Environ Monit Assess (2015) 187:346 DOI 10.1007/s10661-015-4592-5
Heavy metals fractionation and risk assessment in surface sediments of Qarun and Wadi El-Rayan Lakes, Egypt Amaal Mansour Abdel-Satar & Mohamed E. Goher
Received: 15 January 2015 / Accepted: 5 May 2015 # Springer International Publishing Switzerland 2015
Abstract This study establishes a baseline for trace metal speciation in Qarun and Wadi El-Rayan lakes. A five-step sequential extraction procedure was applied for the speciation of the Fe, Mn, Zn, and Cu in sediment samples collected at Qarun and Wadi El-Rayan lakes. Mn and Cu were the most mobile metals, whereas the residue fraction maintained the highest concentrations of Zn and Fe (≈60 %). No significant differences in metal concentrations were detected in the sediments of each lake sites, despite of the large distance between them (P>0.05). Hazardous discharge sources are responsible for the high accumulation of metals in the nonresidual fractions. Qarun Lake showed high mobility factor for all studied metals than Wadi El-Rayan lakes; as such, all the humans, plants, animals and the general biota within the vicinity of this aquatic system are quite vulnerable to the trace metal exposure. According to geoaccumulation index (I-geo), the studied sediments were practically uncontaminated by Fe and Mn and classified as uncontaminated to moderately contaminated with Cu in Qarun and Zn in Wadi ElRayan lakes. The low values of load pollution index
A. M. Abdel-Satar : M. E. Goher Inland Water and Aquaculture Branch, National Institute of Oceanography and Fisheries (NIOF), Cairo, Egypt A. M. Abdel-Satar (*) Chemistry Department, Faculty of Science, Hail University, Hail, Kingdom of Saudi Arabia e-mail: [email protected]
(1 is polluted whereas PLI value 0.05) in metals fractions concentrations were observed in the sediments from the six sites in Qarun and Wadi El-Rayan lakes despite the large distance between them. Total extractable metal contents in studied lakes decrease in the order Fe > Mn > Zn > Cu. The percentage of the exchangeable species, that is, the most
available fraction, was only 0.04 % (Fe), 1.67 % (Mn), 4.60 % (Zn), and 3.84 % (Cu) for Qarun and 0.09 % (Fe), 0.63 % (Mn), 4.43 % (Zn), and 2.29 % (Cu) for Wadi El-Rayan lakes (Figs. 3 and 4). Zn showed the highest exchangeable percent for the studied metals. Despite their low percent association in fraction 1, the risk of environmental and ecological damage from trace metals cannot be ruled out. However, if oxidationreduction condition is changed, the metal bound to reducible or oxidizable fractions can be released (Yang et al. 2014). Iron is the most abundant metal in all sediments because it is one of the most common metals in the Earth’s crust (Kumar et al. 2012). Negligible percentages of Fe were extracted as the exchangeable and carbonate fractions (less than 1 % of the extracted Fe) for the two studied lakes. The analysis of the distribution of Fe in lakes showed that most of it is associated with the residual phase (~65 %) (Figs. 3 and 4). The remaining fractions of Fe were distributed among the reducible and the oxidizable phases. The slight increase in the percentage of Fe in the oxidizable phases than the reducible was probably results from competition between Fe organic complexes and hydrous Fe oxide forms. This situation is complicated because hydrous Fe oxides themselves can complex with organics, especially humic substances in sediments (Fytianos and Lourantou 2004). In the two studied lakes, Fe and Zn were distributed in a similar manner, with the residual, organic bound and to a lesser extent the oxidizable fractions being of greatest significance (Figs. 3 and 4). The highest increase in the mean percentages of Fe and Zn in residual fractions in both Qarun (63.35 and 50.8 %, respectively) and Wadi El-Rayan (65.72 and 61.9 %, respectively), reflecting that these metals were strongly bound to the sediments, where the biological availabilities of those
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Table 4 Trace metal distribution in the Qarun Lake sediment samples Metal
Site
Fraction 1
Fraction 2
Fraction 3
Fraction 4
Fraction 5
TM
Recovery
Fraction 6
Fraction 7
μg/g
%
μg/g
%
μg/g
%
μg/g
%
μg/g
%
μg/g
%
%
%
1
5.44
0.14
1.80
0.05
680.4
17.11
868.2
21.84
2420
60.87
3660
108.6
5.580
17.43
2
1.80
0.08
2.16
0.09
612.9
26.42
424.1
18.31
1276
55.09
2101
110.3
4.760
13.06
3
0.08
0.00
6.36
0.21
345.9
11.47
811.0
26.96
1845
61.35
3214
93.60
5.000
18.60
4
0.04
0.00
1.16
0.03
424.9
9.400
978.8
21.66
3114
68.91
4099
110.2
2.650
12.69
5
0.48
0.02
1.40
0.04
468.9
14.69
584.7
18.32
2137
66.94
3009
106.1
2.120
12.39
6
0.48
0.01
0.80
0.02
494.0
15.41
565.4
17.63
2146
66.93
3501
91.59
2.330
12.94
1
9.64
1.89
19.4
3.81
161
31.6
195
38.2
125
24.5
490.
104
3.65
19.7
2
7.84
1.82
3.92
0.91
146
33.7
133
30.8
141
32.8
501
85.9
3.81
16.6
3
3.28
0.93
16.4
4.67
119
33.7
116
32.8
98.2
27.9
438
80.4
4.06
34.4
4
5.32
1.60
6.04
1.82
130
39.1
98.7
29.7
92.5
27.8
367
90. 6
4.34
20.3
5
1.76
0.56
8.60
2.72
89.2
28.2
96.6
30.5
120.
38.1
401
79.0
5.39
17.9
6
9.24
3.20
6.20
2.15
133
46.1
50.4
17.5
89.9
31.1
301
95.9
4.91
28.3
Fe
Mn
Zn 1
12.4
8.18
5.60
3.69
25.0
16.5
57.8
38.1
50.8
33.5
164
92.4
7.12
27.0
2
6.00
7.18
5.20
6.22
26.6
31.8
15.4
18.4
30.4
36.4
102
82.4
7.18
13.2
3
4.80
4.72
6.40
6.30
17.8
17.5
22.2
21.9
50.4
49.6
118
86.2
1.18
19.1
4
2.00
1.63
0.40
0.33
15.4
12.6
18.6
15.2
86.0
70.3
110.
112
0.98
8.50
5
1.60
1.35
5.60
4.73
14.6
12.3
15.8
13.3
80.8
68.2
131
90.4
1.52
9.29
6
4.40
4.55
3.20
3.31
29.8
30.8
14.2
14.7
45.2
46.7
101
95.9
0.62
15.7
Cu 1
8.21
7.45
3.50
3.18
14.7
13.3
45.6
41.4
38.2
34.7
113
97.6
7.36
27.5
2
4.20
5.10
4.10
4.98
13.2
16.0
29.9
36.3
30.9
37.6
93.6
88.1
7.89
15.6
3
3.00
3.95
3.10
4.08
10.2
13.4
30.1
39.6
29.6
39.0
91.0
83.5
8.74
13.1
4
2.00
1.87
2.00
1.87
15.4
14.4
44.4
41.5
43.2
40.4
110.
97.3
8.61
12.9
5
2.10
2.33
4.10
4.56
13.4
14. 9
41.1
45. 7
29.3
32.6
102
88.0
6.07
11.4
6
1.90
2.35
3.20
3.95
18.6
23.0
29.2
36.1
28.1
34.7
101
80.2
6.75
11.3
trace metals were relatively lower (Ogunfowokan et al. 2013), and it can only be released over time as a function of the weathering process (Yang et al. 2014). However, manganese behaves a different way (Figs. 3 and 4). Mn was distributed primary in the reducible (iron/manganese oxides) (35.4 and 35.44 % for Qarun and Wadi El-Rayan, respectively), residual (30.4 and 32.8 %), and oxidizable (organic matter and sulfides) phases (29.9 and 25.0 %). This agrees Calmano and Forstner (1983) and Fytianos and Lourantou (2004). The large percent of metals associated with the reducible fraction raises concerns their potential mobility in the water phase. However, if
oxidation-reduction potential and oxygen levels in water decrease, these may deoxidize and cause secondary pollution, which can be seen in the environmental pollution associated with extensive human activities (Yang et al. 2014). The nonresidual fractions (available + acidsoluble + reducible + oxidizable) of Mn in sediments were greater (70.8 % for Qarun and 67.2 % for Wadi ElRayan) than residual fractions. Therefore, the results indicate that Mn in sediments from Qarun and Wadi El-Rayan lakes are potentially more available for exchange and/or release into the aquatic environment. The high Cu percentage was recorded in the oxidizable fraction for Qarun and Wadi El-Rayan lakes (40.1
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Table 5 Trace metal distribution in the Wadi El-Rayan lakes sediment samples Metal
Site
Fraction 1
Fraction 2
Fraction 3
Fraction 4
Fraction 5
TM
Recovery
Fraction 6
Fraction 7
μg/g
%
μg/g
%
μg/g
%
μg/g
%
μg/g
μg/g
%
%
%
1
0.04
0.00
1.08
0.06
228.5
12.78
495.7
27.72
1063
59.44
1890.
94.60
13.20
15.20
2
0.04
0.00
1.92
0.10
304.4
16.56
402.6
21.90
1129
61.43
2104
87.38
3.060
4.780
3
2.32
0.09
0.08
0.00
375.1
15.02
459.4
18.40
1660.
66.48
2334
107.0
2.840
4.200
4
4.24
0.25
0.06
0.00
267.8
16.05
242.7
14.55
1153
69.14
1721
96.95
7.200
9.210
5
4.00
0.16
2.00
0.08
368.8
14.75
445.6
17.82
1680.
67.19
2792
89.58
2.010
4.710
6
1.32
0.06
0.24
0.01
397.3
17.35
273.2
11.93
1618
70.65
2240.
102.2
2.610
4.710
1
3.60
0.60
44.5
7.43
250
41.8
146
24.3
155
25.9
710
84.3
3.35
16.0
2
2.96
0.45
33.4
5.13
251
38.5
146
22.4
219
33.5
740
88.1
3.19
9.59
3
3.32
0.56
36.5
6.17
229
38.6
156
26.3
168
28.4
671
88.3
3.57
9.42
4
2.80
0.63
35.3
7.90
135
30.1
139
31.1
135
30.2
425
105
4.66
12.1
5
3.32
0.89
17.3
4.63
103
27.7
90.3
24.2
159
42.6
418
89.2
5.50
15.0
6
2.32
0.62
21.5
5.74
134
35.8
82.0
21.9
135
36.0
330
114
5.58
13.9
1
6.40
4.71
5.60
4.12
24.4
17.9
25.2
18.5
74.4
54.7
162
84.2
6.76
17.1
2
2.00
1.00
2.80
1.40
25.6
12.8
25.6
12.8
144
72.1
184
109
2.50
7.39
3
2.80
1.51
2.40
1.29
20.0
10. 8
36.8
19.8
124
66.6
172
108
3.02
7.65
4
5.20
5.75
7.20
7.96
24.8
27.4
16.8
18.6
36.4
40.3
103
87.7
6.86
16.4
%
Fe
Mn
Zn
5
21.2
9.27
4.40
1.92
26.8
11.7
29.6
12.9
147
64.2
272
84.2
1.92
12.8
6
8.80
4.37
4.00
1.98
23.6
11.7
17.2
8.53
148
73.4
221
91.4
2.18
7.64
1
1.40
1.84
1.20
1.58
12.1
15.9
32.6
42.8
28.8
37.8
64.9
117
12.0
13.4
2
1.50
2.81
0.99
1.86
7.10
13.3
23.1
43.3
20.7
38.8
49.4
108
7.49
9.93
3
0.90
1.83
1.56
3.16
8.50
17.3
19.0
38.6
19.3
39.2
56.7
87.0
9.34
9.54
4
0.60
1.27
1.00
2.12
4.50
9.55
19.1
40.6
21.9
46.5
51.2
91.9
11.0
11.3
Cu
5
0.80
1.89
0.90
2.13
6.20
14.7
18.6
44.0
15.8
37.4
50.7
83.4
8.04
15.8
6
1.30
4.09
2.20
6.92
4.90
15.4
12.2
38.4
11.2
35.2
39.0
81.5
10.7
17.3
and 41.3 %, respectively) (Figs. 3 and 4). Its percentage of partitioning distribution in the studied lakes is in the order: oxidizable > residual > reducible > carbonate bound ≈ exchangeable. The high affinity of Cu to organic matter indicates the strong complexing affinity of organic matter with copper (Morillo et al. 2004; Ramirez et al. 2005). Under oxidizing conditions a significant fraction (up to 40 %) of the Cu reaching the sediment surface may be returned to the overlying water column in the two studied lakes. Several studies have also reported high concentration of Cu associated with organic matter in the sediment (Fytianos and
Lourantou 2004; Ramirez et al. 2005; Wong et al. 2007; Turki 2007; Arias et al. 2008). Also, there is increase in exchangeable percent in the site 1 at Qarun lake (7.45 %) compared with other sites reflect the effect of drainage water from ElBats Drain. The increase in sorption of Cu in the oxidizable fraction in the studied lakes than Zn may be due to the Cu was sorbed more selectively than Zn in the organic surface including humic and fulvic acid (Violante et al. 2010). The increase in non residual percents of Mn and Cu in the studied lakes may be originated from anthropogenic
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Environ Monit Assess (2015) 187:346
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Fig. 3 Mean percent distributions of the trace metals in the Qarun Lake sediment
100 80 60 40 20 0 Fe
Fracon 1
Fracon 2
Zn Fracon 3
Cu Fracon 4
Fracon 5
follow the order Fe ≈ Zn ≈ Cu≈ 15 % < Mn ≈ 23 % in Qarun sediment and Fe ≈ 7 % < Mn ≈ Zn ≈ Cu ≈ 12 % in Wadi El-Rayan lakes (Tables 4 and 5). The increase in this fraction at Qarun Lake for all studied metals is an indication of significant anthropogenic sources. As shown in Tables 4 and 5, results for the analysed sediments indicate that the sums of the five fractions are in good agreement with the amount of total extractable metal (TM), with satisfactory recoveries (79.0–112 % for Qarun and 81.5–117 % for Wadi El-Rayan Lakes), which implies that the accuracy of the extraction procedure. The recovery of the sequential extraction
influences, practically from pesticides used in agriculture, and are found to present a pollution risk (Akcay et al. 2003) The fraction of trace metals associated (chelated or adsorbed) with humic and fulvic acids (fraction 6), show the order of Fe ≈ Zn ≈ Mn < Cu in the studied lakes (Tables 4 and 5). The decrease in the metal content associated with humic and fulvic acids was probably due to either low level of organic matter or the low retention capability of organic matter like humic acids and fulvic acids as a result of weak bonds existing between them (Belzile et al. 2004). Anthropogenic trace metals (fraction 7)
Fig. 4 Mean percent distributions of the trace metals in the Wadi El-Rayan lakes sediment
Mn
100 80 60 40 20 0 Fe
Fracon 1
Mn Fracon 2
Zn Fracon 3
Cu Fracon 4
Fracon 5
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Table 6 I-geo value of trace metals in the studied sediment Metal
Qarun Lake
Wadi El-Rayan lakes
I-geo
Sediment quality
Average
Min/max
Fe
−4.41
−4.92/−3.95
Mn
−1.97
−2.31/−1.48
Zn
−0.37
Cu
0.59
I-geo
Sediment quality
Average
Min/max
Uncontaminated
−5.08
−5.39/−4.81
Uncontaminated
−1.53
−1.94/−1.13
Uncontaminated
−0.77/0.09
Uncontaminated
0.22
−0.66/0.68
Uncontaminated to moderately contaminated
0.34/0.88
Uncontaminated to moderately contaminated
−0.31
−0.92/0.34
Uncontaminated
procedure was calculated as follows: Recovery ¼ ½ðfraction 1 þ fraction 2 þ fraction 3 þ fraction 4 þ fraction 5Þ =TM 100
Pollution intensity of trace metals in the sediment samples
Uncontaminated
sites and Zn at site 1 only. Site 1 at Qarun Lake closest to the dumping site of El-Bats Drain had a highest value of I-geo with respect to most of the studied metals. These findings clearly pointed to high levels of trace metal input from El-Bats Drain into the aquatic ecosystem of Qarun Lake. With respect to Cu, for Wadi EL-Rayan Lakes all the sites investigated had uncontaminated status except for site 1 (in front of El-Wadi Drain).
Geoaccumulation index
Pollution load index
The result of the calculated values of I-geo in the sediment samples are shown in Table 6. The negative values for Fe and Mn at all the studied sites for Qarun and Wadi El-Rayan lakes according to contamination classification (Müller 1969) (Table 7) showed that the sediment was practically uncontaminated by Fe and Mn. However, Qarun Lake had a status of practically uncontaminated to moderately contaminated with respect to Cu for all
The PLI value range from 0.45 to 0.67 for Qarun Lake and from 0.37 to 0.53 for Wadi El-Rayan lakes confirmed that the superficial sediments are in unpolluted condition (Table 8). The pollution load index does not show much fluctuation, where site 1 showed the highest value in Qarun Lake. Lower values of PLI imply no appreciable input from anthropogenic sources.
Table 7 I-geo classification I-geo I-geo class Description of sediment quality
Table 8 Pollution load index (PLI) for Qarun and Wadi El-Rayan lakes Site
PLI Qarun Lake
Wadi El-Rayan lakes
1
0.67
0.51
2
0.45
0.53
Moderately to strongly contaminated
3
0.47
0.53
4
Strongly contaminated
4
0.58
0.37
4–5
5
Strongly to extremely strongly contaminated
5
0.50
0.48
>5
6
Extremely contaminated
6
0.46
0.43
Cu > Zn > Fe. For both studied lakes, high values of mobility factors were observed mostly at site 1 closest to the dumping site of agricultural wastes containing high amount of pesticides. Qarun Lake showed high
Table 10 Criteria of the risk assessment code (RAC) Grade
I II
Exchangeable and bond to carbonate metal (%) 50
Source: Perin et al. (1985)
Risk assessment code The standards of RAC are listed in Table 10. The distribution of RAC for Fe fall in the no risk category (less than 1 % for the studied lakes); however, Mn falls in the low risk category in all sites (mean percentages 4.34 and 6.79 % for Qarun and Wadi El-Rayan lakes, respectively). Both Zn and Cu are mainly in the low risk category, although some sites fall into the medium risk category (Tables 4 and 5). According to analytical approaches based on I-geo, mobility factor, and RAC, the studied lakes suffered from borderline low pollution especially for Mn, Zn, and Cu. Some of the elevated concentrations of some metals are probably due to anthropogenic activities, and these are confirmed by the high anthropogenic trace metals (fraction 7) (Tables 4 and 5). It was obvious that majority of the heightened metal levels measured could be traced to point source input from the dumpsites (ElBats and El-Wadi drains), where Qarun Lake gains 338×106 m3 year−1 agricultural wastewater drainage from these drains, while Wadi El Rayan lakes receive water through the El-Wadi Drain, with discharges 220× 106 m3 year−1 (El-Shabrawy and Dumont 2009).
Low risk
III V
mobility factor for all studied metals than Wadi ElRayan, as such, all the humans, plants, animals and the general biota within the vicinity of this aquatic system are quite vulnerable to the trace metals exposure (Rendina et al. 2001).
Conclusion
Very high risk
In spite of the fact that the contamination of Qarun and Wadi El-Rayan lakes by trace metals is studied by many
Environ Monit Assess (2015) 187:346
researchers, no systematic study on the metal fractionation in the sediments has been carried out. Despite their low percent association in fraction 1 in the studied lakes, the risk of environmental and ecological damage from trace metals cannot be ruled out. The potential ecological risks for Fe and Zn in the studied lakes were low because residual fraction dominated, while Mn and Cu showed higher bioavailability compared to Fe and Zn. High nonresidual percent of Mn and Cu are thought to have resulted from anthropogenic influences, practically from pesticides used in agriculture, and are found to present a pollution risk. The comprehensive assessment of the potential pollution risks of the metals by using the mobility factor and risk assessment code declared that Qarun Lake showed high mobility factor for all studied metals than Wadi ElRayan lakes, Also, Zn and Cu showed high risk assessment code than Fe and Mn. Finally, site 1 at both Qarun and Wadi El-Rayan lakes closest to the dumping sites of El-Bats and El-Wadi drains showed elevated concentrations of some measured metals. Therefore, it is necessary to focus more attention on the distribution of trace metals in the sediment in the future management and pollution control of the studied lakes.
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Heavy metals fractionation and risk assessment in surface sediments of Qarun and Wadi El-Rayan Lakes, Egypt Amaal Mansour Abdel-Satar & Mohamed E. Goher
Received: 15 January 2015 / Accepted: 5 May 2015 # Springer International Publishing Switzerland 2015
Abstract This study establishes a baseline for trace metal speciation in Qarun and Wadi El-Rayan lakes. A five-step sequential extraction procedure was applied for the speciation of the Fe, Mn, Zn, and Cu in sediment samples collected at Qarun and Wadi El-Rayan lakes. Mn and Cu were the most mobile metals, whereas the residue fraction maintained the highest concentrations of Zn and Fe (≈60 %). No significant differences in metal concentrations were detected in the sediments of each lake sites, despite of the large distance between them (P>0.05). Hazardous discharge sources are responsible for the high accumulation of metals in the nonresidual fractions. Qarun Lake showed high mobility factor for all studied metals than Wadi El-Rayan lakes; as such, all the humans, plants, animals and the general biota within the vicinity of this aquatic system are quite vulnerable to the trace metal exposure. According to geoaccumulation index (I-geo), the studied sediments were practically uncontaminated by Fe and Mn and classified as uncontaminated to moderately contaminated with Cu in Qarun and Zn in Wadi ElRayan lakes. The low values of load pollution index
A. M. Abdel-Satar : M. E. Goher Inland Water and Aquaculture Branch, National Institute of Oceanography and Fisheries (NIOF), Cairo, Egypt A. M. Abdel-Satar (*) Chemistry Department, Faculty of Science, Hail University, Hail, Kingdom of Saudi Arabia e-mail: [email protected]
(1 is polluted whereas PLI value 0.05) in metals fractions concentrations were observed in the sediments from the six sites in Qarun and Wadi El-Rayan lakes despite the large distance between them. Total extractable metal contents in studied lakes decrease in the order Fe > Mn > Zn > Cu. The percentage of the exchangeable species, that is, the most
available fraction, was only 0.04 % (Fe), 1.67 % (Mn), 4.60 % (Zn), and 3.84 % (Cu) for Qarun and 0.09 % (Fe), 0.63 % (Mn), 4.43 % (Zn), and 2.29 % (Cu) for Wadi El-Rayan lakes (Figs. 3 and 4). Zn showed the highest exchangeable percent for the studied metals. Despite their low percent association in fraction 1, the risk of environmental and ecological damage from trace metals cannot be ruled out. However, if oxidationreduction condition is changed, the metal bound to reducible or oxidizable fractions can be released (Yang et al. 2014). Iron is the most abundant metal in all sediments because it is one of the most common metals in the Earth’s crust (Kumar et al. 2012). Negligible percentages of Fe were extracted as the exchangeable and carbonate fractions (less than 1 % of the extracted Fe) for the two studied lakes. The analysis of the distribution of Fe in lakes showed that most of it is associated with the residual phase (~65 %) (Figs. 3 and 4). The remaining fractions of Fe were distributed among the reducible and the oxidizable phases. The slight increase in the percentage of Fe in the oxidizable phases than the reducible was probably results from competition between Fe organic complexes and hydrous Fe oxide forms. This situation is complicated because hydrous Fe oxides themselves can complex with organics, especially humic substances in sediments (Fytianos and Lourantou 2004). In the two studied lakes, Fe and Zn were distributed in a similar manner, with the residual, organic bound and to a lesser extent the oxidizable fractions being of greatest significance (Figs. 3 and 4). The highest increase in the mean percentages of Fe and Zn in residual fractions in both Qarun (63.35 and 50.8 %, respectively) and Wadi El-Rayan (65.72 and 61.9 %, respectively), reflecting that these metals were strongly bound to the sediments, where the biological availabilities of those
346
Environ Monit Assess (2015) 187:346
Page 6 of 12
Table 4 Trace metal distribution in the Qarun Lake sediment samples Metal
Site
Fraction 1
Fraction 2
Fraction 3
Fraction 4
Fraction 5
TM
Recovery
Fraction 6
Fraction 7
μg/g
%
μg/g
%
μg/g
%
μg/g
%
μg/g
%
μg/g
%
%
%
1
5.44
0.14
1.80
0.05
680.4
17.11
868.2
21.84
2420
60.87
3660
108.6
5.580
17.43
2
1.80
0.08
2.16
0.09
612.9
26.42
424.1
18.31
1276
55.09
2101
110.3
4.760
13.06
3
0.08
0.00
6.36
0.21
345.9
11.47
811.0
26.96
1845
61.35
3214
93.60
5.000
18.60
4
0.04
0.00
1.16
0.03
424.9
9.400
978.8
21.66
3114
68.91
4099
110.2
2.650
12.69
5
0.48
0.02
1.40
0.04
468.9
14.69
584.7
18.32
2137
66.94
3009
106.1
2.120
12.39
6
0.48
0.01
0.80
0.02
494.0
15.41
565.4
17.63
2146
66.93
3501
91.59
2.330
12.94
1
9.64
1.89
19.4
3.81
161
31.6
195
38.2
125
24.5
490.
104
3.65
19.7
2
7.84
1.82
3.92
0.91
146
33.7
133
30.8
141
32.8
501
85.9
3.81
16.6
3
3.28
0.93
16.4
4.67
119
33.7
116
32.8
98.2
27.9
438
80.4
4.06
34.4
4
5.32
1.60
6.04
1.82
130
39.1
98.7
29.7
92.5
27.8
367
90. 6
4.34
20.3
5
1.76
0.56
8.60
2.72
89.2
28.2
96.6
30.5
120.
38.1
401
79.0
5.39
17.9
6
9.24
3.20
6.20
2.15
133
46.1
50.4
17.5
89.9
31.1
301
95.9
4.91
28.3
Fe
Mn
Zn 1
12.4
8.18
5.60
3.69
25.0
16.5
57.8
38.1
50.8
33.5
164
92.4
7.12
27.0
2
6.00
7.18
5.20
6.22
26.6
31.8
15.4
18.4
30.4
36.4
102
82.4
7.18
13.2
3
4.80
4.72
6.40
6.30
17.8
17.5
22.2
21.9
50.4
49.6
118
86.2
1.18
19.1
4
2.00
1.63
0.40
0.33
15.4
12.6
18.6
15.2
86.0
70.3
110.
112
0.98
8.50
5
1.60
1.35
5.60
4.73
14.6
12.3
15.8
13.3
80.8
68.2
131
90.4
1.52
9.29
6
4.40
4.55
3.20
3.31
29.8
30.8
14.2
14.7
45.2
46.7
101
95.9
0.62
15.7
Cu 1
8.21
7.45
3.50
3.18
14.7
13.3
45.6
41.4
38.2
34.7
113
97.6
7.36
27.5
2
4.20
5.10
4.10
4.98
13.2
16.0
29.9
36.3
30.9
37.6
93.6
88.1
7.89
15.6
3
3.00
3.95
3.10
4.08
10.2
13.4
30.1
39.6
29.6
39.0
91.0
83.5
8.74
13.1
4
2.00
1.87
2.00
1.87
15.4
14.4
44.4
41.5
43.2
40.4
110.
97.3
8.61
12.9
5
2.10
2.33
4.10
4.56
13.4
14. 9
41.1
45. 7
29.3
32.6
102
88.0
6.07
11.4
6
1.90
2.35
3.20
3.95
18.6
23.0
29.2
36.1
28.1
34.7
101
80.2
6.75
11.3
trace metals were relatively lower (Ogunfowokan et al. 2013), and it can only be released over time as a function of the weathering process (Yang et al. 2014). However, manganese behaves a different way (Figs. 3 and 4). Mn was distributed primary in the reducible (iron/manganese oxides) (35.4 and 35.44 % for Qarun and Wadi El-Rayan, respectively), residual (30.4 and 32.8 %), and oxidizable (organic matter and sulfides) phases (29.9 and 25.0 %). This agrees Calmano and Forstner (1983) and Fytianos and Lourantou (2004). The large percent of metals associated with the reducible fraction raises concerns their potential mobility in the water phase. However, if
oxidation-reduction potential and oxygen levels in water decrease, these may deoxidize and cause secondary pollution, which can be seen in the environmental pollution associated with extensive human activities (Yang et al. 2014). The nonresidual fractions (available + acidsoluble + reducible + oxidizable) of Mn in sediments were greater (70.8 % for Qarun and 67.2 % for Wadi ElRayan) than residual fractions. Therefore, the results indicate that Mn in sediments from Qarun and Wadi El-Rayan lakes are potentially more available for exchange and/or release into the aquatic environment. The high Cu percentage was recorded in the oxidizable fraction for Qarun and Wadi El-Rayan lakes (40.1
Environ Monit Assess (2015) 187:346
Page 7 of 12 346
Table 5 Trace metal distribution in the Wadi El-Rayan lakes sediment samples Metal
Site
Fraction 1
Fraction 2
Fraction 3
Fraction 4
Fraction 5
TM
Recovery
Fraction 6
Fraction 7
μg/g
%
μg/g
%
μg/g
%
μg/g
%
μg/g
μg/g
%
%
%
1
0.04
0.00
1.08
0.06
228.5
12.78
495.7
27.72
1063
59.44
1890.
94.60
13.20
15.20
2
0.04
0.00
1.92
0.10
304.4
16.56
402.6
21.90
1129
61.43
2104
87.38
3.060
4.780
3
2.32
0.09
0.08
0.00
375.1
15.02
459.4
18.40
1660.
66.48
2334
107.0
2.840
4.200
4
4.24
0.25
0.06
0.00
267.8
16.05
242.7
14.55
1153
69.14
1721
96.95
7.200
9.210
5
4.00
0.16
2.00
0.08
368.8
14.75
445.6
17.82
1680.
67.19
2792
89.58
2.010
4.710
6
1.32
0.06
0.24
0.01
397.3
17.35
273.2
11.93
1618
70.65
2240.
102.2
2.610
4.710
1
3.60
0.60
44.5
7.43
250
41.8
146
24.3
155
25.9
710
84.3
3.35
16.0
2
2.96
0.45
33.4
5.13
251
38.5
146
22.4
219
33.5
740
88.1
3.19
9.59
3
3.32
0.56
36.5
6.17
229
38.6
156
26.3
168
28.4
671
88.3
3.57
9.42
4
2.80
0.63
35.3
7.90
135
30.1
139
31.1
135
30.2
425
105
4.66
12.1
5
3.32
0.89
17.3
4.63
103
27.7
90.3
24.2
159
42.6
418
89.2
5.50
15.0
6
2.32
0.62
21.5
5.74
134
35.8
82.0
21.9
135
36.0
330
114
5.58
13.9
1
6.40
4.71
5.60
4.12
24.4
17.9
25.2
18.5
74.4
54.7
162
84.2
6.76
17.1
2
2.00
1.00
2.80
1.40
25.6
12.8
25.6
12.8
144
72.1
184
109
2.50
7.39
3
2.80
1.51
2.40
1.29
20.0
10. 8
36.8
19.8
124
66.6
172
108
3.02
7.65
4
5.20
5.75
7.20
7.96
24.8
27.4
16.8
18.6
36.4
40.3
103
87.7
6.86
16.4
%
Fe
Mn
Zn
5
21.2
9.27
4.40
1.92
26.8
11.7
29.6
12.9
147
64.2
272
84.2
1.92
12.8
6
8.80
4.37
4.00
1.98
23.6
11.7
17.2
8.53
148
73.4
221
91.4
2.18
7.64
1
1.40
1.84
1.20
1.58
12.1
15.9
32.6
42.8
28.8
37.8
64.9
117
12.0
13.4
2
1.50
2.81
0.99
1.86
7.10
13.3
23.1
43.3
20.7
38.8
49.4
108
7.49
9.93
3
0.90
1.83
1.56
3.16
8.50
17.3
19.0
38.6
19.3
39.2
56.7
87.0
9.34
9.54
4
0.60
1.27
1.00
2.12
4.50
9.55
19.1
40.6
21.9
46.5
51.2
91.9
11.0
11.3
Cu
5
0.80
1.89
0.90
2.13
6.20
14.7
18.6
44.0
15.8
37.4
50.7
83.4
8.04
15.8
6
1.30
4.09
2.20
6.92
4.90
15.4
12.2
38.4
11.2
35.2
39.0
81.5
10.7
17.3
and 41.3 %, respectively) (Figs. 3 and 4). Its percentage of partitioning distribution in the studied lakes is in the order: oxidizable > residual > reducible > carbonate bound ≈ exchangeable. The high affinity of Cu to organic matter indicates the strong complexing affinity of organic matter with copper (Morillo et al. 2004; Ramirez et al. 2005). Under oxidizing conditions a significant fraction (up to 40 %) of the Cu reaching the sediment surface may be returned to the overlying water column in the two studied lakes. Several studies have also reported high concentration of Cu associated with organic matter in the sediment (Fytianos and
Lourantou 2004; Ramirez et al. 2005; Wong et al. 2007; Turki 2007; Arias et al. 2008). Also, there is increase in exchangeable percent in the site 1 at Qarun lake (7.45 %) compared with other sites reflect the effect of drainage water from ElBats Drain. The increase in sorption of Cu in the oxidizable fraction in the studied lakes than Zn may be due to the Cu was sorbed more selectively than Zn in the organic surface including humic and fulvic acid (Violante et al. 2010). The increase in non residual percents of Mn and Cu in the studied lakes may be originated from anthropogenic
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Fig. 3 Mean percent distributions of the trace metals in the Qarun Lake sediment
100 80 60 40 20 0 Fe
Fracon 1
Fracon 2
Zn Fracon 3
Cu Fracon 4
Fracon 5
follow the order Fe ≈ Zn ≈ Cu≈ 15 % < Mn ≈ 23 % in Qarun sediment and Fe ≈ 7 % < Mn ≈ Zn ≈ Cu ≈ 12 % in Wadi El-Rayan lakes (Tables 4 and 5). The increase in this fraction at Qarun Lake for all studied metals is an indication of significant anthropogenic sources. As shown in Tables 4 and 5, results for the analysed sediments indicate that the sums of the five fractions are in good agreement with the amount of total extractable metal (TM), with satisfactory recoveries (79.0–112 % for Qarun and 81.5–117 % for Wadi El-Rayan Lakes), which implies that the accuracy of the extraction procedure. The recovery of the sequential extraction
influences, practically from pesticides used in agriculture, and are found to present a pollution risk (Akcay et al. 2003) The fraction of trace metals associated (chelated or adsorbed) with humic and fulvic acids (fraction 6), show the order of Fe ≈ Zn ≈ Mn < Cu in the studied lakes (Tables 4 and 5). The decrease in the metal content associated with humic and fulvic acids was probably due to either low level of organic matter or the low retention capability of organic matter like humic acids and fulvic acids as a result of weak bonds existing between them (Belzile et al. 2004). Anthropogenic trace metals (fraction 7)
Fig. 4 Mean percent distributions of the trace metals in the Wadi El-Rayan lakes sediment
Mn
100 80 60 40 20 0 Fe
Fracon 1
Mn Fracon 2
Zn Fracon 3
Cu Fracon 4
Fracon 5
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Table 6 I-geo value of trace metals in the studied sediment Metal
Qarun Lake
Wadi El-Rayan lakes
I-geo
Sediment quality
Average
Min/max
Fe
−4.41
−4.92/−3.95
Mn
−1.97
−2.31/−1.48
Zn
−0.37
Cu
0.59
I-geo
Sediment quality
Average
Min/max
Uncontaminated
−5.08
−5.39/−4.81
Uncontaminated
−1.53
−1.94/−1.13
Uncontaminated
−0.77/0.09
Uncontaminated
0.22
−0.66/0.68
Uncontaminated to moderately contaminated
0.34/0.88
Uncontaminated to moderately contaminated
−0.31
−0.92/0.34
Uncontaminated
procedure was calculated as follows: Recovery ¼ ½ðfraction 1 þ fraction 2 þ fraction 3 þ fraction 4 þ fraction 5Þ =TM 100
Pollution intensity of trace metals in the sediment samples
Uncontaminated
sites and Zn at site 1 only. Site 1 at Qarun Lake closest to the dumping site of El-Bats Drain had a highest value of I-geo with respect to most of the studied metals. These findings clearly pointed to high levels of trace metal input from El-Bats Drain into the aquatic ecosystem of Qarun Lake. With respect to Cu, for Wadi EL-Rayan Lakes all the sites investigated had uncontaminated status except for site 1 (in front of El-Wadi Drain).
Geoaccumulation index
Pollution load index
The result of the calculated values of I-geo in the sediment samples are shown in Table 6. The negative values for Fe and Mn at all the studied sites for Qarun and Wadi El-Rayan lakes according to contamination classification (Müller 1969) (Table 7) showed that the sediment was practically uncontaminated by Fe and Mn. However, Qarun Lake had a status of practically uncontaminated to moderately contaminated with respect to Cu for all
The PLI value range from 0.45 to 0.67 for Qarun Lake and from 0.37 to 0.53 for Wadi El-Rayan lakes confirmed that the superficial sediments are in unpolluted condition (Table 8). The pollution load index does not show much fluctuation, where site 1 showed the highest value in Qarun Lake. Lower values of PLI imply no appreciable input from anthropogenic sources.
Table 7 I-geo classification I-geo I-geo class Description of sediment quality
Table 8 Pollution load index (PLI) for Qarun and Wadi El-Rayan lakes Site
PLI Qarun Lake
Wadi El-Rayan lakes
1
0.67
0.51
2
0.45
0.53
Moderately to strongly contaminated
3
0.47
0.53
4
Strongly contaminated
4
0.58
0.37
4–5
5
Strongly to extremely strongly contaminated
5
0.50
0.48
>5
6
Extremely contaminated
6
0.46
0.43
Cu > Zn > Fe. For both studied lakes, high values of mobility factors were observed mostly at site 1 closest to the dumping site of agricultural wastes containing high amount of pesticides. Qarun Lake showed high
Table 10 Criteria of the risk assessment code (RAC) Grade
I II
Exchangeable and bond to carbonate metal (%) 50
Source: Perin et al. (1985)
Risk assessment code The standards of RAC are listed in Table 10. The distribution of RAC for Fe fall in the no risk category (less than 1 % for the studied lakes); however, Mn falls in the low risk category in all sites (mean percentages 4.34 and 6.79 % for Qarun and Wadi El-Rayan lakes, respectively). Both Zn and Cu are mainly in the low risk category, although some sites fall into the medium risk category (Tables 4 and 5). According to analytical approaches based on I-geo, mobility factor, and RAC, the studied lakes suffered from borderline low pollution especially for Mn, Zn, and Cu. Some of the elevated concentrations of some metals are probably due to anthropogenic activities, and these are confirmed by the high anthropogenic trace metals (fraction 7) (Tables 4 and 5). It was obvious that majority of the heightened metal levels measured could be traced to point source input from the dumpsites (ElBats and El-Wadi drains), where Qarun Lake gains 338×106 m3 year−1 agricultural wastewater drainage from these drains, while Wadi El Rayan lakes receive water through the El-Wadi Drain, with discharges 220× 106 m3 year−1 (El-Shabrawy and Dumont 2009).
Low risk
III V
mobility factor for all studied metals than Wadi ElRayan, as such, all the humans, plants, animals and the general biota within the vicinity of this aquatic system are quite vulnerable to the trace metals exposure (Rendina et al. 2001).
Conclusion
Very high risk
In spite of the fact that the contamination of Qarun and Wadi El-Rayan lakes by trace metals is studied by many
Environ Monit Assess (2015) 187:346
researchers, no systematic study on the metal fractionation in the sediments has been carried out. Despite their low percent association in fraction 1 in the studied lakes, the risk of environmental and ecological damage from trace metals cannot be ruled out. The potential ecological risks for Fe and Zn in the studied lakes were low because residual fraction dominated, while Mn and Cu showed higher bioavailability compared to Fe and Zn. High nonresidual percent of Mn and Cu are thought to have resulted from anthropogenic influences, practically from pesticides used in agriculture, and are found to present a pollution risk. The comprehensive assessment of the potential pollution risks of the metals by using the mobility factor and risk assessment code declared that Qarun Lake showed high mobility factor for all studied metals than Wadi ElRayan lakes, Also, Zn and Cu showed high risk assessment code than Fe and Mn. Finally, site 1 at both Qarun and Wadi El-Rayan lakes closest to the dumping sites of El-Bats and El-Wadi drains showed elevated concentrations of some measured metals. Therefore, it is necessary to focus more attention on the distribution of trace metals in the sediment in the future management and pollution control of the studied lakes.
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