soil properties that affect sulphate adsorption by palexerults in western and central spain

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Soil properties that affectsulphate adsorption bypalexerults in western andcentral SpainRafael Espejo Serrano a , Jesús Santano Arias a

& Pedro González Fernández ba Dpto. Edafología, E.T.S.I, Agrónomos, C.Universitaria, Madrid, 28040, Spainb CIFA, Alameda del Obispo, Apdo 3092,Córdoba, 14080, SpainPublished online: 11 Nov 2008.

To cite this article: Rafael Espejo Serrano , Jess Santano Arias & Pedro GonzlezFernndez (1999) Soil properties that affect sulphate adsorption by palexerults inwestern and central Spain, Communications in Soil Science and Plant Analysis,30:9-10, 1521-1530

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COMMUN. SOIL SCI. PLANT ANAL., 30(9&10), 1521-1530 (1999)

Soil Properties That Affect SulphateAdsorption by Palexerults in Western andCentral Spain

Rafael Espejo Serrano,a Jesús Santano Arias,a and PedroGonzález Fernándezb

aDpto. Edafología, E.T.S.I, Agrónomos, C. Universitaria, 28040 Madrid, SpainbCIFA, Alameda del Obispo, Apdo 3092, 14080 Córdoba, Spain

ABSTRACT

The beneficial action of gypsum in suppressing aluminum (Al) toxicity in Bthorizons of Ultisols is related to the self-liming effect of the adsorption ofsulphate (SO4

2-) ion. The relationship between SO42- adsorption by gypsum-

amended soils and some components and properties of 38 surface andsubsurface horizons from seven Palexerults in western and central Spain wasanalyzed. The highest correlations of maximal SO4

2- adsorption as determinedfrom langmuir isotherms were with clay, free iron oxyhydroxides (Fedcb),and exchangeable Al contents, and pH. Liming reduces SO4

2' ion adsorption;consequently, the joint application of limestone and gypsum to the surface ofthese soils results in increased availability of gypsum for the subsurfacehorizons.

1521

Copyright © 1999 by Marcel Dekker, Inc. www.dekker.com

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1522 ESPEJO SERRANO, SANTANO ARIAS, AND GONZALEZ FERNANDEZ

INTRODUCTION

Ultisols are very common soils in areas with subtropical climate where theirsoil moisture regime is udic. They have argillic horizons with low base saturation(Soil Survey Staff, 1997). The greatest agronomic constraints of these soils arisefrom their high exchangeable Al contents which prevent root development, andthe low availability of several essential nutrient elements as a result of theirextensive weathering, leaching, and acidification. The problem is usually addressedby using lime amendments, but the low mobility of lime added to the soil surfacemakes it inefficient for suppressing Al toxicity in subsurface acidic horizons.

The pH of Ultisols decreases with increasing depth, hence the problems posedby Al toxicity are specially severe in their Bt horizons. This has fostered the useof gypsum which is being increasingly applied to the soil surface in order tocorrect the effects of Al in Bt horizons (Shainberg et al., 1989).

The action of gypsum as suppressor of Al toxicity in acid soils has been ascribedto various effects involving an increased calcium (Ca)/Al ratio (Lund, 1970;Ritchey et al., 1980; Noble et al., 1988; Kinraide et al., 1992), self-liming (Reeveand Sumner, 1972; Pavan et al., 1982), the formation of non-toxic aluminumsulfate [A12(SO4)3] pairs (Kinraide and Parker, 1987), and the precipitation ofalunite and other complex aluminum sulphates (Ritchey et al., 1995). The selfliming effect is directly related to the adsorption of SO4

2" ion by the soil matrix, aprocess which therefore warrants in depth examination.

Regarding Ultisols, the management of Xerults has been less extensively studiedthan that of Udults owing to the more restricted geographical distribution of theformer; this is clearly reflected in the poor taxonomic development of this suborder(Espejo et al., 1993). In the tipically Mediterranean environment of Xerults, witha xeric moisture regime, are common long periods where plants are under waterstress; this calls for a special recommendation of gypsum amendments in thissoils due to the role of Al in increasing water stress in crops (Gonzalez Enrico etal., 1979; Sousa et al., 1992; Ritchey et al., 1995).

We studied the influence of the clay, organic matter, iron oxyhydroxide, andexchangeable Al contents as well as pH on SO4

2' ion adsorption by variousPalexerults from western and central Spain. We also examined the effect of usinglimestone amendments, a rather commonplace practice in managing this type ofsoil on the dynamics of SO4

2" adsorption.

MATERIALS AND METHODS

The soils samples utilized in this study were obtained from surface and sub-surface horizons of seven different Palexerults. Profiles 1 to 6, on rafia surfacesof western Spain, related to "Las Villuercas-Los Montes de Toledo" mountainranges, and profile 7, on rafia surface related to Somosierra, in central Spain. Themorphology of these soils have been described previously (Espejo, 1985, 1986,

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SOIL PROPERTIES THAT AFFECT SULPHATE ADSORPTION 1523

1987). Samples were air dried and passed through a 2-mm mesh sieve. The claycontent was determined by the method of Kilmer and Alexander (1949). Organicmatter (OM) was determined by the method of Walkley and Black (1934).

Exchangeable Al was extracted with 1M potassium chloride (KC1) anddetermined by titration (Yuan, 1959). Free iron oxides (Fedcb) were obtained bythe dithionite-citrate-bicarbonate extraction procedure (Mehra and Jackson, 1960).Sulfate sorption curves were obtained after adding to 6 g of soil, placed in acentrifuge tube, 50 cm3 of 0.001 MKC1 containing 0,0.15,0.30,0.50,0.75,1.00,1.25, and 1.50 mg CaSO4-2H2O I/1. The suspensions were maintained at 35°Cand shaken twice daily for seven days, and then centrifuged. Sulfate concentrationin the supernatant was determined by ionic chromatography. The amount ofadsorbed SO4

2' was calculated by subtracting the amount of SO42' in the supernatant

solution from the amount initially added. The SO42- adsorption data were used

with the Langmuir equation to calculate the maximum SO42- sorption ( S O / ^ ) .

To study the incidence of lime application on SO42- adsorption, a selection of

Ap, AB, and Bt soil samples were incubated with calcium carbonate (CaCO3)doses equivalent to 2.5 and 7.51 ha1. After a month maintained at field capacityat 30°C, 6 g of soil was placed into a centrifuge tube with 50 cm3 0.001 M KC1solution containing the amount of CaSO4-2H2O equivalent to 100 meq kg"1 (1,032mg L'1). The suspensions received the treatment previously exposed and the SO4

2'in the supernatant was determined.

RESULTS AND DISCUSSION

Table 1 lists selected analytical results for the 38 studied soil samples. Samples27 and 28 were from an argillic horizon with plinthic segregations of free ironoxyhydroxides which are very commonplace in the deeper Bt horizons of thesesoils (Espejo, 1986, 1987). In all the profiles Bt horizons contained more claythan surface horizons. The organic matter content in the surface horizons variedwith the prevailing vegetation and soil usage, those soils which had been cultivatedfor years had lower organic matter content. The pH decreased with increasingdepth, in contrast with the Al content. All horizons except some surface ones inlands which had been cultivated for many years and possibly received limestoneamendments (sample 22) were strongly acidic. The free-iron oxyhydroxide contentbehaved similarly to clay, its content increased with increasing depth except atwhite enclaves in argillic horizons with plinthic segregations (sample 27). Inthese Palexerults, the clay fraction is dominated by caolinite and goethita andhematite (Espejo, 1986, 1987). Table 2 gives the single linear correlationcoefficients between the maximum SO4

2' adsorption and the measured soilproperties. Clay, free iron oxyhydroxide (Fedcb), and exchangeable Al contentsare positively correlated, and pH and the organic matter content negativelycorrelated to SO/"^. The negative relationship between the organic matter contentand the S O / ^ can be explained by the specific morphology of these soils in

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TABLE 1. Maximum sulfate adsorption capacity and relevant data in thePalexemlts of western and central Spain.

No.

1234567891011121314151617181920212223242526272829303132333435363738

P*

1

2

3

4

5

6

7

Hor.

ApABBt,Bt2

Bt,

ApABBt,Bt,ApABBt,Bt21

BtaBt,ApABBt,Bt21

BtM

Bt,ApABBt,Bt2

Bt,Bt4,Bt«ApABBt,Bt2

Au,AujBt,Bt2

Bt,2Bt4

Depth(cm)

0-2020-3333-6060-115

115-1800-20

20-4242-7373-115

0-1818-3737-7373-9090-135

135-1800-16

16-2727-5555-105

105-140140-180

0-1818-3838-5959-114

114-1803003000-31

31-7070-9999-180

0-1515-5050-8585-150

150-200>200

PH

5.35.25.14.84.65.45.45.14.95.75.55.35.14.74.45.24.94.84.84.74.76.35.95.14.84.74.64.75.15.35.14.85.85.65.24.64.54.5

OM

4.10.80.30.1

1.60.50.1

.

2.80.90.10.1

3.21.40.40.1

1.50.60.20.1

.4.40.90.20.10.90.4

.

-

Clay~ ( % ) -

10.515.535.033.034.017.022.532.045.011.516.030.044.047.546.0

7.813.924.734.033.031.310.012.025.040.034.052.048.0

8.516.047.550.0

5.05.5

50.547.549.044.0

Fcj*

1.73.56.56.54.52.95.06.17.31.92.73.07.29.8

10.61.22.64.97.47.66.92.43.24.17.47.20.5

11.91.73.26.67.50.90.94.04.49.3#7.1#

Ex.Al3t

cmol kg"1

0.90.94.07.0

10.00.10.54.06.00.40.81.83.14.06.50.51.42.02.53.55.80.10.61.83.04.06.05.01.01.23.55.50.10.12.65.57.05.4

s o 42

m t tmg kg'1

222391853807764291519803986258418669945934

1,038301329702880902802

227

456963821768

1,044201493746953

1030

703779907831

•Profiles: l=Palacio Cigueftuela; 2=Pedro Millan, 3=Anchuras, 4=Castilblanco-0; 5=Castilblanco-3; 6=Canamero-l; 7=Cerro del Moro.

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TABLE 2. Correlation matrix for maximum sulfate adsorption and selectedsoil properties; n=38.

AcFed<*Al3+

OMPH

Ac1

Fej*0.72651

Al3+

0.76810.60931

OM-0.6789-0.5769-0.55031

pH-0.7307-0.6405-0.78870.4262I

s o ^0.90040.83540.7697•0.6456-0.82721

which caolinite, and iron oxihydroxide contents, the major contributors to SO42"

adsorption (Aylmore et al., 1967; Couto et al., 1979; Doloui and Jana, 1997),increase with depth, unlike to organic matter. If we work with only A horizonsdata, the coefficient of single linear correlation between these two variables ispositive (R=0.66; n=8).

The best relationships between S O ^ ^ and clay and exchangeable Al wereobtained by transforming the independent variables logarithmically (Figures 1and 2). With regard to F e ^ (Figure 3), the relationship to SO4

2" adsorption improveswith this transformation if we eliminate the soil sample 27, extracted from a whitestripe of a deep Bt horizon with plinthic segregation, characterized by having ahigh clay and a very low Fedcb contents. The relationships between maximumSO4

2' adsorption capacity and clay, Al, and Fedcb were:

S O 4 2 „ = -793,86 + 440.86 L Ac; R = 0.930; n =38SO4

2™ = 492,86 + 217.13 LA1;R = 0.884; n = 38S O 4 2 m « = - 2 0 - 2 5 + 4 3 6 - 6 5 L F e d d , ; R = ° - 9 0 7 ; n = 3 7

Maximum SO42' adsorption is also closely related to pH (Figure 4). The equation

was:

S 0 4 2 n»x = 3 ' 7 4 7 - 5 - 6 1 8 - 3 1 P H ; R = - ° - 8 2 7 ; n = 3 8

The negative relationship between these two variables can be explained by thesame than in the case of organic matter: The pH decreases with depth, contrariouslyto clay and Fedcb contents.

Table 3 shows the SO42" adsorption values in the selected soil samples previously

amended with CaCO3. A comparison with those for the untreated samples revealsthat the addition of limestone and the consequent increase of pH value have anadverse effect on SO4

2" adsorption. In the Ap and AB horizons, the addition oflime amendments even induces to a desorption of the adsorbed SO4

2' from the soilmatrix. This contrasts with the dynamic of phosphate adsorption in the same typeof soils (Santano et al., 1998), in which this decreases at small limestone rates,when the pH of the amended soil sample does not exceed 5.5, but increases at

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1200

1000

I

_)

8 MO ''~ ^^l J- -793,84 + 440,86 Lx,S 400 S* ' r-0^30

n»38

0

-20010 20 30 4t SO 60

CUy(%)

FIGURE 1. Relationship between maximum sulfate adsorption capacity and clay content.

Eichinge»ble Al (cmol kg"1)

FIGURE 2. Relationship between maximum sulfate adsorption capacity and exchangeableAl+\

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1200

1000

•Q 800

I 600S

. • 400

o200

y»-20J5 +436,65 U

r-0,907

n-37

10 12

-200 1

Fedcb(%)

FIGURE 3. Relationship between maximum sulfate adsorption capacity and free ironoxide content.

-200 J-

pH

FIGURE 4. Relationship between maximum sulfate adsorption capacity and pH.

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TABLE 3. Data of SO42' adsorption after adding to 6 g of soil

sample 50 cm3 of a 0.001 m KC1 solution having 1.032,0 g L'1 ofCaSO4-2H2O (588 mg SO4

2" L1).

Sample(horizon,and profile)

Treatment PH S(V"solmgL'1

S042ad

mg kg"1

1(AP;p*l)

2(AB;p*l)

4(Bt2;p*l)

16(Ap;p*4)

17(AB;p»4)

19(Btj,;p*4)

control+2,5tha'lime+7,5tha'lime

control+2,5tha'lime+7,5tha'lime

control+2,5tha-'lime+7,51 ha-1

lime

control+2,5tha-'lime+7,5tha-'lime

5.35.96.8

5.26.07.2

4.86.07.1

5.26.16.8

4.95.86.9

4.85.96.9

563.8589.1598.5

552.3583.5590.1

498.2549.5579.4

554.4584.9591.7

551.4567.9586.9

492.5553.7576.3

201.5-9.2

-87.5

297.837.5-17.2

748.3320.771.3

279.825.3

-31.2

305.3167.2

9.2

795.2285.497.1

higher rates. This finding is quite significant with a view to improving gypsumavailability by subsurface horizons: the joint addition of limestone and gypsumon the soil surface decreases gypsum adsorption by the Ap horizon, where thesuppressing action of Al toxicity rests on limestone alone. Because limestone isscarcely "mobile" in soil, it does not affect the gypsum adsorption on subsurfacehorizons; as a result, increased amounts of gypsum are available for the Bt horizonswhich usually lie at a depth greater than 50 cm.

CONCLUSIONS

In the Palexerults of western and central Spain, the major contributors to SO42"

adsorption are clay, free iron oxihydroxides ( F e ^ , and exchangeable Al. ThepH of (1/2.5) soil/water suspensions, an easily available data, can give a veryuseful information about the maximum SO4

2' adsorption estimation. The lime

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applied together to gypsum to the Ap horizons improves the SO42- availability in

the Bt horizons.

ACKNOWLEDGMENTS

The authors to the Programa Sectorial I+D del MAPA y a la DGICYT whichhave supported the investigation costs through the projects: SC95-075-C2-2 andPB94-0039-C02-02.

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soil properties that affect sulphate adsorption by palexerults in western and central spain

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