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Page 1: Soil Plant Transfer and Accumulation Factors for Trace ...researchpub.org/journal/jais/number/vol1-no2/vol1-no2-12.pdf · Soil-Plant Transfer and Accumulation Factors for Trace Elements

97

Journal of Applied and Industrial Sciences, 2013, 1 (2): 97-102, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

Research Article

*Corresponding author E-mail: [email protected]

Abstract- Plants acquire nutrients including trace element from

the soil for their growth. At high concentrations in polluted

soil, trace elements can accumulate in the plants and get

introduced in food chain. The elements ( Fe, Mn, Cu, Zn, Pb,

Ni, P, Co and Cr) were determined in nine soil and Sourghm

Color (Abusabeen), samples from the bank of the Blue Nile

(BN) (6 samples) and White Nile (WN) (3samples) around

Khartoum province, Sudan (Fig.1).The concentrations of the

elements in the samples were comparable with local and

international data. The enrichment factors (E.F.) for elements

in the plant were calculated. The elemental concentrations and

(E.F.) of the plants from the BN were comparatively higher

than WN, whereas a relative measure of the transfer of the trace

element from the soil to the plant expressed by transfer factor

(TF) were higher in WN soil. The soil analysis revealed that

WN soil is sandy soil while BN is clay soil. The

physiochemical properties of soil supported the finding. It was

concluded that the uptake of element by plants depends upon

the type of soil and the concentration of available elements.

Index terms: Sorghum color, Trace elements, Transfer &

accumulation factors.

I. INTRODUCTION

udan topography consisted mainly of deserts, except the

narrow strip of the Nile valley which provide fertile

agricultural soil. The study area is the White Nile and Blue

Nile around Khartoum province. The White Nile originates

from Lake Victoria in Uganda while the Blue Nile starts from

the Ethiopian Plateau. The soil of the While Nile is sandy

while that of Blue Nile is black clay soil, and the rocks are

composed of hard igneous rock. Total estimated area is about

126, 000 ha, with almost half in Khartoum State [1]. Plants are

used as bioindicators for pollution extents [2], trace and macro

elements intake [3, 4] and phytoextraction [5 , 6]. Hokura et

al. [7] calculated the accumulation and enrichment factors by

soil and plant analysis and found that the essential elements

(K, Mg, Mn, Cu, Zn, B and P) have large enrichment factors.

The shrub species Pittosoporum tobica was analyzed [8] to

monitor the distribution of element and anthropogenic effects

upon the accumulation of trace elements. On the other hand

Sardans et al. [9] investigated the effect of global climate

change upon the accumulation of trace metals in plants and

found that warming leads to an increase of Al, As, Cr and Cu.

Some plants species were found to have tolerance to toxic

metals uptake in polluted mine soil as they were found to

accumulate high concentrations of Al, As, Cu, Ni, Pb and Zn

[10]. Mingorance et al. [11] found that plant uptake by park

and foliage for trace metals was the same. They also indicated

that Cu and Pb uptake was enhanced by anthropogenic factors.

Petrochemical plants were associated with raised levels of As,

Mo, Ni, S, Se, V and Zn while traffic enhances elements like

Cu, Pb, Pt, Pd and Sb [12]. The trace element pollutants can

risk human life through food chain where plant is the

intermediate path [13]. Plants are used in the process of

phytoremedation for contaminated soil [14-16] due to trace

element uptake from soil.

The objective of this study is to determine the elemental

contents for soil and Sorghum color samples, calculate the

enrichment factor (EF) and transfer factor (TF) and correlate

that to soil properties.

II. MATERIALS AND METHODS

Soil samples were collected from nine sites at the bank of

the B.N. (6 site) and W.N. (3 sites) from 10 cm depth using

stainless steel knife. The samples were kept in plastic bags and

immediately taken to the laboratory where they were oven

dried at 50°C for 24 h. The samples were then stored for

analysis. The plant samples were collected from the same sites.

The stem and leaves were separated from the roots, washed

with tape water then distilled water and left to dry at room

temperature in shade. The soil particle size distribution was

determined to a standard method [17] by passing through

different size sieves. The texture classification was done using

the international society of science scheme (ISSS). Chemicals

used for digestion were of analytical grade (Merck -Germany)

and were used without further purification. The soil digestion

was carried out by transferring 1.0 g of dry soil sample to a

Teflon reactor where a mixture of 5 ml HNO3

Soil-Plant Transfer and Accumulation Factors

for Trace Elements at the Blue and White Niles

Kamal K.Taha*1

, Mona I. Shmou1, Maisoon H.Osman

1, M. H. Shayoub

2

1 College of Applied and Industrial Sciences, Department of chemistry, University of Bahri, Sudan.

2College of Pharmacy, University of Khartoum, Khartoum, Sudan

(Received: April 29, 2013; Accepted: May 31, 2013)

S

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98

Journal of Applied and Industrial Sciences, 2013, 1 (2): 97-102, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

(70% v/v), 5 ml HClO4 (70% v/v), and 10 ml HF (48% v/v)

was added. The solution was then heated to dryness in an open

hot-plate, and the residue was re-dissolved in 5 ml HCl (36%

v/v) and 20 ml distilled water. The resulting solution was

filtered and transferred to a 100 ml volumetric flask. This

analytical protocol is assumed to dissolve the silicate matrix of

the sample and thus yield a ―total‖ digest [18]. The plant

samples were digested by weighing 1.0 gram of a dry sample

in a beaker. About 10.0 ml of HNO3 was added and the

mixture was heated in a sand bath then washed with distilled

water and kept in a volumetric flask. A Perkin –Elmer -1130

atomic absorption spectrometer was employed for atomic

absorption analysis of samples. The reference material lake

sediment (STM5) and hay powder (V-10) obtained from the

international atomic energy (IAEA were digested according to

the method employed for soil and plant. Soil pH was

determined by using pH meter (HANNA HSA) in 1:2.5 (W/V)

by mixture the soil to de-ionized water.

Figure 1. Photo of Study Area

III. RESULTS AND DISCUSSION

Figure 2. USDA textural triangle for textural classification of soil

N

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Journal of Applied and Industrial Sciences, 2013, 1 (2): 97-102, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

Table 1.The particle size distribution for soil from WN and BN

Sample soil from White Nile ,

W=50.78

Sample soil from Blue Nile

, W=50.85

Size of sieve by

(mm)

Mass% Size of sieve by (mm) Mass%

4 - 4 -

2 - 2 0 %

1 3 % 1 0 %

0.5 10 % 0.5 0 %

0.25 22 % 0.25 2 %

0.125 29 % 0.125 28 %

0.063 12 % 0.063 24 %

0.032 6 % 0.032 30 %

0.01 11% 0.01 9 %

94 % 93 %

Table 2. Average value of physiochemical properties of the soil

Property WN BN

Organic matter % 2.64 4.07

ECE (µS) 1020 300

Moisture content % 1.38 2.15

pH 7.89 7.75

Table 3. Average elemental concentration (ppm) in the soil samples from BN and WN

Physiochemical properties are important parameters in soil to

plant nutrients uptake [19, 20]. From the results of soil

particle size distribution (Figure (2) and Table (1) ), it can be

concluded that soil from the WN has 30% fine particles of ≤

63 mm compared to the BN soil that contains about 63%. This

indicates that the WN soil is sandy soil while that of the BN is

clay soil. The average values of physiochemical properties of

the (WN) and (BN) soil indicate that the electrical

conductivity (ECE) is higher at the WN soil, this may due to

more soluble ions which increase the electrical conductivity

(ECE). Both soil are slightly alkaline (WN having a little

higher alkalinity). A T-test was carried out to compare the

elemental concentration at the BN and WN stations. The test

revealed that the elements of lethiogenic origin i.e Fe, Co and

Mn were significantly different in the two areas while those of

anthropogenic origin i.e. Pb, Zn, Cr and Cu were not

significantly different. When the values obtained by were

compared with data obtained by Hassona [21], who worked in

Element BN WN Hassona Elidrisi

Fe 84000 39000 53770 33000 - 94000

P 7100 4200 801

Mn 1523 506 896 816 - 1516

Cr 89.7 71.7 259

Co 92.8 36.7 88 40.8 - 104

Ni 62.0 46.7 41 41.3 - 72

Cu 53.0 45.0 45 40.8 - 106

Zn 199.0 143.0 72 189.8 - 149

Pb 77.1 49.7 -

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Journal of Applied and Industrial Sciences, 2013, 1 (2): 97-102, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

Elguneid scheme, a similarity in the concentrations of Fe, Co,

Ni and Cu can be observed. The high concentration of Zn in

Khartoum may be an indication of pollution taking place. The

results are within the ranges reached by Elidrisi [22] and

Ahmed [23] who worked in the BN at Khartoum.

Table 4. Average elemental concentrations (ppm) in plants samples from BN and WN

Table 5. Enrichment and transfer factor for plants samples from BN and WN

Table (4) shows the elemental concentrations obtained for

plant samples. Similar values of Pb and Zn concentrations

were observed in Kampala city [24]. The concentrations of

elements in plant samples from the WN are higher than those

from BN though the elemental concentration in soil samples

from the latter was higher. This finding agree with the

assumption that Fe and other transition metals like Cr, Co, Ni

that form chelates in with the organics of the clay are not

available for plant uptake[25, 26]. Quartacci et al. [4] used

nitrilotriacetate as chelating agent to desorb trace metals from

soil to avail it for plant uptake. This study supports the low

trace metal uptake by plants from the clay soil of the BN. The

enrichment factor (EFi) or accumulation factor for an element

was calculated using the formula [27].

soili

planti

iFeX

FeXEF

]/[

]/[ (1)

Where Xi, Fe are the concentrations of element (i) and Fe

respectively.

The transfer factor (TFi) which is obtained by dividing

the element concentration in the plant over its

concentration in soil [3] was also calculated. Table (5)

gives the values for (EFi) and (TFi) for the elements under

investigation in the BN and WN plant samples. The

transfer factor is an indication of the plant species ability or

tendency to uptake a certain element from the soil [28-30].

The values obtained for the (EFi) are higher for plant

samples from the BN though the elemental concentrations

have the opposite trend. These high values can be

explained by the lower uptake of Fe (reference) by plants

from BN, hence the numerator in equation (1) will be more

resulting in high values of (EFi). On the other hand the

values of (TFi) are of higher values for plant samples from

Element BN WN Elidrisi

Fe 561 841 47 - 2455

P 3700 2700

Mn 80.0 41.4 7.6 - 162

Cr 10.2 13.6

Co 2.1 2.4 0.003 – 0.63

Ni 3.6 5.2 0.07 – 4.8

Cu 17.6 21.8 2.4 – 15.0

Zn 51.0 37.2 6.6 – 48.9

Pb 4.2 3.5

Element EFi TFi

BN WN BN WN

Fe 0.007 0.022

Cr 18 8.8 0.113 0.190

Mn 7.9 3.8 0.053 0.082

Co 3.4 3.1 0.023 0.066

Ni 8.8 5.2 0.058 0.111

Cu 49.8 22.5 0.033 0.484

Zn 37.9 12.1 0.256 0.253

Pb 81.5 3.4 0.054 0.073

P 77.8 29.8 0.521 0.643

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Journal of Applied and Industrial Sciences, 2013, 1 (2): 97-102, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

the WN, not following the concentration trend. This

contradiction may be justified as follows: the (EFi) were

calculated using the total Fe in soil which is higher than

what may be available, due to chelation of transition

elements with organics in the clay soil of BN. Thus it is

more appropriate to obtain the value employing the

sequential extraction method where the elements available

for plants can be determined[27]. Similar result were

obtained by Abu-Khadra et al. [31], who found that the

uptake of Cs and Sr by wheat grown on sandy soil is

greater than clay soil. This finding indicates that the

element uptake by plants in less clay or sandy soil is higher

than the clay soil. In a similar study Sardans and Peñuelas

[32] suggested that in determining the (EFi) the solubility-

absorption-retention levels should be considered. Thus the

(EFi) values are not linear with the concentration of

elements in soil [33] but depends upon soil properties. The

values of (TFi) obtained in this study were less than those

obtained in an industrial area in Turkey [3]. The low (TFi)

for Zn in the sandy WN soil may be due to the greater soil

pH, at which zinc is precipitated as Zn(OH)2 or ZnCO3[34,

35 ]. In a similar studies it has also been reported that Zn

inhibit the Cu absorption [36, 37]. The low transfer factor

for copper at the BN may be attributed to organic matter

content in the BN soil that chelates with positive ion

rendering them unavailable for plant uptake [38]. This is in

agreement with Benke et al. [39] who reported that

increase in organic matter content decreases the extractable

copper and increases the extractable zinc [40]. The transfer

factor of all elements for plants grown in BN and WN soil

are low may be due to soil alkalinity that reduces the

mobility of ions [41].

VI. CONCLUSIONS

1. According to the particle size distribution we observed

that White Nile soil is sandy while the Blue Nile soil is

clay

2. The elemental concentration of the Blue Nile soil is

higher compared to the White Nile soil.

3. The TF for Sorghum color from (WN) soil is greater

than BN soil.

4. We can conclude that the Sorghum color can be used as

food for animals and the fodder is not polluted with

metals.

REFERENCES

[1] Zaroug, Mahgoub G., Abul Aziz Ahmed Mohamed and

Mahmoud H. Ali (1997). Forage and Pasture Seed Production

in the Sudan: An Overview. Forage and Pasture Seed

Seminar, ICARDA/ILRI.

[2] Sardans J. and Peñuelas J. (2006) Introduction of the

factor of partitioning in the lithogenic enrichment factors of

trace element bioaccumulation in plant tissues, Environ Monit

Assess, 115, pp. 473-98.

[3] Heide Spiegel (2002), Trace element accumulation in

selected bioindicators exposed to emissions along the

industrial facilities of Danube lowland, Turk J Chem., 26,

pp.815 – 823.

[4] María José Martínez-Sánchez, Mari Luz García-Lorenzo,

Carmen Pérez-Sirvent,

and Jaume Bech (2012). Trace

element accumulation in plants from an aridic area affected

by mining activities. Journal of Geochemical Exploration,

123, pp. 8–12.

[5] M.F. Quartacci, A. Argilla, A.J.M. Baker and F. Navari-

Izzo. (2006) Phytoextraction of metals from a multiply

contaminated soil by Indian mustard, Chemosphere, 63, pp.

918-925.

[6] Jan Mertens, , Sebastiaan Luyssaert and Kris Verheyen

(2005,).Use and abuse of trace metal concentrations in plant

tissue for biomonitoring and phytoextraction, Environmental

Pollution, 138, pp. 1-4.

[7] Hokura Akiko, Matsuura Hirotaka, Katsuki Fumie

and

Haraguchi Hiroki (, 2000). Multielement determination of

major-to-ultratrace elements in plant reference materials by

ICP-AES/ICP-MS and evaluation of their enrichment factors.

Analytical sciencesm 16, pp. 1161-1168.

[8] G. Lorenzini, C. Grassi, C. Nali , A. Petiti, S. Loppi and

L. Tognotti (2006). Leaves of Pittosporum tobira as

indicators of airborne trace element and PM10 distribution in

central Italy, Atmospheric Environment, 40, pp. 4025-36.

[9] Sardans, J. Peñuelas and M. Estiarte (, 2008), Warming

and drought change trace element bioaccumulation patterns in

a Mediterranean shrubland, Chemosphere, 70, pp. 874-85.

[10] H. Freitas, M. N. V. Prasad and J. Pratas (2004). Plant

community tolerant to trace elements growing on the

degraded soils of São Domingos mine in the south east of

Portugal: environmental implications, Environment

International, , 30, pp. 65-72.

[11] M.D. Mingorance, B. Valdés and S. Rossini Oliva (

2007). Strategies of heavy metal uptake by plants growing

under industrial emissions, Environment International, 33,

pp. 514-520.

[12] M.L. Bosco, D. Varrica and G. Dongarrà (2005). Case

study: Inorganic pollutants associated with particulate matter

from an area near a petrochemical plant, Environmental

Research, 99, pp. 18-30.

[13] Rajesh Kumar Sharma, Madhoolika Agrawal and Fiona

Marshall (2007). Heavy metal contamination of soil and

vegetables in suburban areas of Varanasi, India,

Ecotoxicology and Environmental Safety, , 66, pp. 258-66.

[14] Wuana and F.E.Okieimen(2010) phytoremedation

potential of maize, Afric job general agric , 6(4); pp.275-287.

[15] Eduardo Moreno-Jiménez,

Saúl Vázquez, Ramón O.

Carpena-Ruiz, Elvira Esteban and, Jesús M. Peñalosa (2011).

Using Mediterranean shrubs for the phytoremediation of a

soil impacted by pyritic wastes in Southern Spain: A field

experiment. Journal of Environmental Management, 92, pp.

1584–1590.

[16] Mery Malandrino, Ornella Abollino , Sandro Buoso ,

Agnese Giacomino, Carmela La Gioia , and Edoardo

Mentasti (2011). Accumulation of heavy metals from

Page 6: Soil Plant Transfer and Accumulation Factors for Trace ...researchpub.org/journal/jais/number/vol1-no2/vol1-no2-12.pdf · Soil-Plant Transfer and Accumulation Factors for Trace Elements

102

Journal of Applied and Industrial Sciences, 2013, 1 (2): 97-102, ISSN: 2328-4595 (PRINT), ISSN: 2328-4609 (ONLINE)

contaminated soil to plants and evaluation of soil remediation

by vermiculite, Chemosphere, 82 (2); pp. 169–178.

[17] Gee G.Wand Bauder J.W. (1986).Particle size analysis

.methods of soil analysis part1 Agron. Mono. 9;pp 583-412.

[18] Eduardo de Miguel, Susanne Charlesworth, Almudena

Ordóñez and Eduardo Seijas (2005). Geochemical fingerprints

and controls in the sediments of an urban river: River

Manzanares, Madrid Spain), Science of The Total

Environment, 340, pp. 137-48.

[19] Zhenfei Lianga, Qiong Ding, Dongpu Wei, Jumei Li,

Shibao Chen, and Yibing Ma (2013). Major controlling

factors and predictions for cadmium transfer from the soil into

spinach plants. Ecotoxicology and Environmental Safety, 93,

pp. 180–185.

[20] Khadija Semhi, Norbert Clauer, ,

and Sam Chaudhuri

(2012). Variable element transfers from an illite-rich substrate

to growing plants during a three-month experiment. Applied

Clay Science 57, pp. 17–24.

[21] Hassona R. K. (1996), M.Sc. thesis, University of

Khartoum.

[22] Elidrisi I. A. (1993), M.Sc. thesis, University of

Khartoum.

[23] Ahmed M. M., PhD thesis, University of Khartoum

(1988).

[24] Grace Nabulo , Hannington Oryem-Origa and Miriam

Diamond (, 2006). Assessment of lead, cadmium, and zinc

contamination of roadside soils, surface films, and vegetables

in Kampala City, Uganda, Environmental Research, 101, pp.

42-52.

[25] P. Planquart, G. Bonin, A. Prone and C. Massiani (1999).

Distribution, movement and plant availability of trace metals

in soils amended with sewage sludge composts: application to

low metal loadings, Science of The Total Environment, 241,

pp. 161-79.

[26] M. Ergin, C. Saydam, O. Basturk, E. Erdem and R.

Yoruk (1991). Heavy metal concentrations in surface

sediments from the two coastal inlets (Golden Horn Estuary

and İzmit Bay) of the northeastern Sea of Marmara, Chem.

Geo., 91, pp. 269–85.

[27] Alina Kabata-Pendias (2004). Soil–plant transfer of trace

elements—an environmental issue, Geoderma, 122, pp. 143-

49.

[28] C. Bitterli, G.S. Bañuelos and R. Schulin (2010).

Use of

transfer factors to characterize uptake of selenium by plants.

Journal of Geochemical Exploration, 107 (2); pp. 206–216.

[29] Fei-li Li, Jin Yuan, and G. Daniel Sheng (2012). Altered

transfer of heavy metals from soil to Chinese cabbage with

film mulching. Ecotoxicology and Environmental Safety, 77

(1), pp. 1–6.

[30] Kassaye YA, Skipperud L, Meland S, Dadebo E, Einset J

and Salbu B (2012). Trace element mobility and transfer to

vegetation within the Ethiopian Rift Valley lake areas. J.

Environ Monit. 14(10); pp. 2698-709.

[31] Abu-Khadra S A;Abdel-Sabour M.F; Abdel-Fattah A.T;

and Eissa H.S.(2008). Transfer factor of radioactive Cs and Sr

from Egyptian soil to root and leaves of wheat plant .radiation

physics and protection conference 15-19,Nasir city ,Cairo

Egypt,185-196.

[32] Sardans J, Peñuelas J. (2005,Trace element accumulation

in the moss Hypnum cupressiforme Hedw. and the trees

Quercus ilex L. and Pinus halepensis Mill. in Catalonia,

Chemosphere, 60, pp. 1293-307.

[33] Tiina S. Tuovinen, Päivi Roivainen,

Sari Makkonen,

Mikko Kolehmainen, Toini Holopainen, and Jukka Juutilainen

(2011). Soil-to-plant transfer of elements is not linear: Results

for five elements relevant to radioactive waste in five boreal

forest species. Science of The Total Environment. 410–411;

pp. 191–197.

[34] Saeed, M., and R.L. Fox. 1977. Relationships between

suspension. pH and zinc solubility in acid and calcareous soils.

Soil Sci. 124: 199-203.

[35] Hai Fang Wang, Noburu Takematsu and Shizuko Ambe

(2000). Effects of soil acidity on the uptake of trace elements

in soybean and tomato plants. Applied Radiation and Isotopes,

52 (4), pp. 4803–811.

[36] Bowen JE. (1987). Physiology of genotypic differences in

Zn and Cu uptake in rice and tomato. Proceedings of 2nd

International Symposium on Genetic Aspects of Plant Mineral

Nutrition. Dordrecht, The Netherlands: Kluwer Academic

Publisher, 413–423.

[37] Cheng Wang, Zhongfang Yang, Xuyin Yuan, Patrick

Browne, Lingxiao Chen, and Junfeng Ji (2013). The influences

of soil properties on Cu and Zn availability in soil and their

transfer to wheat (Triticum aestivum L.) in the Yangtze River

delta region, China, Geoderma, 193–194, pp. 131–139.

[38] Lina Nafeh Kassir, Talal Darwish, Amin Shaban, Guirec

Olivier, and Naim Ouaini (2012). Mobility and bioavailability

of selected trace elements in Mediterranean red soil amended

with phosphate fertilizers: Experimental study, Geoderma,

189–190, pp. 357–368.

[39] Benke, M.B., Indraratne, S.P., Hao, X., Chang, C., and

Goh, T.B. 2008. Trace element changes in soil after long-term

cattle manure applications. J. Environ. Qual. 37:798–807.

[40] Khan ZI, Ashraf M, Al-Qurainy F, Ahmad K, Gondal S

and Fardous A (2011). Studies on the transfer of copper

from soil to pastures at different sampling periods: a case

study of a semiarid region (Sargodha) in Pakistan. Biol Trace

Elem Res. 141(1-3); pp. 126-30.

[41] Krzysztof FIJAŁKOWSKI, Małgorzata KACPRZAK,

Anna GROBELAK and Agnieszka PLACEK (2012). The

influence of selected soil parameters on the mobility of heavy

metals in soils. Inżynieria i Ochrona Środowiska 15 (1), pp.

81-92.