Heavy metal mobility and potential availability in

J Mater Cycles Waste Manag (2016) 18:563–572 DOI 10.1007/s10163-015-0352-4

ORIGINAL ARTICLE

Heavy metal mobility and potential availability in animal manure: using a sequential extraction procedure Ali Sungur • Mustafa Soylak • Selehattin Yilmaz Hasan Ozcan

•

Received: 26 November 2013 / Accepted: 7 January 2015 / Published online: 22 January 2015 Ó Springer Japan 2015

Abstract In this study, dairy cow manure, goat manure, and chicken manure were collected from three farms and analyzed to find out the concentration of Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn. The concentration and potential of mobility and availability of heavy metals were studied in the animal manure samples. BCR Sequential extraction procedure was used to determine the binding forms of the metals. In this study, pseudo total concentrations of Mn and Zn were found out to be predominant in all the types of animal manure samples. According to the results, it was traced that Cr, Cu, and Ni were observed to be at the second highest level while Cd, Co, and Pb were seen at the lowest level in all the manure samples. When extractable amounts of heavy metals are taken into consideration, it is seen that the amount of the mobile fractions of heavy metals except for Cr and Ni are higher in comparison with that of immobile fraction in all the animal manure samples. It was also viewed that Mn, Cd, and Zn are more available in dairy cow manure and chicken manure whereas Cd, Co, and Mn are more available in goat manure. Keywords Animal manure Sequential extraction Heavy metals Mobility Availability A. Sungur H. Ozcan Department of Soil Science and Plant Nutrition, Faculty of Agriculture, Çanakkale Onsekiz Mart University, 17020 Çanakkale, Turkey M. Soylak (&) Department of Chemistry, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey e-mail: [email protected] S. Yilmaz Department of Chemistry, Faculty of Art and Science, Çanakkale Onsekiz Mart University, 17020 Çanakkale, Turkey

Introduction Livestock manures could be seen as the most traditional organic fertilizers that are used in agriculture, and they should be integrated into a closed nutrient cycling strategy under an ideal farm condition. A large number of organic wastes are generated from such industries because of increasing production of livestock and poultry products for human consumption. Using animal manure for the restoration of soil fertility and improvement of crop production is one of the ancient practices and significant ways of recycling nutrient [1]. The fact that organic fertilizers like manures contain a substantial amount of heavy metal is well known. Increasing concern of recycling of manure as soil amendment has caused a debate about the possible metal contamination due to their use. For that reason, if essential precautions are not taken to reduce heavy metal content, it is possible to restrict manure use in the near future [2–5]. The features of the particle surface and the type of strength of the bond along with the properties of the solution in connection with the solid samples are really significant for the bioavailability of heavy metals [6]. Methods which have been employed to extract heavy metals from solid samples such as soil, plant, and dusts are possible to be categorized under two groups [7–9]. These are respectively single extraction and sequential extraction methods [10–14]. As known, the potential impact of heavy metals upon environment is commonly assessed through identifying total amounts. Yet, the fact that the assessment of total elements does not reveal a precise estimation of the potential environmental effects is generally accepted. This might be related with that: not only bioavailability but also toxicity depend on the chemical form of heavy metals, and such a case becomes more apparent. At this point, applying speciation methods are indeed essential to reach valuable data about bioavailability and toxicity [15–19].

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The determination of heavy speciation metal patterns in the soil is more significant than assessing their total pedogenic concentrations and this is also acknowledged by the scientific communities. Such a situation could be used in environmental impact studies like agricultural recycling of organic wastes and soil cleaning methods [20]. Identifying the different fractions of heavy metals by using several sequential extractions is the key to the understanding of the mobility and availability. To efficiently evaluate the results thus determined by the various sequential extraction methods, the standard sequential extraction method designed by the European Community Bureau of Reference (BCR) has most often been used [21–26]. BCR sequential extraction method consider heavy metal fractions in three steps as of exchangeable and bond to carbonates; reducible (bound to Fe–Mn oxides) and oxidizable (bond to organic matter and sulfides). The last step represents non-extractable residual portion and includes the metals bond to minerals soluble in strong acid solutions. In this study, a sequential extraction of Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn in relation with BCR scheme was applied to manure samples which had been collected from three farms. The mobility, immobility and availability of these heavy metals were investigated.

Materials and methods Reagents and apparatus All the chemicals that were benefited in this study had analytical reagent grade (Merck, Germany). Throughout the experiment, double deionized pure water (TKA, GenPure, 18.2 MX/cm resistivity) was employed. A LECO Model TruSpec C/N analyzer, a Heidalph Model UNIMAX 2010 shaker, a Nuve Model NF 800 centrifuge, an M-tops Model HP 330 hotplate, an inoLab Model WTW pH meter, and a HACH Model HQ 40d conductivity meter were employed in this study. An Analytic Jena Model novAA350 flame atomic absorption spectrometer was used to analyze the concentrations of heavy metals in the manure samples. The wavelengths (nm) which were benefited to determine the analyses can be listed out as such: cadmium 228.8, cobalt 240.7, chromium 357.9, copper 324.8, manganese 279.5, nickel 232.0, lead 283.3, and zinc 213.9. Purchased stock solutions (SCP SCIENCE, 1000 lg/ml, AA Standard) were used for each element. Sampling Mature animal manure samples including dairy cow manure (DCM), goat manure (GM), and chicken manure (CM) were collected from three farms in Çanakkale, Turkey. It should

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J Mater Cycles Waste Manag (2016) 18:563–572

also be stated that ten samples were randomly collected in each sampling and they were mixed to obtain a composite animal manure sample. All samples were randomly collected at different depths. All samples were also taken from manure heaps which had been left to rot 8–10 months ago before having been employed in the research area. During the process in which samples were collected, nonmetallic tools were benefited, and all samples were taken to laboratory in polyethylene containers in a safe way. These samples were air dried at a room temperature (20–25 °C) and sieved to 2 mm sieve. The portions of the samples were prepared by passing them through a 105 lm sieve after they were also homogenized in a mortar. Then, the portions of the samples were kept in a plastic bag prior to chemical analysis. Analysis and quality control By making use of pH meter and conductivity meter, pH and electrical conductivity (EC) were identified in 1:5 sample-water suspensions [27]. Total carbon and total nitrogen amounts were also measured through dry combustion method by means of C/N analyzer [28]. Hotplate digestion technique with an EPA method (EPA-3050B) was benefited to determine pseudo total heavy metal content. Modified BCR sequential extraction method that was developed by European Community Bureau of Reference was also employed to determine the concentration of heavy metals in supernatant. The analysis of BCR-144R Sewage Sludge (domestic origin) also validated the procedure that was presented. In Table 1, the recovery rate of heavy metals in the standard reference material was indicated. BCR sequential extraction procedure Manure samples were analyzed by making use of the sequential extraction method to investigate the binding forms of heavy metal contents in animal manure samples. It is possible to attain the modified BCR extraction elsewhere [21–23, 26, 29, 30]. Analysis procedures which are employed could be listed out as such: Fraction 1 (acid soluble, bound to carbonate and cation exchange site) 1.00 g was measured from each animal manure sample. Then, they were transferred to centrifuge tube by adding 40 mL acetic acid solution (0.11 M) to animal manure sample in centrifuge tube. Samples were shaken for 16 h by making use of an automatic shaker. Later, these shaken samples were centrifuged at 4000 rpm for 20 min so that solid phase could be separated from liquid phase. Subsequent to centrifugation process, liquid phase was filtered by using Whatman-42. Then, 20 ml deionized pure water was also added to solid phase in the


565

Table 1 The results of determined and certified values for Certified Reference Material (BCR-144R), n = 3 Elements

Acid soluble (F1)

Reducible (F2)

Oxidizable (F3)

Residual (R)

Sum

0.20 ± 0.02

0.46 ± 0.05

0.76 ± 0.06

0.49 ± 0.04

1.91 ± 0.08b

–

–

–

–

1.84

Recovery (%)

Cd Found valuea Certified value

c

103.8

Co Found value

2.94 ± 0.12

1.12 ± 0.08

7.56 ± 0.22

0.72 ± 0.05

12.34 ± 0.26

Certified value

–

–

–

–

13.30

92.8

Cr Found value

2.24 ± 0.08

4.76 ± 0.14

44.80 ± 2.56

52.05 ± 3.45

Certified value

–

–

–

–

103.85 ± 3.82

115.4

41.72 ± 2.04 –

49.56 ± 3.98 –

28.53 ± 1.06 –

35.02 ± 1.12 –

154.83 ± 3.16 189.00

81.9

Found value

3.92 ± 0.26

4.23 ± 0.12

12.62 ± 0.65

17.11 ± 1.05

37.88 ± 1.17

84.4

Certified value

–

–

–

–

44.90

90.00

Mn Found value Certified value Ni

Pb Found value

4.84 ± 0.13

10.08 ± 0.72

15.12 ± 0.92

79.04 ± 2.55

Certified value

–

–

–

–

109.08 ± 2.76

113.6

96.00

Zn Found value

144.21 ± 4.62

214.23 ± 8.71

234.64 ± 12.42

170.74 ± 5.74

763.82 ± 15.28

Certified value

–

–

–

–

919.00

a

Mean, lg/g ± standard deviation (SD)

b

Total concentration of the four fractions ± SD lg/g

c

centrifuge to wash it prior to the next step. Then, it was shaken for 15 min and centrifuged for 20 min so that liquid phase could be discharged. Fraction 2 (reducible, bound to Fe–Mn oxides) After adding 40 mL hydroxylamine hydrochloride solution (0.5 M) to residuals in centrifuge from the first step, it was shaken for 16 h. Subsequent to centrifugation process, liquid phase was filtered to storage container by using Whatman-42. Washing process similar to that of first step was also repeated in this step. Fraction 3 (oxidizable, bound to organic matter and sulfides) Before shaken at laboratory temperature for 1 h, 10 mL hydrogen peroxide solution (8.8 M) was added to residuals in centrifuge tubes from the second step. After closing the tube, it was shaken by automatic shaker at ambient temperature for 1 h. It was placed in a sand bath to heat at 85 °C for 1 h. The solution was evaporated to near dryness, and, after cooling, another 10 mL of hydrogen peroxide solution was added to the residue. The tube was heated at 85 °C for 1 h and again evaporated to near dryness. After sample had cooled, 50 mL ammonium acetate solution was added and it was shaken for 16 h. Subsequent to centrifugation process, liquid phase was filtered to storage container.

83.1

Residual (remaining residue) After the first three steps, the last remaining solid phase was digested with 20 mL aqua regia solution on a hot plate without boiling. By using of Whatman-42, it was filtered and diluted with 0.5 M HNO3 to 15 mL.

Results and discussion Result of manure samples characteristics The mean of values of some parameters that were analyzed in each animal manure sample are given in Table 2. As could be seen, pH and EC values and C:N ratio which were taken from different animal manure samples indicate the following equation: GM [ DCM [ CM. It was also found out that the results gained through this study were in harmony with pH [31, 32] and EC values of the former studies [33, 34]. In general terms, animal manures are applied to agricultural areas after they are matured. The most important parameter indicating the level of maturity is C:N. In a similar way, C:N ratio gives the nutritional balance [32]. If C:N ratio is less than 20, it shows an advanced degree of organic matter stabilization

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566 Table 2 Results of mature animal manure samples characteristics (Mean ± SD) and pseudo total concentration of heavy metals (lg/g dry wt ± SD), n = 3


DCM pH

Typical ranges in farmyard manure, lg/g [36]

b

Maximum allowable concentration limits for organic fertilizer in Republic of Turkey, lg/g

8.18 ± 0.13

8.01 ± 0.18

6.92 ± 0.14

10.19 ± 0.44

15.64 ± 0.53

6.52 ± 0.29

C (%)

18.35 ± 0.35

32.30 ± 0.27

18.00 ± 0.24

N (%)

1.39 ± 0.04

2.11 ± 0.05

2.11 ± 0.04

13.20 ± 0.41

15.29 ± 0.44

8.55 ± 0.26

TRFMa

MACLb

Cd

0.97 ± 0.08

0.88 ± 0.06

0.93 ± 0.11

(0.1–0.8)

3

Co

5.23 ± 0.82

2.52 ± 0.08

7.47 ± 0.95

(0.3–24)

–

Cr

52.24 ± 1.42

6.42 ± 0.86

33.68 ± 1.03

(1.1–55)

270

Cu

49.23 ± 1.92

49.75 ± 1.06

184.98 ± 2.32

(2–172)

450

Mn

261.72 ± 4.98

278.35 ± 3.85

502.08 ± 6.82

(30–969)

–

Ni

55.26 ± 1.86

18.73 ± 0.78

45.25 ± 1.30

(2.1–30)

120

Pb

13.91 ± 0.43

14.57 ± 0.16

17.32 ± 0.22

(1.1–27)

150

Zn

168.95 ± 4.26

158.96 ± 3.76

364.93 ± 8.38

(15–566)

1100

along with reflecting a satisfactory degree of maturity of the organic waste [35]. In this point, according to C:N results, it could be alleged that DCM, GM, and CM samples are mature and have a good nutritional balance. Pseudo total heavy metals contents of manure samples The ranges of pseudo total concentration of heavy metal contents of animal manure taken from three farms are indicated in Table 2. According to these results, it could be pointed out that the results of heavy metal contents in the DCM (except Cd and Ni), GM (except Cd), and CM (except Cd, Cu and Ni) samples are in typical range for farmyard manure [36]. In this study, generally, the heavy metal content order of animal manure samples was found out as such: CM [ DCM [ GM. The highest concentration of Co, Cu, Mn, Pb, and Zn were found in the CM whereas the highest concentrations of the other heavy metals (Cd, Cr, and Ni) were identified in the DCM. It is seen that Mn and Zn concentrations were dominant in animal manure samples. Metal group with the second highest level included Cr, Cu, and Ni. Besides, from highest to lowest levels, Cd, Co, and Pb consisted of metal groups found at the lowest levels in all manure samples. CM samples included the highest values of Co and Pb whereas Cd was present in similar levels in all types of manure samples (Table 2). Heavy metal concentrations of the present study were less than the standards for soils [37–39] and biosolids [40] and fertilizers [41]. In Turkey, regulations were issued by the Ministry of Food, Agriculture, and Livestock for organic fertilizer quality and the metal concentrations of the current study were also lower than allowable concentrations of heavy metals in organic fertilizer (Table 2). As a

123

CM

EC (mS/cm)

C/N

a

GM

consequence of the analysis of the animal manure, heavy metal addition rates to soil might be different from the typical values indicated here. It should not also be overlooked that heavy metal accumulation rates in the soil (especially Mn, Zn and Cu) are more likely to be at their greatest in agricultural areas in which animal manures have been applied for many years and applications are expected to continue.

Application of sequential extraction scheme BCR-144R Sewage Sludge (domestic origin) validates the BCR sequential extraction procedure presented. It was found out that the recovery rates for heavy metals in the standard reference material were between 81.9 and 115.4 %. In Table 1, the results were indicated. Besides, the accuracy of the results was controlled by recovery studies. The recovery values for DCM samples have a variety between 94.8 and 112.3 % while it is between 81.7 and 103.4 % for GM samples and between 86.7 and 98.5 % for CM samples; and this is similar to that recorded by other authors using the same procedure [29, 42, 43]. BCR sequential extraction recovery was determined using the following Eq. (1): % Recovery ¼ ½ðFraction 1 þ Fraction 2 þ Fraction 3 þ ResidualÞ=Pseudototal 100 ð1Þ When the sequential extraction scheme offered by BCR is employed, the behavior of heavy metals in different types of animal manure is given in Tables 3, 4, and 5. Despite the fact that certain parallels could be drawn among metal groups for all the animal manures, metal fractions’ distribution was observed to be different for each metal.


567

Table 3 Metal concentration (lg/g dry wt) in the extractions for DCM, n = 3 Acid soluble fraction (F1)

Reducible fraction (F2)

Oxidizable fraction (F3)

Residual (R)

Mean ± SD

Mean ± SD

Mean ± SD

Mean ± SD

% Ratio

% Ratio

% Ratio

Sum: R (F1 ? F2 ? F3 ? R) % Ratio

Mean ± SD

% Ratio

Cd

0.35 ± 0.07

34.65

0.27 ± 0.06

26.73

0.06 ± 0.01

5.94

0.36 ± 0.08

32.67

1.01 ± 0.14

100.00

Co

1.34 ± 0.12

22.78

0.67 ± 0.06

11.33

1.85 ± 0.16

31.52

2.02 ± 0.36

34.37

5.88 ± 0.45

100.00

Cr Cu

0.12 ± 0.05 3.21 ± 0.48

0.22 6.54

0.06 ± 0.01 1.08 ± 0.12

0.11 2.19

14.32 ± 1.02 28.95 ± 3.00

27.20 58.96

38.14 ± 2.86 15.86 ± 1.24

72.46 32.31

52.63 ± 3.22 49.10 ± 3.51

100.00 100.00

Mn

87.39 ± 4.42

34.99

79.24 ± 3.63

31.73

36.22 ± 2.04

14.50

46.93 ± 2.18

18.79

249.7 ± 6.58

100.00

Ni

3.06 ± 0.76

5.83

2.16 ± 0.12

4.12

17.19 ± 1.12

32.82

29.98 ± 1.86

57.23

52.38 ± 3.18

100.00

Pb

3.45 ± 0.27

24.79

2.32 ± 0.15

16.63

4.85 ± 0.33

34.84

3.31 ± 0.28

23.75

13.93 ± 0.72

100.00

Zn

38.53 ± 2.19

23.24

47.92 ± 3.28

28.91

46.77 ± 3.24

28.22

32.53 ± 2.04

19.63

165.7 ± 3.86

100.00

Table 4 Metal concentration (lg/g dry wt) in the extractions for GM, n = 3 Acid soluble fraction (F1)



Residual (R)

Mean ± SD

Mean ± SD

Mean ± SD

Mean ± SD

% Ratio

% Ratio

% Ratio

Sum: R (F1 ? F2 ? F3 ? R) % Ratio

Mean ± SD

% Ratio

Cd

0.32 ± 0.04

35.16

0.26 ± 0.03

28.57

0.05 ± 0.01

5.49

0.28 ± 0.04

30.77

0.91 ± 0.05

100.00

Co

0.73 ± 0.05

30.88

0.57 ± 0.04

24.18

0.07 ± 0.01

2.82

1.00 ± 0.12

42.12

2.37 ± 0.14

100.00

Cr Cu

0.42 ± 0.04 1.85 ± 0.12

6.33 3.82

0.05 ± 0.01 1.17 ± 0.16

0.69 2.41

2.27 ± 0.22 31.36 ± 1.74

34.38 64.72

3.86 ± 0.28 14.07 ± 1.02

58.60 29.05

6.59 ± 0.32 48.45 ± 2.26

100.00 100.00 100.00

Mn

42.45 ± 2.32

16.77

83.16 ± 5.23

32.85

74.31 ± 3.02

29.35

53.23 ± 2.34

21.03

253.1 ± 7.24

Ni

2.13 ± 0.18

13.88

1.83 ± 0.11

11.94

6.16 ± 0.86

40.21

5.20 ± 0.25

33.97

15.31 ± 0.94

100.00

Pb

1.78 ± 0.12

12.15

2.50 ± 0.18

17.06

7.86 ± 0.52

53.60

2.52 ± 0.14

17.19

14.66 ± 0.88

100.00

Zn

10.91 ± 1.06

8.10

22.00 ± 2.12

16.33

69.78 ± 4.06

51.80

32.02 ± 2.48

23.77

134.7 ± 4.86

100.00

Table 5 Metal concentration (lg/g dry wt) in the extractions for CM, n = 3 Acid soluble fraction (F1)



Residual (R)

Mean ± SD

Mean ± SD

Mean ± SD

Mean ± SD

% Ratio

% Ratio

% Ratio

Sum: R (F1 ? F2 ? F3 ? R) % Ratio

Mean ± SD

% Ratio

Cd

0.30 ± 0.05

34.88

0.25 ± 0.04

29.07

0.06 ± 0.01

6.98

0.25 ± 0.06

29.07

0.86 ± 0.08

100.00

Co

0.55 ± 0.06

7.69

0.22 ± 0.02

3.12

2.93 ± 0.18

40.92

3.46 ± 0.28

48.26

7.16 ± 0.52

100.00

Cr Cu

0.40 ± 0.03 11.35 ± 0.92

1.38 6.33

0.48 ± 0.03 8.16 ± 0.72

1.64 4.55

8.32 ± 0.76 77.9 ± 5.87

28.51 43.44

19.99 ± 1.51 81.94 ± 6.44

68.47 45.68

29.19 ± 1.86 179.37 ± 7.14

100.00 100.00

Mn

121.1 ± 8.32

24.48

137.4 ± 6.06

27.77

88.0 ± 6.33

17.80

148.1 ± 12.03

29.95

494.7 ± 11.25

Ni

2.32 ± 0.16

5.29

2.21 ± 0.18

5.04

15.9 ± 1.09

36.22

23.45 ± 1.93

53.45

43.87 ± 2.16

100.00 100.00

Pb

2.42 ± 0.09

14.50

2.07 ± 0.14

12.40

6.30 ± 0.53

37.76

5.90 ± 0.42

35.35

16.69 ± 0.88

100.00

Zn

81.21 ± 5.28

24.12

94.28 ± 5.45

28.01

80.9 ± 5.04

24.03

80.27 ± 5.57

23.84

336.65 ± 6.12

100.00

123

568

Mobility and potential availability of heavy metals It could be underlined that the mobility and immobility of heavy metals along with their availability in waste large depend on their types of binding forms. The mobility and availability of the metals decrease in the order of acid soluble forms [ reducible forms [ oxidizable forms [ residual forms [14]. In such a situation, the first two fractions (acid soluble and reducible) constitute a more available fraction. Similarly, the last two fractions (oxidizable and residual) were accepted to form a less available fraction [16]. Taking the extractable amounts of heavy metals, it could be accepted that the concentrations of the first three fractions (acid soluble ? reducible ? oxidizable) are mobile fractions [10]. Figure 1 gives the average amounts of heavy metal fraction obtained by means of BCR sequential extraction method. The extractability order of the heavy metals based on the sum of the first three fractions (acid soluble ? reducible ? oxidizable) for DCM samples, which does not include the residual phase, could be given as such: Mn & Zn [ Pb [ Cu [ Cd [ Co [ Ni [ Cr. It is obviously observed that the most mobile elements in DCM samples are Mn, Zn, Pb, Cu, Cd, and Co whereas the least mobile elements are Ni and Cr as can be viewed in Fig. 1 and Table 3. On the other hand, taking the easily available fractions (acid soluble ? reducible) into consideration, it is traced that Mn (67 %), Cd (61 %), and Zn (52 %) are found as easily available forms while Pb, Co, Ni, Cu, and Cr are found in less available fractions (oxidizable ? residual) as seen in Table 6. Considering mobile fraction containing the first three fractions for GM samples, the mobility order of heavy metal was observed as such: Pb [ Mn [ Zn [ Cu [ Cd [ Ni [ Co [ Cr. When extractable amounts of heavy metals were taken into account, it was found out that


the concentration of the mobile fractions (acid soluble ? reducible ? oxidizable) of heavy metals except for Cr was higher compared to that of immobile fraction (Fig. 1; Table 4). Considering easily available acid soluble and reducible fractions, it was revealed that Cd, Co, and Mn were easily available elements. Their values were respectively 64, 55, and 50 %. On the other hand, it was traced that Cu, Cr, Zn, Ni, and Pb elements were found in oxidizable and residual fractions which were less available fractions as indicated in Table 6. Considering the mobile fraction including the first three fractions for CM samples, the mobility order of heavy metals was found as such: Zn [ Cd [ Mn [ Pb [ Cu [ Co [ Ni [ Cr. Similar to DCM samples, the mobile fractions of the metals except for Ni and Cr were found to be higher than those of immobile fractions in residual fractions as can be traced in Fig. 1 and Table 5. Besides, taking the availability of heavy metals in CM samples, it was observed that they were similar to DCM samples to a great extent. In a similar way to DCM samples, it was viewed that Cd (64 %), Mn (52 %), and Zn (52 %) elements were bound to acid soluble and reducible fractions which were in easily available fractions. Likewise, it was also found that Pb, Co, Ni, Cu, and Cr were in less available fractions as in Table 6. When all kinds of manure samples are considered, it was found out that Cr was of highly value in immobile fraction while Ni was moving between mobile and immobile fractions. It was also observed that Mn, Zn, Pb, Cd, Cu, and Co had higher value in mobile fractions. Metals found in mobile fraction could be categorized in two groups. In the first group, there are some elements like Mn, Zn, and Pb, and these metals were highly found to be bound in mobile fractions. As to the second group, there are Cd, Co, and Cu, and it was clearly observed that they were highly bound to mobile fractions.

Fig. 1 Relative abundance in each fraction of heavy metals in the DCM, GM, and CM samples

123

Cu & Cr (93 %) [ Zn (76 %) [ Ni (74 %) [ Pb (71 %) Cr (99 %) [ Cu & Ni (90 %) [ Co (66 %) [ Pb (59 %)

569

On the other hand, for all samples, Mn and Cd were found in the easily available fractions with high rates as given in Table 6. Such a situation clarifies that Mn and Cd have the highest ability and susceptibility to be released from the manure samples by the simple ion exchange mechanism. This outcome is in parallelism with the other studies focusing on high mobility of Mn and Cd in the acidic environment [20]. Due to the fact that Mn and Cd in this fraction is the most labile, it might be available for uptake by the total biota. Higher concentration of metals in this fraction could be a symbol of pollution indicator [44]. As given in Table 6, Zn in DCM and CM samples was found to have high rates in easily available forms (for both samples, Zn was 52 %) like Mn and Cd. Zn shows the greatest degree of bioavailability because of the high proportion of metal mobilized in the exchangeable and reducible fraction which is a result reflecting the findings of literature [16, 29]. On the other hand, Co was extracted in high rates (55 % Co) in GM samples like Mn and Cd. As a consequence, Mn, Cd, and Zn were in easily available forms in DCM and CM whereas Mn, Cd, and Co were easily available fractions in GM. In general terms, using organic fertilizer in agriculture is better than chemical fertilizer for food safety. However, amount of heavy metals in poultry and livestock manure is usually high. At the same time, the similar results in our study were obtained. Hence, when these manures were applied, heavy metals in these manures will pass to soil and cause soil and water pollution [45, 46]. A great number of studies usually focused on the identification of the total metal concentrations. However, necessary information about potential toxic elements’ mobility and availability cannot be provided by total concentration, and speciation is highly acknowledged as a useful instrument to gain such kind of information [15–19]. These identifications are substantially significant so that the mobility and immobility of heavy metals can be understood, and the content of the chemical forms of heavy metals may be traced before being benefited in agricultural areas. Ecological risk assessment

(Less available)

Equations (2)–(4) were used to calculate potential ecological risk index (RI) and eventually to assess the degree of potential risk of heavy metal pollution in DCM, GM, and CM [47].

3?4

Cd (64 %) [ Mn & Zn (52 %) Cd (64 %) [ Co (55 %) [ Mn (50 %) Mn (67 %) [ Cd (61 %) [ Zn (52 %) (More available) 1?2

Cr (97 %) [ Ni & Co & Cu (90 %) [ Pb (73 %)

Cr [ Co [ Ni [ Cd [ Cu [ Zn [ Mn [ Pb Insolubility

Cr [ Ni [ Co [ Cu [ Pb [ Mn [ Cd [ Zn

Cu [ Co [ Pb [ Ni [ Cr [ Zn [ Mn [ Cd Cu [ Pb [ Zn [ Ni [ Cr [ Mn [ Cd [ Co Cu [ Pb [ Ni [ Co [ Zn [ Cr [ Mn [ Cd

Cr [ Ni [ Co [ Cd [ Cu [ Pb [ Zn [ Mn

3

4

Oxidation reaction

Cd [ Mn & Zn [ Pb [ Ni & Cu [ Co [ Cr Mn [ Cd [ Co [ Pb [ Zn [ Ni [ Cu [ Cr Mn [ Zn [ Cd [ Pb [ Co [ Ni [ Cu [ Cr Reduction reaction 2

Cd [ Mn & Zn [ Pb [ Co [ Cu [ Ni [ Cr Cd [ Co [ Mn [ Ni [ Pb [ Zn [ Cr [ Cu Mn & Cd [ Pb [ Zn & Co [ Cu [ Ni [ Cr Ion exchange and acid dissolution 1

Condition Step

Table 6 Mobility and availability order of heavy metals in DCM, GM and CM samples

Mobility order in CM Mobility order in GM Mobility order in DCM


Cf ¼ Ci =Cn

ð2Þ

Er ¼ Tr Cf

ð3Þ

RI ¼ RðEr Þ

ð4Þ

Where, Cf is the contamination factor; Ci and Cn are respectively the mobile and stable fractions of the heavy

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570 Table 7 Indices for ecological risk assessment [50]

Table 8 Ecological risk assessment of heavy metals in DCM, GM, and CM


Cf (metal contamination)

Er (metal potential ecological risk)

RI (potential ecological risk)

Cf \ 1 (clean)

Er \ 40 (low)

RI B 50 (low)

1 \ Cf \ 3 (low)

40 B Er \ 80 (moderate)

50 \ RI B 100 (moderate)

3 \ Cf \ 6 (moderate)

80 B Er \ 160 (considerable)

100 \ RI B 200 (considerable)

6 \ Cf \ 9 (considerable)

160 B Er \ 320 (high)

RI [ 200 (high)

Cf [ 9 (high)

Er C 320 (very high)

Heavy metals

Tr

Contamination factor (Cf)

Potential ecological risk index (Er)

DCM

DCM

GM

GM

CM

Cd

30

2.06

2.25

2.44

61.82

67.50

73.20

Co

5

1.91

1.37

1.07

9.55

6.87

5.36

Cr

2

0.38

0.71

0.46

0.76

1.41

0.92

Cu

5

2.10

2.44

1.19

10.48

12.21

5.95

Mn

1

4.32

3.76

2.34

4.32

3.76

2.34

Ni

5

0.75

1.94

0.87

3.74

9.72

4.35

Pb

5

3.21

4.82

1.83

16.05

24.09

9.14

Zn

1

4.10

3.21

3.19

Potential ecological risk index (RI)

metals, Er is the potential ecological index for individual heavy metal; Tr is toxic factor of the individual heavy metal; and RI is the potential ecological risk index. The Tr values used for calculation of potential ecological index for individual metal are Cd (30), Co (5), Cr (2), Cu (5), Mn (1), Ni (5), Pb (5), and Zn (1) [48]. The contamination factor (Cf) of a heavy metal represents the ratio of the sum of the concentrations of the heavy metal extracted in the first four fractions of the sequential extraction (F1 ? F2 ? F3) to the concentration of the heavy metal in the residual fraction (R) [49]. The potential ecological risk index of a heavy metal (Er) is then obtained by multiplying the contamination factor of the heavy metal with the toxic factor (Tr) of the relevant heavy metal [50]. The potential ecological risk index (RI) of the solid (DCM, GM, and CM) is finally obtained by summing the potential ecological index of each heavy metal. The significance of the Cf, Er, and RI along with their risk potential is presented in Table 7. Cf, Er, and RI values of DCM, GM, and CM were determined to present the heavy metal risk levels and the values are provided in Table 8. As it can be seen from the Table, Mn, Pb, and Zn values of DCM and GM samples exhibited moderate contamination with regard to Cf. Other metals exhibited clean or low contamination. While only Zn of CM samples exhibited moderate contamination, other metals yielded clean or low contamination. With regard to Er values of each metal, it was observed that only Cd created moderate ecological risk in entire manure samples (DCM, GM and CM) and other metals created a

123

CM

4.10

3.21

3.19

110.81

128.77

104.46

low risk. On the other hand, with regard to potential ecological risk assessment of DCM, GM, and CM samples, DCM had an RI value of 110.8, GM had a value of 128.8, and CM had a value of 104.5 and they all exhibited considerable potential ecological risk. According to the results of this study, it was seen that Cd was found in moderate potential ecological risk, and this makes us think that despite the low total Cd levels, we should be careful about toxic impacts of Cd upon environment. Although all metals, except for Cd, of entire manure samples exhibited low risks individually, all manure samples were placed in considerable potential risk group with regard to potential ecological risk index (RI) values considering the entire metals. It has been revealed that animal manures should carefully be employed during the production process of edible plants, leaves, and fruits.

Conclusion It was observed that the amount of the mobile fractions (acid soluble, reducible, and oxidizable) of heavy metals except for Cr and Ni are higher in comparison with that of immobile fraction (residual) in all the types of animal manure samples. Besides, Mn, Cd, and Zn were easily available forms in DCM and CM samples while the other elements were found to be in less available fractions. As to GM samples, considering acid soluble and reducible fractions which are easily available in GM samples, it was viewed that Cd, Co, and Mn were easily


available elements while the other elements were found in oxidizable and residual fractions which were less available fractions. Cd exhibited moderate potential ecologic risk in entire manure samples. DCM, GM, and CM samples were placed in considerable potential risk group with regard to potential ecological risk index (RI) values considering the entire metals. Current findings revealed that BCR sequential extraction schemes yielded noteworthy information about the mobility of heavy metals, availability, and potential ecological risk to assess the contamination risk.

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