Int. J. Environ. Sci. Technol.

(2014) 11:33–42
DOI 10.1007/s13762-013-0433-7

ORIGINAL PAPER

Interaction of organic acids and pH on multi-heavy metal

extraction from alkaline and acid mine soils
Y. Z. Ding • Z. G. Song • R. W. Feng •

J. K. Guo

Received: 26 October 2011 / Revised: 5 June 2012 / Accepted: 23 August 2012 / Published online: 11 December 2013
Ó Islamic Azad University (IAU) 2013

Abstract Vegetation at mining sites can produce increased Keywords Chelating  Contamination  Leaching 
heavy metal leaching by the organic acids and protons origi- Mining  Trace metals  Revegetation
nating from root secretion and litter degradation. Batch
experiments were conducted to investigate the effects of
organic acids and pH on the extraction of Pb, Cd, Zn and Cu Introduction
from an alkaline mine soil (sampled from a mining site of
Chenzhou City, Hunan Province) and an acid mine The exploitation of mineral resources provides us with
soil (sampled from a mining site of Daxin county, Guangxi strategic resources, but also causes environmental pollution
Province). The results showed that in the presence of organic and ecological damage. In China, the total destroyed and
acids (acetic, oxalic, malic, fumaric, tartaric and citric acids) at occupied land due to mining has reached 7.43 million hm2
pH 7, the extraction of Pb, Cd, Zn and Cu from the acid mine and is estimated to increase annually by 40,000 hm2 (Qiu
soil was much higher than that from the alkaline mine soil, in et al. 2009). Multi-metal pollution in the soils within the
which only citric acid with higher concentration was capable vicinity of mines has become one of the most serious
of extracting some heavy metals. Citric acid had the strongest environmental issues (Conesa and Schulin 2010). These
ability in extracting heavy metals, followed by oxalic acid. heavy metals may be released via the erosion of wind and
Heavy metal extraction dramatically decreased with increas- water and can ultimately enter the food chain (Navarro
ing pH. Moreover, at low pH, oxalic acid promoted the risk of et al. 2008). Today, great efforts are being made to reme-
Cu leaching; at high pH, the leaching of Pb, Zn, Cd and Cu was diate polluted mining sites, in which revegetation or phy-
enhanced by both oxalic and citric acids. This indicated that tostabilization is considered to be an efficient way to
those plants, which can produce substantial citric acid or achieve long-term reclamation (Arienzo et al. 2004; Men-
oxalic acid by root secretion and litter degradation, should not dez and Maier 2008a, b). However, disadvantageous con-
be selected for the revegetation of mining sites. sequences after revegetation cover may arise due to organic
acids excreted by the roots and/or decomposed by the lit-
ters of inhabiting plants. It was evidenced that organic
Y. Z. Ding (&)  Z. G. Song  R. W. Feng  J. K. Guo
acids could enhance the desorption of heavy metals from
Agro-Environmental Protection Institute, Ministry
of Agriculture, No. 31, Fukang Road, Nankai District, soils, resulting in more heavy metals leaching into the
Tianjin 300191, People’s Republic of China water body (Zhu et al. 1999). Lu et al. (2007) showed that
e-mail: [email protected] exchangeable Cd was positively related to total organic
acids in rhizosphere soils. Burckhard et al. (1995) found
Y. Z. Ding  Z. G. Song  R. W. Feng  J. K. Guo
Key Laboratory of Production Environment and Agro-product that organic acids, especially citric acid, promoted the
Safety, Ministry of Agriculture, Tianjin 300191, leaching of Zn in mine tailings.
People’s Republic of China Low molecular weight organic acids, mainly originating
from the decomposition of soil organic matter, plant root
Y. Z. Ding  Z. G. Song  R. W. Feng  J. K. Guo
Tianjin Key Laboratory of Agro-environment and Food Safety, exudates and microbial metabolites (Jones 1998; Strobel
Tianjin 300191, People’s Republic of China 2001), play important roles in controlling the solubility of

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34 Int. J. Environ. Sci. Technol. (2014) 11:33–42

heavy metals and their subsequent uptake by plants due to acidity of rhizosphere soil is usually different from that of
the chelation or complexation between organic acids and bulk soil, and many plants can contribute to soil acidifi-
heavy metals (Krishnamurti et al. 1997; Han et al. 2006). cation (Zhu et al. 1999). Although the effect of organic
Naidu and Harter (1998) reported that organic ligands acids on the solubility of heavy metals has been researched
increased the extractability of Cd from soils. It was found widely, people are still unclear about the interaction among
that citric acid could significantly reduce Cd adsorption on organic acids, pH and heavy metals in mine soils. Better
soils due to the formation of soluble Cd–organic complexes understanding the interactions will help to construct more
(Zhou et al. 2003). Schwab et al. (2008) found that citric environmentally friendly vegetative covers in mining sites
acid greatly enhanced the movement of Zn and Cd in soils, and decrease the leaching of heavy metals into the ambient
but had little influence on Pb movement. And some surroundings.
researchers also found that citrate had the most efficiency In order to clarify the interaction of organic acids and
in releasing Cd, Pb and Zn than other organic acids (Wuana pH on the leaching of multi-heavy metals from mine soils,
et al. 2010; Vesely et al. 2011). Low concentration of two typical mine soils (an alkaline soil and an acid soil) in
tartrate and citrate inhibited the desorption of Cd and Cu, South China were selected, and the effects of organic acids
but high concentration of tartrate and citrate promoted the on the extractability of Pb, Cd, Zn and Cu were investi-
desorption (Gao et al. 2003). Citric acid, malic acid and gated under different concentrations and different acidity.
acetic acid more effectively desorbed Cu, Cd and Pb from The study was carried out in Agro-Environmental Protec-
soils than inorganic salts such as CaCl2 and NaNO3 (Qin tion Institute, Ministry of Agriculture, Tianjin, in August–
et al. 2004). Increasing citric, oxalic or malic acid con- September, 2010.
centrations resulted in increases in Cd adsorption on acidic
paddy and red soils at low pH, but citric acid dramatically
increased Cd solubility at high pH (Ding et al. 2008). These Materials and methods
results suggested that organic acids might stimulate either
the solubility or the immobility of heavy metals in soils, Soil sampling
depending upon the type and concentration of organic
ligands, the type of metals, the soil properties and other An alkaline mine soil (Chenzhou soil) and an acid mine
environmental factors (Collins et al. 2003; Ding et al. soil (Daxin soil) were sampled from mining sites of
2008). Chenzhou City (112°130 –112°550 E, 25°270 –26°130 N),
In order to choose suitable plant species for revegetation Hunan Province, and Daxin county (106°390 –107°290 E,
of mining sites, people must investigate the leaching risks 22°290 –23°050 N), Guangxi Province, respectively. Both
of heavy metals affected by organic acids and protons from soil samples were collected from the surface layer
root exudates and litter degradation. Stresses to plants (0–20 cm) and were air-dried, ground to pass through a
resulting from nutrient deficiency and heavy metal toxici- 60-mesh sieve (0.25 mm), and stored for analysis.
ties in mine soils often induce increased root exudates that Soil pH was measured in distilled water at a soil-to-
are rich in organic ligands (Ryan et al. 2001). It is still solution ratio of 1:2.5 (w:v). The content of soil organic
unclear whether organic acids are exuded by roots as free matter (SOM) was determined by the method of Nelson
acids or alkali metal salts (Jones 1998). In any case, the and Sommers (1996). Cation exchange capacity (CEC)

Table 1 Properties of the mine soils studied

Item Chenzhou soil Daxin soil

pH (H2O) 7.93 ± 0.01a 6.28 ± 0.02

-1
CEC (cmol kg ) 43.2 ± 0.28 11.2 ± 0.07
Organic matter (g kg-1) 3.89 ± 0.53 25.58 ± 1.61
Pb (mg kg-1) 7,200 ± 14.6 (350)b 829.5 ± 3.73 (250)
Zn (mg kg-1) 2,471 ± 12.7 (300) 4,130 ± 14.5 (200)
Cu (mg kg-1) 2,020 ± 13.5 (100) 29.2 ± 0.11 (50)
Cd (mg kg-1) 77.4 ± 0.91 (1.0) 45.87 ± 0.49 (0.3)
a
Mean ± SD (n = 3)
b
Values in brackets are the National Soil Environmental Quality Standard of China

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Int. J. Environ. Sci. Technol. (2014) 11:33–42 35

was determined by the method of Bao (Bao 2000). Total Extractability of Pb, Cd, Zn and Cu in mine soils
concentrations of Pb, Cd, Zn and Cu in the soils were by different organic acids with initial pH 7
determined by HF–HClO4 digestion (Tessier et al. 1979)
and ICP-OES analysis (Optima 2000 DV, PerkinElmer, Organic acid solutions were prepared, with the concentra-
America). Accuracy was evaluated by the use of a cer- tion of 0, 0.2, 0.5, 1.0, 2.0, 5.0 and 10.0 mmol L-1,
tified reference material (Institute of Geophysical and respectively. All solutions contained a background elec-
Geochemical Exploration, NO. GBW07430). Multi-ele- trolyte of 0.01 mol L-1 NaNO3, and solution pH was
ment standards, which were used as the certified refer- adjusted to pH 7 using diluted NaOH/HNO3. A total of
ence material, were purchased from Sigma-Aldrich Co. 1.5 g soil was placed in a 50-mL polypropylene centrifuge
LLC. All other reagents were analytical-reagent grade tube, 30 mL organic acid solution was added, and then 2
and were obtained from Sinopharm Chemical Reagent drops of toluene was added to inhibit microbial activity
Beijing Co., Ltd. The physicochemical properties of both (Naidu and Harter 1998). The suspension was shaken end-
mine soils are listed in Table 1. Both mine soils were over-end for 5 h at 25 °C, centrifuged at 3,000g for
heavily polluted with Pb, Cd, Zn or Cu compared with 15 min, and then filtered using 0.45-lm nylon membrane
the individual National Soil Environmental Quality filters. The equilibrium pH was determined, and the con-
Standard of China (GB 15618–1995). Although the Cu centrations of Pb, Cd, Zn and Cu in the filtrates were
concentration in the Daxin soil was not high, the data measured by ICP-OES. In this experiment, there were three
are still shown in this study for comparison with that of replicates in each treatment.
the Chenzhou soil.
Extractability of Pb, Cd, Zn and Cu in mine soils
Organic acids tested by citric acid and oxalic acid as a function of pH

Acetic acid, oxalic acid, malic acid, fumaric acid, tartaric Many plants can produce organic acids and protons
acid and citric acid were selected to extract heavy metals from root exudation or litter degradation. Citric and
(Pb, Cd, Zn and Cu). These organic acids are commonly oxalic acids were chosen to study the combined effects
present in soils, and the tested concentrations ranging from of pH and organic acids on heavy metal extraction
0 to 10.0 mmol L-1 are reasonable for soils, especially in because they have the highest chelating abilities with
the rhizosphere soils (Krishnamurti et al. 1997; Jones heavy metals according to the results of the above
1998). The organic acids were purchased from Sigma- experiment. A total of 1.5 g soil was placed in a
Aldrich Co. LLC. 50-mL polypropylene centrifuge tube, 30 mL organic

Table 2 Extraction of Pb, Cd, Zn and Cu (mg kg-1) from Chenzhou soil by organic acids at initial pH 7
Organic acids Heavy Concentrations of organic acids (mmol L-1)
metals
0 0.2 0.5 1.0 2.0 5.0 10.0
a
Acetic/Fumaric Pb/Cd/Zn nd nd nd nd nd nd nd
acid Cu 0.20 ± 0.01a b
0.20 ± 0.01a 0.20 ± 0.01a 0.20 ± 0.01a 0.20 ± 0.01a 0.20 ± 0.01a 0.20 ± 0.01a
Oxalic acid Pb/Cd/Zn nd nd nd nd nd nd nd
Cu 0.20 ± 0.01c 0.23 ± 0.04c 0.25 ± 0.05c 0.24 ± 0.05c 0.31 ± 0.03c 2.42 ± 0.01b 12.5 ± 0.21a
Tartaric acid Pb/Cd/Zn nd nd nd nd nd nd nd
Cu 0.20 ± 0.01e 0.22 ± 0.03e 0.22 ± 0.02e 0.31 ± 0.03d 0.44 ± 0.02c 1.09 ± 0.03b 2.19 ± 0.01a
Malic acid Pb/Cd nd nd nd nd nd nd nd
Zn nd nd nd nd nd nd 0.67 ± 0.13
Cu 0.20 ± 0.01e 0.21 ± 0.01e 0.33 ± 0.01e 0.69 ± 0.01d 1.59 ± 0.07c 3.48 ± 0.12b 8.41 ± 0.34a
Citric acid Pb nd nd nd nd nd 7.79 ± 1.19b 47.1 ± 3.20a
Cd nd nd nd nd 0.74 ± 0.05c 4.20 ± 0.03b 9.19 ± 0.21a
Zn nd nd nd 0.51 ± 0.25d 7.95 ± 0.17c 47.1 ± 1.34b 102 ± 3.78a
Cu 0.20 ± 0.01f 0.61 ± 0.04f 4.69 ± 0.18e 21.2 ± 0.65d 67.0 ± 0.82c 149 ± 3.02b 204 ± 1.71a
a b
nd = not detected; values ± SD (n = 3), means in the same row followed by the same letters are not significantly different, whereas means
by the different letters are significantly different at p \ 0.05

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36 Int. J. Environ. Sci. Technol. (2014) 11:33–42

acid (citric acid or oxalic acid) solution containing Results and discussion
0.01 mol L-1 NaNO3 was added, and then 2 drops of
toluene was added. The tested concentration of citric Extractability of heavy metals in mine soils by different
acid and oxalic acid was 0, 0.5, 1.0 and 5.0 mmol L-1, organic acids
respectively, and their solution pH was adjusted to
different values using diluted NaOH/HNO3. The sub- The extraction of heavy metals from both mine soils varied
sequent procedure was the same as described above. greatly (Tables 2, 3). Except citric acid with higher con-
Finally, the equilibrium pH was determined, and the centration, organic acids hardly extracted heavy metals
concentrations of Pb, Cd, Zn or Cu in the filtrates from Chenzhou soil. Contrarily, all organic acids could
were measured by ICP-OES. In this experiment, there extract well heavy metals from Daxin soil. The heavy
were three replicates in each treatment. metals of Daxin soil were much easily extracted than that
of Chenzhou soil. Soil properties such as pH, CEC, OM,
Statistical analysis clay content and oxides of iron and manganese play
important roles in controlling the solubility of heavy metals
The statistical analysis was performed in triplicate samples, (Naidu et al. 1994). Chenzhou soil was a permanent charge
and the mean values with standard error were recorded. soil with high surface negative charges, so its soil char-
The data were subjected to one-way analysis of variance acteristics dominantly control the solubility of heavy metal
(ANOVA) and Duncan’s multiple range test using SPSS solubility, and the extraction of heavy metals was hardly
(version 16.0, SPSS Inc., USA). The significant differences affected by environmental factors such as organic acids. On
between treatments were calculated at 5 % probability the contrary, Daxin soil was a variable charge soil where
levels (p \ 0.05). the charge could be regulated by the adsorption of

Table 3 Extraction of Pb, Cd, Zn and Cu (mg kg-1) from Daxin soil by organic acids at initial pH 7
Organic Heavy Concentrations of organic acids (mmol L-1)
acids metals
0 0.2 0.5 1.0 2.0 5.0 10.0

Acetic acid Pb 1.17 ± 0.22cda 0.99 ± 0.01e 1.14 ± 0.08d 1.09 ± 0.02de 1.27 ± 0.07c 1.53 ± 0.10b 2.27 ± 0.02a
Cd 2.46 ± 0.02c 2.66 ± 0.16b 2.69 ± 0.03b 2.66 ± 0.01b 2.76 ± 0.14b 2.76 ± 0.06b 2.95 ± 0.31a
Zn 202 ± 0.71a 204 ± 1.10a 202 ± 2.78a 206 ± 1.56a 206 ± 11.8a 199 ± 4.61a 203 ± 2.46a
Cu 0.44 ± 0.00d 0.47 ± 0.01cd 0.50 ± 0.01bc 0.52 ± 0.01b 0.52 ± 0.01b 0.53 ± 0.01b 0.77 ± 0.09a
Fumaric Pb 1.17 ± 0.22e 1.11 ± 0.04e 1.23 ± 0.06e 1.46 ± 0.10d 1.76 ± 0.04c 2.69 ± 0.04b 3.86 ± 0.14a
acid Cd 2.46 ± 0.02f 2.82 ± 0.04e 2.87 ± 0.05e 3.04 ± 0.02d 3.22 ± 0.02c 3.76 ± 0.08b 4.55 ± 0.07a
Zn 202 ± 0.71d 230 ± 2.12c 225 ± 5.37c 226 ± 4.95c 231 ± 1.56c 251 ± 8.21b 274 ± 4.95a
Cu 0.44 ± 0.00f 0.43 ± 0.00f 0.49 ± 0.02e 0.48 ± 0.01e 0.56 ± 0.02c 0.68 ± 0.04b 0.87 ± 0.01a
Oxalic acid Pb 1.17 ± 0.22g 2.20 ± 0.03f 4.42 ± 0.06e 7.32 ± 0.05d 9.74 ± 0.10c 14.8 ± 2.10b 21.0 ± 0.09a
Cd 2.46 ± 0.02a 1.98 ± 0.03b 1.62 ± 0.03c 1.49 ± 0.03d 1.14 ± 0.03f 1.05 ± 0.03g 1.23 ± 0.01e
Zn 202 ± 0.71g 242 ± 0.35f 327 ± 4.24e 432 ± 10.2d 484 ± 18.3c 589 ± 10.2b 741 ± 20.3a
Cu 0.44 ± 0.00g 0.64 ± 0.01f 1.26 ± 0.00e 2.34 ± 0.04d 4.48 ± 0.33c 7.41 ± 0.10b 10.1 ± 0.11a
Tartaric Pb 1.17 ± 0.22f 1.13 ± 0.04f 1.55 ± 0.06d 2.42 ± 0.02c 3.61 ± 0.21c 9.51 ± 0.04b 21.4 ± 1.26a
acid Cd 2.46 ± 0.02a 2.30 ± 0.02b 2.08 ± 0.06c 1.92 ± 0.01e 1.76 ± 0.03f 1.75 ± 0.04f 1.98 ± 0.01d
Zn 202 ± 0.71d 184 ± 7.34f 192 ± 1.16ef 199 ± 0.95de 234 ± 12.4c 319 ± 2.69b 383 ± 15.0a
Cu 0.44 ± 0.00d 0.54 ± 0.00d 0.54 ± 0.01d 0.59 ± 0.00d 0.81 ± 0.19c 1.13 ± 0.17b 1.90 ± 0.26a
Malic acid Pb 1.17 ± 0.22f 1.26 ± 0.02f 2.35 ± 0.03e 5.47 ± 0.05d 7.21 ± 0.07c 12.6 ± 0.11b 18.3 ± 0.07a
Cd 2.46 ± 0.02a 2.25 ± 0.03b 1.95 ± 0.04c 1.64 ± 0.03d 1.47 ± 0.03f 1.39 ± 0.02f 1.42 ± 0.02f
Zn 202 ± 0.71g 223 ± 0.05f 265 ± 1.12e 286 ± 0.82d 337 ± 9.51c 426 ± 6.89b 532 ± 10.5a
Cu 0.44 ± 0.00f 0.59 ± 0.03f 0.92 ± 0.23e 1.32 ± 0.15d 2.63 ± 0.37c 4.78 ± 0.12b 6.45 ± 0.32a
Citric acid Pb 1.17 ± 0.22f 4.39 ± 0.08f 15.1 ± 0.35e 38.0 ± 0.02d 77.3 ± 1.77c 120 ± 7.09b 177 ± 2.40a
Cd 2.46 ± 0.02f 2.17 ± 0.01f 3.88 ± 0.07e 6.45 ± 0.16d 9.88 ± 0.40c 12.8 ± 0.74b 16.2 ± 0.25a
Zn 202 ± 0.71f 219 ± 3.68f 349 ± 8.85e 604 ± 15.4d 820 ± 16.9c 971 ± 50.1b 1,091 ± 59.7a
Cu 0.44 ± 0.00g 1.60 ± 0.02f 2.91 ± 0.20e 3.36 ± 0.17d 4.86 ± 0.15c 6.44 ± 0.29b 8.27 ± 0.71a
a
Values ± SD (n = 3), means in the same row followed by the same letters are not significantly different, whereas means by the different
letters are significantly different at p \ 0.05

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potential-determining ions (H? and OH-) on the surface. Apparently, citric acid changed the desorption orders of Cu
Subsequently, the adsorption of heavy metal ions on Daxin and Zn in both mine soils, which could be attributed to
soils was easily affected by environmental factors such as higher stability constant of Cu–citric acid complex than
chelating organic acids. Zn–citric acid complex. Furthermore, for most metals,
Different organic acids showed different influences on citric acid has the strongest chelating ability among low
the solubility of heavy metals in both mine soils molecular weight organic acids.
(Tables 2, 3). For example, the extraction amounts of Cu Citric acid has the strongest ability to extract heavy
from the Chenzhou soil by acetic acid, fumaric acid, metals because it has three carboxyl groups, which can
oxalic acid, malic acid, tartaric acid and citric acid at a form stable five- or six-member chelate rings (Qin et al.
concentration of 10.0 mmol L-1 were 0.20, 0.20, 12.5, 2004). However, Cu extraction from Daxin soil by citric
2.19, 8.41 and 204 mg kg-1, respectively, whereas from acid with higher concentration was less than that by
the Daxin soil, the values were 0.77, 0.87, 10.1, 6.45, oxalic acid under the same conditions (Table 3), perhaps
1.90 and 8.27 mg kg-1, respectively. Elkhatib et al. because the equilibrium pH of soil citric acid was higher
(2007) also found that citric acid had higher Cu than that of soil oxalic acid, as shown in Table 4.
extraction ability than other organic acids. The Zn Equilibrium pH plays another important role in control-
extraction amounts from the Daxin soil by these organic ling the solubility of heavy metals (Appel and Ma 2002).
acids were 203, 274, 741, 383, 532 and 1,091 mg kg-1, The acid-buffering capacity of mine soils had different
respectively, while from the Chenzhou soil, only a small response to organic acids (Table 4). The values of
quantity of Zn was extracted by citric acid. So, citric equilibrium pH of Daxin soil ranged from 5.77 to 7.23
acid had the strongest ability to extract heavy metals, when different organic acids with initial pH 7 were
followed by oxalic acid. added, whereas that of Chenzhou soil ranged from 8.06
In the presence of citric acid of 10.0 mmol L-1, the to 9.43, that is, Chenzhou soil had greater acid-buffering
desorption rate of metals from Daxin soil followed the capacity than Daxin soil. This partly explained why the
order: Pb (21.3 %) \Zn (26.4 %) \Cu (28.3 %) \Cd extraction of heavy metals from the former was much
(35.3 %) and that from Chenzhou soil followed the same lower than that from the latter. Additionally, the different
order: Pb (0.7 %) \Zn (4.1 %) \Cu (10.1 %) \Cd equilibrium pHs of the Daxin soil may partly explain
(11.9 %). However, the common sequence of metal why the extraction amounts of Cd decreased as the
adsorption on soils is Pb [ Cu [ Zn [ Cd, which it is concentration of some organic acids (oxalic, tartaric and
related to the first hydrolysis equilibrium constant (Usman malic acid) increased (Table 3). Herein, it is necessary to
2008). In the absence of citric acid, the desorption rate of consider the interaction effect of organic acids and pH
heavy metals from Daxin soil followed the order: Pb on the extractability of heavy metals in mine soils.
(0.14 %) \Cu (1.5 %) \Zn (4.9 %) \Cd (5.4 %).

Table 4 Equilibrium pH values after organic acids added to mine soils with initial pH 7
Soils Organic acids Concentrations of organic acids added to the soils (mmol L-1)
0 0.2 0.5 1.0 2.0 5.0 10.0

Chenzhou soil Acetic acid 8.44 ± 0.02a 8.14 ± 0.01 8.15 ± 0.01 8.19 ± 0.01 8.21 ± 0.01 8.12 ± 0.00 7.97 ± 0.03
Fumaric acid 8.44 ± 0.02 8.45 ± 0.03 8.47 ± 0.02 8.48 ± 0.03 8.51 ± 0.02 8.53 ± 0.02 8.55 ± 0.03
Oxalic acid 8.44 ± 0.02 8.53 ± 0.01 8.66 ± 0.01 8.88 ± 0.01 9.18 ± 0.02 9.35 ± 0.01 9.43 ± 0.03
Tartaric acid 8.44 ± 0.02 8.47 ± 0.01 8.51 ± 0.01 8.51 ± 0.02 8.48 ± 0.02 8.53 ± 0.01 8.55 ± 0.01
Malic acid 8.44 ± 0.02 8.06 ± 0.02 8.14 ± 0.03 8.24 ± 0.01 8.27 ± 0.01 8.36 ± 0.04 8.40 ± 0.03
Citric acid 8.44 ± 0.02 8.31 ± 0.02 8.40 ± 0.01 8.62 ± 0.02 8.79 ± 0.02 8.85 ± 0.02 8.90 ± 0.02
Daxin soil Acetic acid 5.77 ± 0.02 5.84 ± 0.01 5.86 ± 0.01 5.90 ± 0.01 6.02 ± 0.00 6.07 ± 0.01 6.24 ± 0.00
Fumaric acid 5.77 ± 0.02 5.87 ± 0.01 5.92 ± 0.01 5.91 ± 0.02 5.98 ± 0.04 6.04 ± 0.02 6.11 ± 0.01
Oxalic acid 5.77 ± 0.02 5.87 ± 0.01 6.03 ± 0.05 6.14 ± 0.02 6.46 ± 0.06 6.70 ± 0.02 7.00 ± 0.05
Tartaric acid 5.77 ± 0.02 5.87 ± 0.01 5.96 ± 0.01 5.99 ± 0.03 6.02 ± 0.04 6.11 ± 0.02 6.26 ± 0.01
Malic acid 5.77 ± 0.02 5.87 ± 0.01 5.99 ± 0.02 6.07 ± 0.02 6.21 ± 0.03 6.56 ± 0.02 6.89 ± 0.03
Citric acid 5.77 ± 0.02 5.90 ± 0.04 6.12 ± 0.03 6.30 ± 0.03 6.70 ± 0.07 7.07 ± 0.03 7.23 ± 0.01
a
Values ± SD (n = 3)

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30
Citric acid Oxalic acid
Cd Cd
20
0

10

a b
0

Citric acid Oxalic acid

300
Cu Cu

200
Extractable heavy metals (mg kg -1 )

100

c d
0

450
Citric acid Oxalic acid
Zn Zn
300

150

e f
0

210
Citric acid Oxalic acid
Pb Pb
140

70

g h
0
3 4 5 6 7 4 5 6 7 8
Soil solution pH
Fig. 1 Extraction of Pb, Cd, Zn and Cu from Chenzhou soil by citric acid and oxalic acid as a function of pH. Error bars represent standard
deviations of triplicate measurements

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Int. J. Environ. Sci. Technol. (2014) 11:33–42 39

40
Citric acid Oxalic acid
Cd Cd
30

0
20

10

a b
0

16
Citric acid Oxalic acid
Cu Cu
12

8
Extractable heavy metals (mg kg -1)

c d
0

4000
Citric acid Oxalic acid
Zn Zn
3000

2000

1000

e f
0
800
Citric acid Oxalic acid
40 Pb Pb
600 30
20 30
10 20
400 0
4 5 6 7 10
0
200 4 5 6 7
g h
0
2 3 4 5 6 7 8 2 3 4 5 6 7 8
Soil solution pH
Fig. 2 Extraction of Pb, Cd, Zn and Cu from Daxin soil by citric acid and oxalic acid as a function of pH. Error bars represent standard
deviations of triplicate measurements

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40 Int. J. Environ. Sci. Technol. (2014) 11:33–42

Extractability of heavy metals in mine soils by organic and soil pH played dominant role in controlling the solu-
acids as a function of pH bility of heavy metals.
Different concentrations (0–5 mmol L-1) of citric acid
The extraction amount of heavy metals significantly or oxalic acid exerted different effects on heavy metal
decreased with increasing pH (Figs. 1 and 2). In the solubility, depending on the soil solution pH and the
absence of organic acids, for Chenzhou soil, when specific organic acid. For example, citric acid promoted
equilibrium pH increased from 4.4 to 6.8, the extraction Cd adsorption at low pH, whereas it enhanced Cd
of heavy metals decreased as follows: Cd from 25.7 to desorption at high pH; oxalic acid had little effect except
1.04 mg kg-1, Cu from 198 to 0.34 mg kg-1, Zn from it enhanced Cd adsorption at high concentration
379 to 5.44 mg kg-1 and Pb from 105 to 1.50 mg kg-1. (5 mmol L-1). Some previous researchers (Naidu and
For Daxin soil, when pH increased from 2.1 to 6.8, the Harter 1998; Ding et al. 2008) also found that Cd
corresponding decrease was: Cd from 37.3 to adsorption was enhanced in the presence of organic
0.88 mg kg-1, Cu from 11.6 to 0.90 mg kg-1, Zn from ligands at low pH. However, other studies have shown
3,538 to 80.0 mg kg-1 and Pb from 777 to that Cd extraction increased with an increase in citrate
1.56 mg kg-1, respectively. The dependency of heavy concentration (Gao et al. 2003; Hu et al. 2006). Copper
metals on soil pH was consistent with the results extraction increased as the concentration of citric or
obtained by some previous researchers (Appel and Ma oxalic acid increased, indicating that dissolved citric and
2002; Qin et al. 2004). The net negative surface charge oxalic acids compete over soil adsorption sites for Cu. For
of soils increases with increasing pH, resulting in higher Zn, the effect of citric acid was similar to Cd, whereas
affinity between soil surfaces and heavy metal ions that of oxalic acid differed between both soils. The oxalic
(Harter and Naidu 2001). Further, pH changes the ion acid had similar effects as citric acid on the Daxin soil
forms of metals adsorbed on soil surfaces where the but had little effect on the Chenzhou soil. For Pb, the
hydrolysis of metal cations increases with increasing pH. citric and oxalic acid enhanced desorption on the Daxin
In addition, soil pH also affects the solubility of heavy soil. In the Chenzhou soil, Pb was little affected by
metals by influencing the surface potential, clay edge organic acids, but the strong complexing ligand, citrate,
charge, ion-pair formation, the solubility of organic reduced Pb sorption at a high concentration
matter and the stability of metal carbonates and phos- (5.0 mmol L-1). Overall, citric acid and oxalic acid could
phates (Appel and Ma 2002). In a word, due to these increase the leaching risk of heavy metals at high pH,
changes of heavy metals in adsorption, solubility, sta- whereas only oxalic acid could increase Cu leaching at
bility, etc., the extractability of heavy metals was low pH.
affected strongly by soil pH, in which there is usually With the introduction of organic acids, the solubility of
marked decrease in the extraction of heavy metals with heavy metals could be changed due to the interaction
the increase in soil pH. among soil surfaces, soil solution pH, organic ligands and
In the presence of organic acids, the extraction of heavy heavy metals. On the one hand, organic acids enhanced the
metals from mine soils also decreased with increasing pH mobility of heavy metals by forming stable metal–ligand
(Figs. 1, 2). However, for Daxin soil, the extraction of Cd, complexes, or by directly competing for cation adsorption
Cu and Pb by citric acid had different trend with increasing sites or by reducing the negative electrostatic potential of
pH, where the extraction amounts decreased sharply at soil surfaces (Collins et al. 2003). On the other hand,
first, then increased dramatically and then declined sig- organic acids could also decreased the mobility of heavy
nificantly again (Fig. 2). Ding et al. (2008) also found the metals by co-adsorbing on soil surfaces and forming soil
similar behavior for Cd on red soil and paddy soil. The organic acid–metal bridge (ternary) complexes (Naidu and
main form of citric acid (denoted as H3L) changed from Harter 1998). In short, the effect of organic acids on the
H3L to H2L- to HL2- and finally to L3- with the increase solubility of heavy metals in soils is not simple or constant.
in soil pH. Because the latter two forms had higher che- For example, in this study, organic acids at low concen-
lating ability to heavy metals and restricted stronger the tration can extract more heavy metals than at high con-
hydrolysis of heavy metals than other formers, there was centration in some cases (Figs. 1, 2), and weak organic
more extraction of heavy metals at higher pH (Qin et al. acids can extract more heavy metals than strong organic
2004). For Chenzhou soil, the extraction of heavy metals acids (Fig. 2c, d). Therefore, more researches should be
continually decreased with increasing pH (Fig. 1), it could focused on the interaction among soils, organic acids,
be explained that there had higher affinity to heavy metals heavy metals and soil solution pH.

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Acknowledgments This research was financially supported by the Am J 62(3):644–650
National Natural Science Foundation of China (No. 41101306, Naidu R, Bolan NS, Kookana RS, Tiller KG (1994) Ionic-strength
41371463) and the Central Public Research Institutes Basic Funds for and pH effects on the sorption of cadmium and the surface
Research and Development (Agro-Environmental Protection Institute, charge of soils. Eur J Soil Sci 45(4):419–429
Ministry of Agriculture, No. 2008-zxq-13). Navarro MC, Perez-Sirvent C, Martinez-Sanchez MJ, Vidal J, Tovar
PJ, Bech J (2008) Abandoned mine sites as a source of
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