Environ Earth Sci (2009) 59:603611 DOI 10.

1007/s12665-009-0058-9

ORIGINAL ARTICLE

Application of sugar foam to red soils in a semiarid Mediterranean environment

s Ortiz-Villajos a Navarro J. A. Amoro F. J. Garc nchez Jime nez S. Bravo Mart n-Consuegra C. J. Sa rquez Cubero Raimundo Jime nez Ballesta E. Ma

Received: 15 June 2008 / Accepted: 8 January 2009 / Published online: 10 February 2009 Springer-Verlag 2009

Abstract The study described here involved evaluating the effects that the application of one by-product (sugar foam waste) has upon red soils in the region of La Mancha (Central Spain). In view of the fact that this is a location where this type of soil abounds, this technique has been a common practice for many years. The principal goal was to investigate the impact of this approach on some of the soil properties and, secondly, on its level of fertility. As a result, this represents an investigation into the effects that this type of waste has on some soil quality parameters. The results showed that, after the addition of by-products over 25 years, sugar foam waste is of agricultural interest mainly due to the increase in organic matter concentration (about 2%) and, to a lesser extent, by increases in calcium carbonate (more than 30%) and P (four times more). The soil pH was also found to increase slightly (1.4), while the electrical conductivity almost did not change. The properties associated with these pedological qualities therefore had a positive effect by improving nutrient availability. As a result, foams arising from sugar industries have a positive effect on soil quality and the application of such foams to

soils is benecial since the need to dispose this residue is also removed. Keywords Sugar foam waste Red soils Semiarid Mediterranean environment La Mancha Spain

Introduction The combination of agricultural and industrial activity generates residues that must be disposed of owing their negative effects on the environment and to maintain the natural ecological equilibrium (Ros 2000). The generation of agro-industrialist residues has grown quickly in recent decades, with soils being one of the main destinations for this material. The addition of wastes, such as sugar foam, compost and wine vinasse wastes, to agricultural soils is a common cultural practice, especially in the last 23 decades, due to the improvements observed in some soil properties (Sikora and Azad 1993), and the increase in crop yield and quality (Tejada and Gonzalez 2003, etc.). Amongst the better known residues used in La Mancha (agricultural semiarid Mediterranean region situated in central Spain), wine vinasse, beet vinasse and sugar foam waste are worth mentioning. This product (sugar foam waste) is known as foam is not t for consumption; is often applied to red soils that, apart from having an appreciable agronomic value, have a paleoclimatological and paleopedological signicance and are therefore of environmental interest. The potential impact of the materials accumulated in the so-called sugar foam wastes in soils used for dry-farmed crops is undoubtedly of interest, especially given that such waste has been applied to red soils with a great paleoclimatological, paleodophological, and in general

a Navarro J. A. Amoro s Ortiz-Villajos F. J. Garc n-Consuegra E. Ma rquez Cubero S. Bravo Mart cola, UCLM, Esc. Univ. Ing. Tecn. Agr Ronda de Calatrava, 7, 13071 Ciudad Real, Spain e-mail: FcoJesus.Garcia@uclm.es a Navarro C. J. Sa nchez Jime nez F. J. Garc mica y Medioambiental Unidad de Suelos, Instituto Tecn. Qu (ITQUIMA-UCLM), 13071 Ciudad Real, Spain nez Ballesta (&) R. Jime a y Geoqu mica, Departamento de Geolog noma de Madrid, Facultad de Ciencias, Universidad Auto Campus Cantoblanco, 28049 Madrid, Spain e-mail: raimundo.jimenez@uam.es

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604 Fig. 1 Location map of studied area

Environ Earth Sci (2009) 59:603611

lez Mart n et al. 2007). environmental signicance (Gonza This material may also cause a modication in agronomic soil quality. The concept of soil quality appears to be relatively new but, at the same time, this topic is widely debated. Agricultural productivity has usually been put on the same level as the sustainability, the fertility of the soil and its usefulness. In any case, it is necessary to dene the functions of the soil and, in this respect, the most recent denitions of the soils quality are based on its multifunctionality rather than on a single specic use, bearing in mind that the concept is continually evolving (Singer and Ewing 2000). Thus, the inappropriate use of the soil might lead to a disruption in its chemical, physical and biochemical properties, such as a decrease in the cationic exchange capacity, pH, permeability, etc. Such changes could even affect the nutrients available for the microorganisms and plants (Clark et al. 1998). The extraction of sugar from sugarcane is a very old process. More than 50% of the sugar consumed worldwide is obtained from sugar cane, which grows in tropical and subtropical climates. The rest of the sugar comes from sugar beet, which is planted in temperate countries like Spain. The roots are cut into strands in order to extract the juice. During the extraction process for sugar from sugar beet it is necessary to separate the non-sweet substances from the beetroot juice in a rening process that consists of two steps. The colloidal substances must rst be occulated by whitewashing with lime. The occulated substances are called foams and these, in the traditional manufacture process considered here, are swept away by water to large pools for a natural drainage (Espejo 2001). After the extraction, lime is usually added to the juice and the rest of the process continues. The sugar foam waste is therefore a relatively new

and unknown organic residue that has emerged from the signicant growth in the sugar beet industry. Another characteristic of these residues is that they are difcult to deposit although they can provide certain nutrients to the soils. The addition of amendments is currently being considered as an effective technique to improve soils quality, e.g. for the remediation of contaminated soils. For this reason, in this study we deal with the impact that the different supercial disposal of these by-product over the last 25 years has had on soil quality. The treatment has been carried out on red soils that are mainly used for dry farming and are occasionally left fallow.

Materials and methods Study area and sampling procedure The work was carried out upon typical red soils used for dry farming in the semiarid Mediterranean region (La Mancha). The foams were obtained from the Azucarera de Ciudad Real S.A. industry and they were deposited at different levels over a time that spanned more than 25 years. The amounts involved can be estimated as between 20 and 40 tons/ha per year. The area of La Mancha spreads over the central Iberian Peninsula (Fig. 1) and is characterised by great geodiversity. This region is dominated by Rhodoxerafs together with Xerochrepts, (Soil Survey Staff 2006) with some calcium carbonate accumulation. According to FAO ISRIC ISSS (2006) the soils are Luvisols and Cambisols. In this study, two soil proles, one disturbed and the other one undisturbed (treated with sugar foam and

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605

untreated) were described and sampled from widely distributed soils series in La Mancha. The soil moisture regime for the area is Xeric and the temperature regime is Mesic (Soil Survey Staff 2006). Soil samples were collected from two geo-referenced locations throughout La Mancha (Central Spain). In each location a typical red soil was described according to FAO (2006) criteria (Table 1). Samples collected from both soils were air dried at room temperature and carefully sieved through a 2-mm mesh; the coarser material was discarded and the remaining ne-earth fraction was gently mixed until it appeared to be homogeneous. The dried samples were used for subsequent analysis. Aliquots of this fraction were taken randomly for chemical and physico-chemical analysis. Analytical methods The analytical determinations were carried out according to SCS-USDA (1972). In particular, soil texture was determined using the hydrometer method (Gee et al. 1986) with three replicates. Soil pH was measured in H2O and in 0.1 M KCl using a 1:2.5 soil/solution ratio. Electrical conductivity was measured in a 1:5 soil:water extract. For calcium carbonate determination CO2 was measured in a calcimeter. The active calcium carbonate equivalent (ACCE) or active lime was determined with NH4-oxalate as described by Drouineau (1942). The method of Olsen et al. (1954), which is based on extraction with 0.5 M NaHCO3, was used to estimate available P. Soil organic matter was determined by potassium dichromate oxidation and titration of dichromate remaining with ammonium ferrous (II) sulphate (Anne 1945). Exchangeable cations were determined using an ammonium acetate extraction method (Thomas 1982). Exchangeable Na, K, Ca and Mg were determined by atomic absorption spectrometry. Total nitrogen content was determined by the Kjeldahl method (Bremner and Mulvaney 1982). All samples were extracted and analysed in duplicate. The semi-quantitative mineralogical analyses were carried out by X-ray diffraction (XRD) techniques; about 2 g of sample was hand-milled to below 53 lm in an agate mortar and used for the determination of the bulk mineralogy (random powder method). For the detailed study of phyllosilicates, 100 g of sample was treated to remove components that prevent complete dispersion (e.g. carbonates, sulphates, organic matter, etc.). The \2 lm (clay fraction) particles were extracted by sedimentation techniques and analysed on thick glass slides by XRD according to Moore and Reynolds (1989); samples were chemically treated [(a) ethylene glycol, to detect expandable minerals; and (b) dimethyl sulphoxide, to differentiate chlorite and kaolinite] and thermally treated (550C for 2 h, to study the behaviour of phyllosilicates). The samples were analysed using a CuKa

radiation source (Philips-Panalytical X-PERT diffractometer) with a graphite monochromator, 40 kV and 40 mA, and sensitivity of 2103 cps. The ranges measured were 275 or 250 2h, goniometer speed of 0.04 or 0.05 and time constant of 0.4 or 1 s for random powder or glass slides, respectively. The chemical compositions of whole samples were determined using an X-ray uorescence spectrometer (PHILIPS PW 2404) in solid mode.

Results and discussion A 25-year study was conducted with a view to assessing the effect of sugar foam waste on moderately basic red soils. Representative proles of degraded and undegraded morphological red soils of La Mancha were examined for morphological physico-chemical and mineralogical properties. The impact of sugar foam addition is manifested by the changes in the soil morphology as a new and quite different new Ap horizon appear (a change is observed in structure, colour, porosity, etc.). The addition of sugar foam also causes noticeable effects on certain soil properties. An increase in the pH, (Fig. 2a), is observed due to the presence of by-products with basic pH values. Nevertheless, it was observed that in the upper horizon, Ap1, the increase is less marked, probably due to the washing. The electrical conductivity barely changes, (Fig. 2d). Carbonate and the active lime are common components in a large number of soils in the surrounding areas, but not in the samples used in this study as we employed a moderately acidic soil, developed on a lithological substrate without carbonates (quartzite and slate). However, this component increased clearly (more than 30%) as can seen in Fig. 2a and b, after the application of sugar foam, similar to obtained by Lopez et al. (2001). Moreover, the soil contained traces of calcium oxide and was rich in organic matter and some nutrients such as Mg, P, Zn, and Cu. It is not unexpected that having applied the sugar foam, a considerable rise in P (four times more) and organic matter (Fig. 2a, b) took place. The behaviour of N mirrors that shown by the organic matter. The organic matter content grows and this must help to increase the stability of the aggregates, followed by the number and the size of the macropores, which will in turn enhance the structure and quality of the soil. (Chaney and Swift 1984). The normal levels of organic matter in soil in the area studied do not exceed 2%. Therefore, despite the high content of organic matter caused by the addition of the molasses under investigation, the increase in organic matter (2%) is important in comparison to the level in the initial soil (Fig. 2). This nding is attributed to the rapid mineralization of organic

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606

Table 1 General description and macromorphological characteristics of two soils investigated Parent material Slates and quartzites Dry farming Undulating C-2 Gently sloping C-3 Moderately well drained Vegetation/use Topography Slope Drainage Stoniness C-1 Few stoniness

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Structure Moderate, subangular blocky, coarse Moderate, subangular blocky, coarse Moderate, subangular blocky, coarse Common very ne Few ne Very few ne Strong, prismatic, coarse Strong, prismatic, coarse Parent material Slates and quartzites Pasture and dry farming Vegetation/use Very stickily, very plastic, rm, hard Stickily, plastic, rm, hard Slightly sticky, slightly plastic, friable, slightly hard Few ne Slightly sticky, slightly plastic, friable, slightly hard Common very ne Few ne Slightly sticky, nonplastic, friable, slightly hard Common ne and Few ne and very ne very ne Consistence Roots Pores Limit Gradual and wavy Stoniness (%) 5 Abrupt and smooth 2 Abrupt and smooth 2 Common ne Gradual and irregular Common ne and very ne Topography Hillside Slope C-4 Moderately steep Roots Abundant ne Pores Common coarse Sticky, plastic, friable, slightly hard Sticky, plastic, friable, slightly hard Abundant ne Common coarse None Common coarse Drainage C-5 Somewhat excessively drained Limit Gradual and irregular Diffuse and wavy 2 10 Stoniness C-2 Common stoniness Stoniness (%) 20 Structure Moderate, subangular blocky, medium Moderate, subangular blocky, medium Moderate, subangular blocky, medium Consistence Sticky, plastic, friable, slightly hard 20 Gradual and irregular 25

Soil type FAO/soil taxonomy Location/coordinates

Terric Anthrosol (eutric, clayic)/typic Rhodoxeralf

LAS CASAS 39010 2100 N 03560 3200 W, 0418432.73 (X), 4319768.58 (Y)

Horizons depth (cm)

Colour (dry)

Ap1 (012)

10 YR 7/3

Ap2 (1220)

10 Y 7/2

Ap3 (2032)

10 Y 7/2

2Bw(3260)

7.5 YR 8/3

2Bt(60110)

10 R 4/6

Soil type FAO/soil taxonomy

Location/ coordinates

Leptic Luvisol (skeletic, chromic)/typic Haploxeralf.

Fuente El Fresno

Horizons depth (cm)

Colour (dry)

Ap (025)

7.5 YR 6/4

Bt1 (2565)

7.5 YR 5/8

Bt2 (6596)

5 YR 5/8

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C ([96)

Environ Earth Sci (2009) 59:603611

607

a
A p1

pH

E.C. (dS/m)

% Ca carbonate

% A. Limestone

% O.M. A p1
Ap1

P (mg/Kg)
%N

A p1

A p1

A p1

Ap1

A p2

A p2

A p2

A p2

A p2

A p2

Ap2

A p3

A p3

A p3

A p3

A p3

Ap3

Ap3

2B w

2B w

2B w

2B w

2B w

2B w

2B w

2B t
7,2 7,8 8,4 9 2B t

2B t
0,3 0,4

2B t
0 10 20 30 40 50
0 4 8 12 16 20

2B t
0 1 2 3 4 5

2Bt

2B t
0 2 4 6 8 1012

pH H2O pH KCl

0,2

0,05 0,15 0,25

E.C.: Electrical conductivity A. Limestone: Active Limestone

Ca carbonate: calic carbonate O.M.: Organic matter

% O.M.

b
Ap

pH Ap

E.C.

%N Ap Ap

P (mg/Km)

Ap

B t1

B t1

B t1

B t1 B t1

B t2

B t2

B t2

B t2

B t2

5,8 6,6 7,4

pH H2O pH KCl

0,2

0,25 0,3

0,35 0

0,1

0,2

E.C. Electrical Conductivity

O.M. Organic Matter

Fig. 2 a, b Some pedological properties of selected the two soils

matter that occurs in well-aerated soil (Levi-Minzi et al. 1985) and at high temperature. The percentages of sand, lime and clay from the horizons and according to the texture classes diagram (Soil Survey Staff 2006), are shown in Table 2. These are classied as loam-clay. A substantial contrast can be seen in the clay content between the argilic (Bt) and the Ap horizons. The mineralogy corresponding to degradation prole is shown in Fig. 3ac and these are qualitatively and quantitatively similar to those in prole 2 (undegraded prole)

(Table 1). The diffractograms for the bulk mineralogy of the seven analysed samples are shown and it can be seen that the major component is calcite in the rst three samples (Ap1Ap3) (6585%). Quartz is found in all of the samples. On the other hand, in samples Ap1Ap3 it is evident that there is a very low level (\5%) of alkaline feldspar, while in the Bw and Bt samples this feldspar is of the plagioclase type. The latter samples, were analysed in a separated form (\2 lm), with the existence of Illite and Kaolinite at low levels in both samples. This fraction was solvated with

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608 Table 2 Particle size distribution and textural class % Gravels ([2 mm) Prole 1 Ap1 Ap2 Ap3 2Bw 2Bt 5.2 6.2 0.2 12.2 15.5 34.6 65.8 23.9 35.8 26.6 28.6 41.8 11.8 16.2 49.0 29.3 28.0 23.6 22.9 59.9 15.2 44.1 43,4 Silta Silt Silta Loam-clay-sand Clay Loam Clay Clay % Sand % Silt % Clay Textural classication

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Prole 2 Ap 33.8 Bt1 Bt2

a

45.9 49.7

Texture resolute by touch

ethylene glycol in order to detect the presence of Smectitetype minerals and was heated at 550C in order to conrm the presence of Kaolinite. However, only the presence of Kaolinite (1530%) and Illite (5065%) was detected and Smectite was absent. Therefore, from the study of diffractograms, it can be deduced that the samples Ap1, Ap2 and Ap3 belongs together with the horizons described as anthropogenic, where the addition of the foams has led to high contents in calcite, as well as their possible concentration in lower horizons (Ap3 mainly). The result obtained is consistent with the composition of the foam, which contains calcium carbonate and traces of calcium oxide. It was observed that the level of exchangeable K? remained unaltered although there was an increase in exchangeable Ca2? in the surface horizons. The retention in situ of toxic elements by the application of amendments is a remediation technology for contaminated soils (Vangronsveld and Cunningham 1998) as it aids the mechanism for the retention of these materials in the soil (Karaka 2004). As a result, we analysed a series of chemical elements. The interest in the chosen elements is based on their presence in different contamination processes, on their varied mobility and their different ionic forms and different geochemical performance (McBride 1994). The contents in silica, aluminium and iron show an imbalance in favour of the soil and to the detriment of the added materials, which are lost in large amounts due to calcination (Table 3). Mg and Ca are two of the chemical elements that are added in large amounts to the soil after the application of sugar foam. Mn, Na, K, Ti and Ba also increase in 2Bt or in the horizon 2Bw. Different effects of sugar foam waste on the morphological, chemical and mineral composition of red soils have been investigated. Hence, it can be assumed that although we could have expected a much more marked impact [as pointed out by (Clark et al. 1998) because of handling

effects], this does not seem to show a clear trend. Thus after at least 25 years of treatment the only major changes observed concern the carbonate, organic matter, phosphorus and nitrogen. Consequently, the properties related with these edaphic qualities have been affected positively. Furthermore, although the pH and the electrical conductivity do not change signicantly, we can conclude that these foams have a positive nal effect on the quality of the soil and can therefore recommend the application of this material (under the same conditions) to this kind or any other kind of soil. In fact, the observed increase in pH will enhance the availability of the elements and nutrients for plants and microorganisms; therefore, improving the edaphical conditions of the environment. Based on the increase in the organic matter in the soil, as well as on the small or insignicant effects on soil mineralogy, these agro-industrial products can be considered as effective alternatives for organic matter accumulation and for the improvement of soil quality in agriculture. The results obtained are consistent with those reported by various authors (Madejon pez et al. 2001; et al. 1996, 2001; Diaz et al. 1996; Lo Garrido et al. 2003; Vidal et al. 2004; Alonso et al. 2006; Vidal et al. 2006). The disposal of sugar foam is one the main environmental problems related to sugar industries. Since numerous studies have shown a positive correlation between soil organic matter and microbial biomass concentration (Bending et al. 2000; Tejada and Gonzalez 2003), we expected that the supply of sugar foam waste would enhance soil microbial biomass. Many authors, including Cegarra et al. (1996), Tomati et al. (1995), advocate the use of certain agricultural products and waste in some industries as an alternative, simple and yet costeffective way to reuse and dispose of such waste. An increase in the amount of Na was not observed in the work described here, but futures studies should focus on this aspect. The control of salinity is essential when dealing with an area of low rainfall, as there is a risk of reaching high saline values, with the consequent impact this has on the availability of water for the crops. These by-products can contain heavy metals, either added from the original matter or from industrial origin, and as such they can be a source of soil pollution (Fauziah et al. 1996). However, one of the remediation technologies used today on soils contaminated with heavy metals is the application of amendments for the retention of these metals (Vangronsveld and Cunningham 1998). Therefore, the addition of the foams will minimize the possibility of these metals reaching phreatic levels. Carbonell et al. (1999) have used phosphogypsum with at least 60% of the sulphates. Materials rich in calcium carbonate, such as the sugar foam from the sugar renery, have been used for the recovery of the soils in the Aznalcollar mines (Spain). It

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609

Fig. 3 X-ray diffractograms of samples

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610 Cr2O3 (mg/kg)

Environ Earth Sci (2009) 59:603611

SrO (g/kg)

0.05

0.06

0.03

SO3 (g/kg)

was also mentioned that such treatments contribute to the vegetable growth and the microbial activity (Mennch et al. 2000). The present project reveals the necessity to investigate the benecial effect of the latter possibility. Given the fact that most of these industrial by-products do not have a suitable site for disposal, it is clear that the possibility of using them to improve soil quality opens a whole new prospect for their reuse. Moreover, we believe that the addition of sugar foam could prove more useful than treatment with lime, as has traditionally been carried out (Ahmad and Tan 1986; Mennch et al. 2000; Gunn et al. 2001), bearing in mind that the effectiveness of the application of this byproduct can lead to the reduction of mobility of some toxic elements as it increases the capacity for their retention. Our future research will be concentrated in this area.

0.03

NiO (mg/kg)

0.02

0.03 0.03 0.05 0.10

0.02

0.04 0.04 0.10 0.03

ZrO2 (mg/kg)

0.02

0.02

0.04

BaO (mg/kg)

0.02

0.03

0.02

0.04

0.04

0.36

0.59

0.53

0.11

0.07

6.33

0.34

0.34

0.03

Conclusions The continuous application over 25 years of sugar foam waste to a red soil produces a positive impact on the soils characteristics. Such treatment improves the mineral fertilization satisfactorily, opening a new and interesting alternative from an environmental point of view. Treatment with sugar foam leads to an increase in pH, but not the electrical conductivity. Such treatment also leads to increase in the contents of N, P and Ca, as well as in the organic matter. Due to the contents of phosphorus and nitrogen, such foam can be used as a fertilizer and as an alterative to lime for soil amendment. Therefore, sugar foam waste has appropriate characteristics to improve soil quality. As a key conclusion, we can state that the use of molasses to replace traditional fertilization has three effects: the economic cost is lower, it produces a similar effect to fertilizer and solves the problem of nding locations to dispose of such waste. However, in the future it will be necessary to investigate whether this treatment causes stimulation of the microbiological activity and therefore alters the biological and biochemical properties.

P2O5 (g/kg)

0.18 0.67 1.94 0.13 0.80 0.81 0.05 4.17 12.7

0.13 1.19 1.63 0.11 1.43 1.15 0.03 9.14 21.4

0.36

0.55

0.53

0.19

TiO2 (g/kg)

0.21

0.26

0.04

0.78

1.14

0.12

K2O (g/kg)

0.83

0.87

0.16

1.77

Na2O (g/kg)

2.00

0.08

0.10

0.04

0.14

CaO (g/kg)

0.93

21.51

36.92

35.34

1.55

0.10

MgO (g/kg)

1.54

1.64

1.06

0.86

1.12

Table 3 Chemical composition of soil samples and sugar foam

MnO (g/kg)

0.02

0.04

0.06

0.03

Fe2O3 (g/kg)

1.13

1.51

0.27

4.06

9.16

Al2O3 (g/kg)

4.01

3.83

0.78

12.05

23.17

6.7

2.3

0.2

9.7

42.8

1.12

1.19

0.2

0.51

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21.39

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73.42

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Prole 1

2Bw

Ap1

Ap2

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2Bt

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