d'evaporation capillaire. Rev. Geogr. Phys. Geol. Dynam., 16: 161-170. Bullock, P., Federoff, N., Jongerius, A., Stoops, G. and Tursina, T., 1985. Handbook for Soil Thin Section Description. Waine Research Publications, Wolverhampton. De la Pefia, J.A., Garcia-Ruiz, J.M., Martil, R. and Prieto, M., 1982. Growth features of magnesium and sodium salts in a recent playa lake of la Mancha (Spain). Estudios Geol., 38: 245-257. Doorenbos, J. and Pruitt, W.O., 1977. Crop water requirements. Irrigation and Drainage Paper 24, FAO. Rome, 144 pp. Gillor6, P., 1980. M6thode de fabrication m6canique et en s6rie des lames minces. Institut Agronomique, Thiverval Grignon 78850. Jafarzadeh, A.A. and Burnham, C.P., 1992. Gypsum crystals in soils. J. Soil Sci., 43: 409-420. Jaranta, J.E., 1989. Modelos matemfiticos del regimen de humedad de los suelos. Thesis Doctoral, ETSIA-UPC L~rida. Keller, L.P., McCarthy, G.J. and Richardson, J.L., 1986. Laboratory modeling of Northern Great Plains salt efflorescence mineralogy. Soil Sci. Soc. Am. J., 50: 1363-1367. Mees, F. and Stoops, G., 1991. Mineralogical study of salt efflorescences on soils of the Jaquetepeque Valley, northern Pe~. Geoderma, 49: 255-272. Milton, C. and Eugster, H.P., 1959. Mineral assemblages of the Green River formation. I 18-150. In: P.H. Abelson (Editor), Research in Geochemistry. Wiley, New York. Porta, J. and Rodriguez-Ochoa, R., 1991. Traslocaciones s61idas en suelos con caracteristicas s6dicas en MonegrosFlumen (Huesca): Procesos e implicaciones de uso agrfcola. Suelo y Planta, 1: 603--617. Quirantes, J., 1978. Estudio sedimentologico y estratigrLfico del Terciario Continental de los Monegros. Inst. Fernando el Cat61ico (Editor), Zaragoza, 200 pp. Stoops, G., 1973. Optical and electron microscopy, a comparation of their principles and their use in micropedology. In: G. Rutherford (Editor), Proc. 4th Int. Work-meeting on Soil Microscopy. Kingston, Ontario, pp. 101118.

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C. Vizcayno et al. / Geoderma 68 (1995) 193-210

Stoops, G., 1987. Mineralogy of desertic areas. In: M. de Boodt and R. Hartman (Editors), Eremologie Rug. Ghent, pp. 105-113. Stoops, G., Eswaran, H. and Abtahi, A., 1978. Scanning electron microscopy of authigenic sulphate minerals in soils. In: M. Delgado (Editor), Proc. 5th Int. Working Meeting on Soil Micromorphology, Granada, Spain, pp. 1093-1113. Timpson, M.E., Richardson, J.L., Keller, L.P. and McCarthy, G.J., 1986. Evaporite mineralogy associated with saline seeps in southweatern North Dakota. Soil Sci. Soc. Am. J., 50: 490--493. Tursina, T.V. and Yamnova, V.V., 1986. Identification of salt mineral in soils. Sov. Soil Sci., 18: 97-107. Tursina, T.V., Yamnova, I.A. and Shoba, V.V., 1980. Combined stage by stage morphological, mineralogical and chemical study of the composition and organization of saline soil. Sov. Soil Sci., 12:81-94. Vergouwen, L., 1981a. Salt minerals and waters from soils in Konya and Kenya. Thesis Doctoral, Univ. Wageningen. Vergouwen, L., 1981b. Scanning electron microscopy applied on saline soils from the Konya Basin in Turkey and from Kenya. In: E.B.A. Bisdom (Editor), Submicroscopy of Soils and Weathered Rocks. Pudoc, Wageningen, pp. 237-248.