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Journal of Environmental Management 133 (2014) 374e377

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Journal of Environmental Management

journal homepage: www.elsevier .com/locate/ jenvman

Using marble wastes as a soil amendment for acidic soil neutralization

Gulsen Tozsin a,*, Ali Ihsan Arol b, Taskin Oztas c, Ekrem Kalkan d

aAtaturk University, Faculty of Earth Sciences, Department of Mining Engineering, 25400 Oltu, Erzurum, TurkeybMiddle East Technical University, Department of Mining Engineering, 06800 Ankara, TurkeycAtaturk University, Department of Soil Science and Plant Nutrition, 25240 Erzurum, TurkeydAtaturk University, Department of Geological Engineering, 25400 Oltu, Erzurum, Turkey

a r t i c l e i n f o

Article history:Received 7 November 2013Received in revised form16 December 2013Accepted 22 December 2013Available online 10 January 2014

Keywords:Marble quarry wasteMarble cutting wasteSoil aciditySoil amendments

* Corresponding author. Tel.: þ90 442 816 62 66; fE-mail address: gulsentozsin@gmail.com (G. Tozsi

0301-4797/$ e see front matter � 2013 Elsevier Ltd.http://dx.doi.org/10.1016/j.jenvman.2013.12.022

a b s t r a c t

One of the most important factors limiting plant growth is soil pH. The objective of this study is todetermine the effectiveness of marble waste applications on neutralization of soil acidity. Marble quarrywaste (MQW) and marble cutting waste (MCW) were applied to an acid soil at different rates and theireffectiveness on neutralization was evaluated by a laboratory incubation test. The results showed thatsoil pH increased from 4.71 to 6.36 and 6.84 by applications of MCW and MQW, respectively. It wassuggested that MQW and MCW could be used as soil amendments for the neutralization of acid soils andthus the negative impact of marble wastes on the environment could be reduced.

� 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Liming is a commonmethod to increase the pH of acid soils. Theliming material reacts with carbon dioxide and water in the soil toyield HCO�

3 , which removes the Hþ and Al3þ from the solution,raising the soil pH (Safari and Bidhendi, 2007; Muthukrishnan andOleske, 2008). Naturally occurring minerals such as lime (pre-dominantly CaCO3) are commonly used to reclaim acid soils (Wanget al., 2011).

Marble is a crystalline metamorphic limestone, basically con-taining calcite (CaCO3) and maybe dolomite (CaMg(CO3)2)(Segadães et al., 2005). Turkey has approximately 3872 million m3

of valuable marble reserve (Celik and Sabah, 2008). On the otherhand, as a result of the marble production activities, marble-manufacturing industry produces high amount of waste. Wastegeneration continues from mining process to final product and isabout 50% of mineral mined; the dried slurry product is quite fine.90% of the particles are below 200 mm. The waste of marble cancause environmental problem and economic loss if it is not used.However, waste marble can be used as a neutralization material foracid soil (Aruntas et al., 2010).

Marble wastes are generated by quarries (marble quarry waste-MQW) and processing plants (marble cutting waste-MCW). The

ax: þ90 442 816 33 32.n).

All rights reserved.

proportion of marble discharged as waste during block productionat the quarries is equal to 40e60% of the overall production volume.The waste generation rate at marble processing plants is around30e35% and this varies according to shape and kind of blocks beingcut (Celik and Sabah, 2008). The large amount of marble wastes is aserious problem for the industry and the environment because ofbeing discarded into rivers and lagoons without any treatment. Thistype of waste has a good potential to be used as an amendment forthe neutralization of acid soils (Xenidis et al., 2002; Karasahin andTerzi, 2007; Bilgin et al., 2012).

The objective of this incubation study is to determine theeffectiveness of marble waste applications on neutralization of soilacidity. More specifically, this study aimed to investigate how soilpH changes resulting from MQW and MCW amendments variedwith incubation time and thereby determine an optimum incuba-tion period and optimum amendment ratios for the neutralizationof acid soils.

2. Materials and methods

2.1. Soil and liming materials

A composite surface soil sample (0e20 cm) was taken from theKelali garden, Inece village, Bulancak town, Giresun, Turkey(38�1406000E, 40�5105400N). They were air-dried, passed through a 2-mm sieve and thoroughly mixed. Some chemical and physicalproperties of the soil samples are shown in Table 1. Particle size

Table 1Some physical and chemical properties of the studied soil. CEC; cation exchange capacity.

Texture Field capacity(%)

Bulk density(g cm�3)

pH 1:2.5(v/v)

Exchangeable cations (cmolc kg�1) CEC(cmolc kg�1)

H saturation(%)

Clay (%) Silt (%) Sand (%) Textural class Ca Mg Na K

21.0 34.8 44.2 Loam 37.0 1.3 4.71 6.95 1.79 0.70 0.70 23.1 56.0

G. Tozsin et al. / Journal of Environmental Management 133 (2014) 374e377 375

distribution was determined using the Bouyoucos hydrometermethod (Gee and Bauder, 1986). Field capacity was determined in0.033 MPa pressure using a membrane extractor (Cassel andNielsen, 1986). Bulk density was determined as described byBlake and Hartge (1986) and pH measured in soil suspensions witha soil to water ratio of 1:2.5 (v/v). The exchangeable cations weredetermined to be the difference between the soluble salts extractedwith deionized water using the fixed-ratio extract method(Rhoades, 1982) and the total extractable cations extracted usingthe ammonium acetate method (Thomas, 1982). The cation ex-change capacity was determined with a flame photometer usingsodium acetate-ammonium acetate buffered at pH 7 (Rhoades,1982).

The materials used as soil amendment, marble quarry wastes(MQW) and marble cutting wastes (MCW), were taken fromAfyonkarahisar region of Turkey. Moreover, agricultural lime (AL)produced by Niksar AS was applied to soil in order to compare theeffectiveness of marble waste applications for the neutralization ofsoil acidity. The pH and CaCO3 contents of the liming materials aregiven in Table 2.

The chemical compositions of the AL, MQW and MCW weredetermined using the X-ray fluorescence (XRF-Philips PW 1400)technique. The X-ray diffraction method (XRD-Rigaku Geigerflex D/max-series) was used to determine the mineralogical compositionsand the laser diffraction technique (Coulter LS 230) was used for thedefinition of the particle size distribution.

2.2. Soil incubation

A column (V10 cm � 35 cm) test was conducted for evaluatingthe effectiveness of the liming materials on neutralization of acidsoil under laboratory conditions. The total amount of marble wasteapplied was calculated as described by Brady and Weil (2004). Aseach molecule of CaCO3 neutralizes two Hþ ions through thefollowing reaction:

CaCO3 þ 2Hþ / Ca2þ þ CO2 þ H2O

Table 2The pH and CaCO3 (%) contents of the liming materials.

Agriculturallime (AL)

Marble quarrywaste (MQW)

Marble cuttingwaste (MCW)

pH 13.03 8.44 8.08CaCO3 (%) 100.00 99.24 94.12

Table 3Chemical composition of the AL, MQW and MCW materials determined by XRF (wt%). LoI: Loss on ignition (CO2).

Oxide compound (%) AL MQW MCW

CaO 55.86 55.04 50.80Na2O 0.04 1.87 0.68MgO 0.58 2.01 9.84Al2O3 0.70 0.63 0.76Fe2O3 0.29 0.22 0.48K2O 0.08 0.05 0.04LoI 42.60 35.20 37.20

the mass of lime needed was 5 g CaCO3 per kilogram of soil, a bulkdensity of 1.3 g cm�3 for the surface soil to a depth of 20 cm.Considering the purity of MQW (99.24% CaCO3) and MCW (94.12%CaCO3) and taking into account that not all the CaCO3 in theamendment completely reacts with the soil, the amount of limerequired was adjusted with three additional rates for MQW andMCW (0, 100% (1:1), 150% (1.5:1) and 200% (2:1)) each with threereplications. A non-amended control treatment was alsoconducted.

Fig. 1. X-ray diffraction patterns of the AL, MQW and MCW materials.

0.1

1

10

100

0.1 1 10 100 1000 10000

Cum

ulat

ive

pass

ing

(%)

Particle size (µm)

AL

MQW

MCW

Fig. 2. Particle size distribution of AL, MQW and MCW materials by laser diffraction.

Table 4The ANOVA test results for treatment effects on soil pH. All interactions (LMxIP,LMxAR, IPxAR and LMxIPxAR were not significant at p < 0.05.

Source of variation df F p

Liming material (LM) 3 77.1 0.01Incubation period (IP) 4 23.6 0.01Application rate (AR) 2 40.1 0.01LM � IP 12 1.257 0.26LM � AR 2 0.010 0.99IP � AR 8 0.418 0.91LM � IP � AR 8 0.443 0.89

Table 5The Duncan’s multiple comparison test results for the means. Means shown by thesame letter in each category were not different at p < 0.05 significant level (a, b, cand d are the Duncan grouping letters).

Treatments Levels Means of soil pH

Liming material Control 4.71cAL 5.90bMQW 6.26aMCW 5.83b

Incubation period 15 days 5.42d30 days 5.73c45 days 5.92b60 days 6.08a75 days 6.15a

Application rate 1:1 5.50c1.5:1 6.14b2.1 6.30a

G. Tozsin et al. / Journal of Environmental Management 133 (2014) 374e377376

In each case, the MQW and MCW doses were thoroughly mixedwith 2 kg air-dried soil, and then adjusted to 70% of field capacity.Soils were incubated at 25 �C and sub-sampled after 15, 30, 45, 60and 75 days, respectively, for the determination of soil pH. Soilmoisture content was adjusted gravimetrically every 2 days. Ateach sampling time, soil samples at two different pointsthroughout the column were taken using a corer (V1 cm) andmixed, then the holes were leveled out. The samples taken fromeach column was thoroughly mixed and immediately extracted forpH analysis. At the end of the 75-day incubation, soil pH wasdetermined.

2.3. Statistical analysis

The treatments (liming materials þ control (4), incubation pe-riods (5), application rates (3) were designed with three replicatesin a factorial arrangement. The analysis of variance (ANOVA) wasperformed to determine the effects of treatment, and the Duncan’smultiple comparison test procedure was used for mean compari-sons (SAS Institute Inc., 1989).

3. Results and discussion

The chemical compositions of the AL, MQWand MCWare givenin Table 3. All three materials are rich in CaO, which is changedbetween 50.8 and 55.86%. Fig. 1 shows the X-ray diffraction pat-terns of the liming materials. Calcite mineral was the maincomponent for AL and MQW, and dolomite was the main compo-nent for MCW. No other minerals were present at detectable levels.The crystalline phases identified by XRD are in agreement with theresults obtained by XRF (Table 3).

The results of particle size analysis of AL, MQW and MCW aregiven in Fig. 2. 80% of the particles were found to be less than 55 mmin diameter for AL (d80 ¼ 55 mm), 400 mm in diameter for MQW(d80 ¼ 400 mm) and 35 mm in diameter for MCW (d80 ¼ 35 mm).

Data was subjected to variance analysis (ANOVA) in order todetermine the treatment effects. The ANOVA results indicated thatall treatment effects were statistically significant at p < 0.01 level(Table 4). However, all interactions: liming material(LM) � incubation period (IP), LM � application rate (AR), IP � ARand LM � IP �AR were not statistically significant at p < 0.05 level.Results of this study indicated that MQW and MCW, alternative toagricultural lime, significantly increased soil reaction under allconditions. However, the increasing rate in soil pH was dependenton incubation period and application rate.

The Duncan’s multiple comparison test results showed that theMQW was the most effective amendment and no significant dif-ference existed between the AL and MCW in terms of soil reaction(Table 5). On the average, while soil pH of the control was 4.71, itincreased up to 6.26 with MQW. In evaluating the effect of incu-bation period of liming materials on soil pH, soil pH increased withincreasing incubation period and there was no significant differ-ence in pH values at the longest two incubation periods (60 and 75days). This meant that 60 days could be enough for incubation ofliming materials for the soil and experimental conditions in thisstudy. The effect of application rate of marble wastes on soil pHchanges was very clear, and increasing the application rateincreased soil pH. Since the multiple comparison test resultsshowed the overall effect of all treatment factors, more detailedeffects of liming materials and incubation periods were presented

Fig. 3. Changes in soil pH as a function of incubation period for different limingmaterials.

G. Tozsin et al. / Journal of Environmental Management 133 (2014) 374e377 377

in Fig. 3. It also helps compare and evaluate the results of MQWandMCW with AL and the control.

Fig. 3 clearly indicated that all treatments increased soil pH ascompared to the control. Throughout the incubation period, the pHof the control was relatively constant with a mean of 4.71 � 0.18. Inall of the treated samples, just 15 days after liming, the pH valuesrapidly increased from 4.71 to 5.37e5.81 depending on the typeand the application rate of the liming material. Increase in pH wasfaster in samples having larger waste material additions with 1.5:1and 2:1 application rates relative to agricultural lime than thosewith 1:1 application rate. Muthukrishnan and Oleske (2008)emphasized that samples having larger lime additions reacheddesirable pH faster than those with smaller amendments. From theremaining time to the end of the incubation period, increasing rateof pH was relatively small, reaching 6.2 and 6.84. As explained byFernández-Caliani and Barba-Brioso (2010) dissolution of calcitepromoted the neutralization of the acidity by the followingreactions;

CaCO3 þ H2CO3 ¼ Ca2þ þ 2HCO�3

CaCO3 þ H2O ¼ Ca2þ þ HCO�3 þ OH�

The closest values to the control were produced by MCW 1:1,which meant that it was the least effective liming material andapplication rate for amendment. The best result for soil pHarrangement was obtained with MQW 2:1 followed by MQW 1.5:1treatments. The treatments MQW 1:1, MCW 1.5:1 and MCW 2:1were still good enough and they produced almost the same effectthat with AL.

4. Conclusions

All the above-mentioned results suggest that marble cuttingwaste (MCW) and especially the marble quarry waste (MQW) could

be used alternatively to agricultural lime for the neutralization ofacid soils. Carbonate resulting from the processing of marble is aneffective amendment to neutralize soil acidity. The use of MQWandMCW due to their great potential as an acid-neutralizing materialmay also help reduce the negative effects of these materials as awaste disposal on environment.

Acknowledgment

The authors gratefully acknowledge the financial support byAtaturk University BAP project through grant number 2012/186.

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