Journal of Research in Environmental Science and Toxicology (ISSN: 2315-5698) Vol. 1(10) pp. 267-274, November 2012 Available online http://www.interesjournals.org/JREST Copyright ©2012 International Research Journals Full Length Research Paper Transfer coefficients of some toxic and trace elements into Siam weed along highways in Ado-Ekiti, Nigeria *1 Falusi Bamidele Ayodeji and 2Olanipekun Edward Olorunsola 1 Department of Chemistry, Federal College of Education (Special), P.M.B. 1089, Oyo, Oyo State, Nigeria 2 Department of Chemistry, Ekiti State University, P.M.B. 5363, Ado-Ekiti, Nigeria Accepted November 13, 2012 Transfer coefficients of the trace and toxic elements: arsenic, cadmium, mercury, lead, and zinc into Siam weed collected along Nigerian highways have been determined with the view to quantify the differences in bio-availability to the plant species. The samples were acid-digested and analyzed by flame atomic absorption spectrophotometry. TCs of the elements along the low traffic road (LTR) and high traffic road (HTR) respectively ranged as follows: As (0.00 – 3.20, 0.75 – 2.40), Cd (1.13 – 2.79, 0.88 – 1.59), Zn (1.11 – 1.42, 1.25 – 1.45), Hg (0.27 – 1.51, 0.48 – 1.65) and Pb (0.63 – 1.16, 1.05 – 1.23). Whereas Cd and Zn were within the expected ranges, other values far exceeded the normal values (i.e. 1 – 10 for Cd and Zn; and 0.01 – 0.10 for As, Hg and Pb respectively), which was indicative of the rather elevated levels of these elements in the top soil along the highways. Transfer coefficients are a key component of human exposure to metals and metalloids through consumption of food and or traditional medicines. The findings suggest that plant samples sourced along the highways should not be used for therapeutic purposes. Keywords: Transfer coefficients, Siam weed, therapeutic purposes, physico-chemical parameters, Ado-Ekiti. INTRODUCTION Roadside soils have been shown to contain high concentrations of metallic contamination (Jaradat and Momani, 1999). The bioavailability and environmental mobility of the metals vary with the forms in which they exist within the soil. Trace metal concentrations of Cd, Cu, Zn and especially Pb, in surface soils have been the focus of major investigations (Jaradat and Momani, 1999; Sutherland, 2000). The volume of traffic affects the accumulation of these metals in topsoil, introducing a number of toxic metals into the atmosphere (Wixon and Davies, 1994). The lead in roadside soil is mainly found in the form of lead sulphate (Jaradat and Momani, 1999). Metals such as Cu, Fe, Zn, and Cd are essential components of many alloys, wires, tyres and many industrial processes, and could be released into the roadside soils as a result of mechanical abrasion and normal wear, and subsequently be absorbed by plants *Corresponding Author E-mail: deledoncattle@yahoo.com (Ferguson and Kim, 1991). The heavy metal pollution of soils can have serious health implications especially through consumption of crops grown in the soils (Nyagababo and Hamya, 1986; Birley and Lock, 1999). Plant material such as fungi, lichens, tree bark, tree rings and leaves of higher plants have been used as indicators of the deposition, accumulation and distribution of metallic pollution. Lower plants, especially, mosses and lichens, in view of their higher capacity for metal accumulation, are probably the organisms most frequently used for monitoring such pollution in urban environments (Markert, 1993; Al-Shayeb et al., 1995; Aksoy and Sahin, 1999). Leaves of higher plants have been used for the biomonitoring of heavy metals since the 1950s (Al-Shayeb, et al., 1995). In recent decades, there has been increased use of higher plant leaves as indicators of heavy metal pollution in the terrestrial environment (Djingova and Kuleff, 1993; Aksoy and Ozturk, 1996; Aksoy and Ozturk, 1997). Siam weed (Chromolaena odorata) has many reported medicinal values, particularly among Africans (Akubue, 1986; Gill, 1992; Omotayo, 2000; Chamratpan and Hom- 268 J. Res. Environ. Sci. Toxicol. Chuen, 2002; Obuekwe and Obuekwe, 2002). For instance, crushed fresh leaves of the plant, when added to alum and chewed and applied on wounds have been used as an antidote for snake bite (Chamratpan and Homchuen, 2002). The leaves when chewed alleviate headache and toothache and have been proven to have antimicrobial and anti-coagulant properties (Akubue, 1986). The infusion of the leaves is a remedy for dysentery; and the decoction of the leaves with Azadirachta indica is used for the cure of malaria (Gill, 1992). The juice of the leaves can stop bleeding (Gill, 1992). The plant is a febrifuge, reduces backache, is a styptic for bleeding, and can be used as a poultice for wounds and sores (Omotayo, 2000). The leaves of the plant taken with some other leaves (Occimum gratissimum and Vernonia amygdalina) and local chalk have been used traditionally to treat diarrhea (Obuekwe and Obuekwe, 2002). Siam weed has antifungal properties. The presence of oxalates and tannins is said to be responsible for the anticoagulant properties (Omotayo, 2000). Active constituents of Siam weed include essential oil (terpenoids), abeled s-pinene, limonene, cardinene and oxygenated sesquiterpenoids (Okogun, 1986); flavonoids and oxalates (Bose et al., 1973). These benefits however depend on clean sources. Siam weed collected within the vicinity of highways has been shown to be unsuitable for therapeutic purposes, because of high metal burdens (Falusi and Olanipekun, 2011). Metals such as Cd, Pb and Hg are not essential to living organisms and their accumulation over time in mammals can cause serious illnesses (Hawkes, 1997). Consequently this study was conducted with the following aims: (1) To investigate the concentrations of five elements; As, Cd, Hg, Pb, and Zn in the plant and soil samples collected at different sites along two highways of different traffic densities in Ado-Ekiti, Nigeria (2) To determine the transfer coefficients of the elements from the soil into the plant so as to quantify the relative differences in bio-availability of the elements to the plant species. MATERIALS AND METHODS Sample collection A total of fourteen soil samples (~100g), and fourteen plant leaf samples (also~100g), were collected along two highways in Ado-Ekiti, Nigeria (Lat. 26.50°S, Long. 12.70°W). Samples were collected at distances of 2.0 m, 5.0 m, 10.0 m, 15.0 m and 20.0 m on roadsides away from the highways. Top-soil samples were collected at depths of 0–15 cm using a stainless steel hand trowel, which was cleaned between sampling points. The soil and plant samples were packaged in polythene bags and clearly abeled. They were transported immediately to the laboratory for processing and preservation. Only fresh leaves of Siam weed in prime condition were collected in order to produce good quality dried products (Audu and Lawal, 2005). Digestion and analysis of soil samples The soil samples were air-dried, mechanically ground for 30 minutes using a ball mill and sieved to obtain a fraction with a particle size < 2 mm. This fraction was used to determine pH (1:5 soil-water extract), electrical conductivity (EC) (1:5 soil-water extract), and particle size analysis using standard laboratory methods (Rayment and Higginson, 1992). Smaller samples of 20–30 g were drawn from the same fraction and reground using mortar and pestle to obtain a sample with particle size < 200 µm. This material was used to determine organic matter (OM), cation exchange capacity (CEC) and total metal concentrations. The OM was determined by the modified Walkley and Black method (Mc Leod, 1973); the CEC was determined by the silver thiourea method (Rayment and Higginson, 1992). An adapted technique (Berrow and Ure, 1981; Paveley and Davies, 1988) was employed for analysis. One-gram samples of dried and sieved soil materials were ashed in a muffle furnace; the weighed ash was digested in 10 mL aqua regia in an Erlenmeyer digestion tube (300 mL) on a heating block for a total of 9 h with the sequence and duration of temperatures: 2 h each at 25 ºC, 60 ºC, and 105 ºC, and finally 3 h at 125 ºC. All digested samples were centrifuged and made up to volume with 1% HNO3. Triplicate digestions of each sample together with blank were carried out. Digestion and analysis of plant leaf samples The samples were thoroughly washed under the tap and distilled water and dried in an oven at 105 ºC for 24 h until they were brittle and crisp. The dried samples were finely ground using clean-acid washed mortar and pestle. A described method (Al-Shayeb et al., 1995) was used for digestion. One-gram samples of dried and ground plant material were ashed; the weighed ash was digested in concentrated HNO3 and evaporated to near dryness on a hot plate. Digested samples were centrifuged and brought up to the mark with 1% HNO3. Triplicate digestions of each sample as well as blanks were carried out. Concentrations of As, Cd, Pb, and Zn were determined directly in soil and plant material using a Shimadzu flame atomic absorption spectrophotometer (model AA-6200). Hg levels were determined using cold vapour generation ICP-AES (Varian Liberty Series II). Validation of digestion methods was done using certified Ayodeji and Olorunsola 269 Table 1. Concentration of elements [mg/kg] (mean ± SD, N =14) in soil samples along the two highways. Code SL1 SL2 SL3 SL4 SL5 SL6 SL7 SH1 SH2 SH3 SH4 SH5 SH6 SH7 As 1.00 ± 0.10 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00 0.50 ± 0.04 1.60 ± 0.10 0.50 ± 0.03 0.65 ± 0.07 1.00 ± 0.60 1.25 ± 0.03 1.68 ± 0.12 1.56 ± 0.13 2.00 ± 0.84 Cd 0.18 ± 0.02 0.13 ± 0.01 0.12 ± 0.02 0.10 ± 0.01 0.03 ± 0.01 0.10 ± 0.02 0.42 ± 0.03 0.60 ± 0.14 0.49 ± 0.11 0.50 ± 0.06 0.41 ± 0.01 0.34 ± 0.05 0.85 ± 0.14 0.77 ± 0.18 Hg 0.15 ± 0.01 0.13 ± 0.01 0.12 ± 0.03 0.11 ± 0.03 0.08 ± 0.02 0.55 ± 0.08 0.36 ± 0.07 0.25 ± 0.03 0.22 ± 0.10 0.15 ± 0.03 0.14 ± 0.00 0.12 ± 0.02 0.75 ± 0.10 0.89 ± 0.07 Pb 104 ± 10 97.1 ± 9.7 80.9 ± 7.5 74.3 ± 8.6 68.9 ± 7.6 142 ± 20 159 ± 23 307 ± 25 302 ± 24 299 ± 26 286 ± 22 271 ± 28 346 ± 40 388 ± 42 Zn 53.9 ± 7.2 53.8 ± 6.1 52.8 ± 6.1 52.7 ± 6.1 52.6 ± 5.7 54.8 ± 6.5 54.5 ± 6.4 53.9 ± 7.1 52.9 ± 6.5 52.9 ± 6.4 52.8 ± 6.1 52.7 ± 6.2 55.5 ± 8.2 55.3 ± 7.2 Note- L1 and H1 = 2.0 m; L2 and H2 = 5.0 m; L3 and H3 = 10.0 m; L4 and H4 = 15.0 m; L5 and H5 = 20.0 m away from the roadside; L6 and H6 = dumpsite; L7 and H7 = road junction; L = low traffic highway; H = high traffic highway and S = soil. Table 2. Comparison of mean concentrations of metals (mg/kg) in soils with other studies worldwide. As 6.00 0.10–40.00 – – – – – 0.00–2.00 Cd 0.06 0.01–2.00 1.97–9.80 0.21 0.75 1.10 0.36–0.82 0.03–0.85 Hg 0.03 0.01–0.50 – – – – – 0.08–0.89 Pb 10.00 2.00–300.00 15.28–76.92 34.70 188.80 991.00 16.04–80.34 68.90–388.00 Zn 50.00 1.00–900.00 41.66–237.96 42.60 121.70 663.00 20.91–61.07 52.70–55.50 Reference WAL, London (BN) Glasgow (HG) Kaduna, Nigeria (OK) Spain (RJ) Amman (JM) Hong Kong (JM) Akungba, Nigeria(OL) Present Study Note: BN = Bowen, 1996; HG –Holdgate, 1997; OK = Okunola et al., 2007; RJ = Rojo, 2004; JM = Jaradat and Momani, 1999; OL = Olanipekun et al, 2008; WAL = WAL reference materials: CRM 142 R (soil) and SRM 1547 (peach leaves). The recoveries for soil were 96.6, 90.0, 97.8, 95.7 and 96.2% for As, Cd, Hg, Pb and Zn, respectively. The corresponding recoveries for plant samples were 90.0, 92.8, 102.2, 96.8 and 98.2%. RESULTS AND DISCUSSION Levels of metals in soil samples Table 1 shows the concentration (mean ± standard deviation) in mg/kg of As, Cd, Hg, Pb and Zn in soil samples collected along the low traffic road (LTR) and the high traffic road (HTR). It can be observed that the concentrations of the elements along the LTR and HTR respectively ranged as follows: As (0.00 – 1.60, 0.50 – 2.00); Cd (0.03 – 0.42, 0.34 – 0.85); Hg (0.08 – 0.55, 0.12 – 0.89); Pb (68.9 – 159, 271 – 388) and Zn (52.6 – 54.8, 52.7 – 55.5). Maximal concentrations of all the elements were recorded in the samples collected along the HTR while the lowest concentrations of all the metals occurred in the samples collected along the LTR. The trend of occurrence of the elements in the study areas was in the order: Pb > Zn > As > Cd > Hg. Positive correlations (p<0.05) exist between pairs of all elements in the soil samples indicating common sources, most likely automobiles. Table 2 compares the results of our study with those 270 J. Res. Environ. Sci. Toxicol. Table 3. Physico-chemical properties of soils samples along the two highways Codes pH SL1 6.23±0.43 SL2 6.15±0.38 SL3 6.04±0.42 SL4 5.98±0.36 SL5 5.86±0.31 SL6 6.44±0.42 SL7 6.54±0.34 SH1 6.58±0.56 SH2 6.51±0.42 SH3 6.52±0.44 SH4 6.27±0.38 SH5 6.23±0.41 SH6 6.92±0.67 SH7 6.74±0.68 OM (%) 2.80±0.18 2.76±0.22 2.84±0.28 2.64±0.32 2.52±0.12 3.00±0.28 3.10±0.30 3.60±0.41 3.40±0.38 3.00±0.42 2.98±0.40 2.72±0.25 3.68±0.26 2.90±0.27 CF (%) 11.56±0.78 11.80±0.24 11.89±0.72 12.04±0.82 11.98±0.68 12.86±0.26 12.77±0.25 12.50±0.78 12.78±0.82 13.40±0.75 12.94±0.67 13.75±0.84 14.28±0.62 14.86±0.87 EC (µScm-1) 368±34 366±27 361±33 359±41 272±42 375±40 389±28 426±25 417±28 406±24 399±36 372±42 434±26 443±33 CEC (mmolkg1) 144±38 146±27 142±23 139±30 133±26 147±28 148±40 155±28 150±34 147±29 148±30 144±42 153±31 156±39 Note- SL1 – SL7 and SH1 – SH7 have same notations as those in Table 1; EC = Electrical conductivity; CEC = cation exchange capacity; OM = organic matter; CF= clay fractions. Table 4. Concentration of elements [mg/kg] (mean ± SD, N =14) in plant samples along the two highways. Code PL1 PL2 PL3 PL4 PL5 PL6 PL7 PH1 PH2 PH3 PH4 PH5 PH6 PH7 As 0.50 ± 0.02 0.08 ± 0.00 0.00 ± 0.00 0.00 ± 0.00 0.00 ± 0.00 1.60 ± 0.04 1.86 ± 0.07 1.00 ± 0.06 1.56 ± 0.07 1.62 ± 0.06 1.72 ± 0.05 1.82 ± 0.03 2.00 ± 0.04 3.00 ± 0.06 Cd 0.35 ± 0.01 0.25 ± 0.02 0.15 ± 0.00 0.11 ± 0.00 0.08 ± 0.00 0.15 ± 0.03 0.56 ± 0.04 0.85 ± 0.03 0.78 ± 0.02 0.71 ± 0.04 0.59 ± 0.02 0.49 ± 0.01 0.75 ± 0.03 0.87 ± 0.04 Hg 0.20 ± 0.03 0.19 ± 0.01 0.15 ± 0.02 0.12 ± 0.01 0.02 ± 0.00 0.15 ± 0.02 0.40 ± 0.02 0.37 ± 0.01 0.30 ± 0.02 0.25 ± 0.00 0.21 ± 0.01 0.19 ± 0.02 0.35 ± 0.01 0 .68 ± 0.02 Pb 120 ± 12 103 ± 12 89.7 ± 11.5 83.3 ± 10.9 72.3 ± 11.1 89.8 ± 10.9 145 ± 24 378 ± 24 345 ± 22 323 ± 26 321 ± 20 311 ± 26 389 ± 32 406 ± 30 Zn 59.9 ± 8.2 65.6 ± 7.8 63.3 ± 7.5 66.2 ± 8.2 73.1 ± 8.7 72.3 ± 8.4 77.4 ± 8.7 69.1 ± 7.6 66.2 ± 7.7 70.8 ± 8.1 76.5 ± 8.6 70.1 ± 8.3 76.6 ± 8.6 69.1 ± 8.4 Note- L1 - H1 = 2.0m; L2 and H2 = 5.0m; L3 and H3 = 10.0m; L4 and H4 = 15.0m; L5 and H5 = 20.0m away from the roadside; L6 and H6 = dumpsite; L7 and H7 = road junction; L = low traffic highway; H = high traffic highway and P = plant. found at some other places. Concentration of ‘As’ recorded here was lower than levels recorded in London (Bowen, 1996) and Glasgow (Holdgate, 1997). Cd had an average concentration that compared favourably with those r ecorded in Amman (Jaradat and Momani, 1999), London (Bowen, 1996), Glasgow (Holdgate, 1997), Spain (Rojo et al., 2004), and Akungba, Nigeria (Olanipekun et al., 2008) but was lower than levels recorded in Hong Kong (Jaradat and Momani, 1999), Nigeria (Okunola, et al., 2007). The levels of Hg recorded in our study compared favourably with results from other places (Bowen, 1996; Holdgate, 1997). Furthermore, the concentration of Pb recorded in this study was lower than in Hong Kong (Jaradat and Momani, 1999) but higher than in Amman (Jaradat and Momani, 1999), London (Bowen, 1996), Glasgow (Holdgate, 1997), Kaduna, Nigeria (Okunola et al., 2007), Spain (Rojo et al., 2004) and Akungba, Nigeria (Olanipekun et al., 2008). Zn levels recorded in this study were higher than those Ayodeji and Olorunsola 271 Table 5. Comparison of mean concentrations of metals (mg/kg) in plant samples with other studies worldwide. As 0.20 0.0 –7.00 – – – 5.00–20.00 0.00–3.00 Cd 0.60 0.10–2.40 4.88–14.93 ND 0.06 – 0.31 5.00–30.00 0.08–0.87 Hg Pb Zn 0.015 2.70 100.00 0.0005–0.17 0.20–30.00 1.00–400.00 – 0.00–32.37 27.78–185.19 – 7.30 98.70 – 0.40 – 4.26 8.15 – 14.53 1.00–3.00 30.00–300.00 100.00–400.00 0.02–0.68 72.30–406.00 59.90–77.40 Reference (BN) WAL, London (HG) Glasgow (OK) Kaduna, Nigeria (JM) Amman (OL) Akungba, Nigeria (HG) Critical levels Present Study Note: BN = Bowen, 1996; HG = Holdgate, 1997; OK = Okunola et al., 2007; JM = Jaradat and Momani, 1999; OL = Olanipekun et al., 2008; ND = Not detected Table 6. Correlation coefficients between concentrations of elements in soil and plant samples along the two highways. Metals As Cd Hg Pb Zn RHSP 0.8757 0.7256 0.8459 0.9029 0.9983 RLSP 0.8021 0.9585 0.4174 0.7325 0.5730 Note – RHSP = Correlation coefficients between concentrations of elements in soil and plant samples along the HTR. RLSP = Correlation coefficients between concentrations of elements in soil and plant samples along the LTR. recorded in London (Bowen, 1996), Spain (Rojo et al., 2004) and Akungba, Nigeria (Olanipekun et al., 2008) but lower than those recorded in other places (Holdgate, 1997; Jaradat and Momani, 1999; Okunola et al., 2007). Table 3 shows that the soils have a wide range of values of measured properties. Soil pH in water varied from 5.9 – 6.5 and 6.2 – 6.9 respectively along the LTR and the HTR. The pH values indicate that the soils were mildly acidic. The values of electrical conductivity (EC) along the LTR and HTR respectively ranged as follows: 272 – 389 and 372 – 443 µScm-1. These suggest non-saline growing conditions in the regions studied. The OM lay in the range 2.5 – 3.1% along the LTR and 2.7 – 3.7% in the soil samples collected along the HTR. The clay fractions (CF) of the soil samples collected along the LTR and the HTR respectively ranged as follows: 11.6 – 12.9 % and 12.5 – 14.9 %. The CEC recorded in the soil samples collected -1 along the LTR ranged 133 – 148 and 144 – 156 mmolkg along the HTR. Levels of elements in plant leaf samples and their transfer coefficients Table 4 shows the mean concentration of elements (As, Cd, Hg, Pb and Zn) in the samples of Siam weed (Chromolaena odorata) collected along the LTR and the HTR. From the results, it can be observed that the general trend of the concentrations of the elements in the plant samples followed the order Pb > Zn > As > Cd > Hg. Highest concentrations of all the elements were recorded in plant samples collected along the HTR while lowest concentrations of all the elements occurred in samples collected along the LTR. The concentrations of the elements recorded in our study compared to other studies, as contained in Table 5, show that most elements with the exception of Pb, have similar concentrations. Positive significant (p<0.05) correlations existed between concentrations of all the elements in the soils and plant samples along both the LTR and HTR as 272 J. Res. Environ. Sci. Toxicol. Figure 1. Transfer Coefficients of elements from the soils to the plant samples along the LTR. Figure 2. Transfer Coefficients of elements from the soils to the plant samples along the HTR. shown in Table 6. These positive correlations reflect similar sources of the elements in the plant tissues and soil samples. The transfer coefficients (TC) of the five elements from the soils to the plant tissues in Ado-Ekiti (Nigeria) are calculated using equation 1 (Kloke et al., 1984; Alloway, 1995; Kachenko and Singh, 2004; Awode et al., 2008; Falusi et al., 2010). Figures 1 and 2 present the results for the LTR and HTR respectively. TC = CP / CS --------------------------- (1) where TC = transfer coefficient; CP = concentration of element in plant tissues above ground and CS = total elements concentration in the soil. The TCs were determined for the elements (As, Cd, Hg, Pb and Zn) to quantify the relative differences in their bioavailability to the plant species and to identify the efficiency of the plant species to accumulate the elements. These coefficients were based on the root uptake of the elements and discount foliar absorption of atmospheric metal deposits (Alloway, 1995; Kachenko Ayodeji and Olorunsola 273 and Singh, 2004; Awode et al., 2008; Falusi et al., 2010). TC ranges of 0.00 – 3.20 and 0.75 – 2.40 were recorded for ‘As’ along the LTR and HTR respectively. TCs of other elements along the LTR and HTR respectively ranged as follows: Cd (1.13 – 2.79, 0.88 – 1.59), Zn (1.11 – 1.42, 1.25 – 1.45), Hg (0.27 – 1.51, 0.48 – 1.65) and Pb (0.63 – 1.16, 1.05 – 1.23). Most of the sites investigated have higher TCs than those suggested in reference (Kloke et al., 1984), i.e., 1 – 10 for Cd and Zn; and 0.01 – 0.10 for As, Hg and Pb respectively. The high numbers of samples exceeding the suggested TC range of As, Hg and Pb in our study reflects the elevated topsoil concentrations of the elements found along the two highways. The soil physico-chemical properties may have further influenced the soil-plant transfer of the elements. Low organic matter content, acidic nature of soil, low cation exchange capacity, low clay fractions, and non saline growing conditions (as reflected by values of electrical conductivity) have been reported to enhance bioavailability of elements for plant uptake (Kachenko and Singh, 2004; Awode et al., 2008; Falusi et al., 2010). Positive correlations that were recorded between the concentrations of the elements in the soils and the physico-chemical parameters of the soils along the two highways corroborated these findings. The TC has been reported to be one of the major key components of human exposure to trace and toxic elements through the food chain (Awode et al., 2008; Falusi et al., 2010). As a result, we would recommend that Siam weed leaves picked from plants growing along highways should not be used for therapeutic purposes. This is to minimize the effect of health hazards associated with ingestion of toxic elements. 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