Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio...

24
Heavy metals Deposition in Topsoil, Road Side Dust and Application of Doedonea viscose as Biomonitor in Tripoli Area, Libya. Almathnani, A.M. Alshergawi, M.I. Elssaidi, M.A. Kahled, B.Y. Inamul Haq Environmental Science Departmental, Faculty of Engineering & Technology Sebha University, Brack-Libya ABSTRACT Present paper deals with the monitoring and assessment of heavy metals in soil, road side dust and particulate matter (PM) deposits on plant leaves around Tripoli areas/ roads (Zawya, Khums, Sawani, Tarhuna) at different sites (0, 2, 5, 10 & 20 km) on each road. Plant, Doedonea viscosa, specie of Doedonea shrub, widely distributed in Libya was used for monitoring of heavy metals in PM deposition or accumulated on leave. The heavy metal monitored during the study period includes Zn, Cu, Pb & Cd. The level of Zn and Cu in Environmental samples such as soil, road side dust and in plant. unwashed leaves were much higher than the level of Pb & Cd. The metal concentration order in these samples were Zn > Cu > Pb > Cd. Metal concentration trend variation was also discussed in relation with traffic density and other sources of fugitive emission around different sites on each roads/areas. A comparative evaluation in variation of heavy metals was also made with other data reported in other countries. Preliminary data provides some insight to undertake expensive survey using Doedonea viscosa, as biomonitor and low cost tool for monitoring of trace toxic inorganic and organic atmospheric air emission in urban and industrial area of Libya for preparation of environmental map for taking necessary environmental production measures. 1

Transcript of Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio...

Page 1: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

Heavy metals Deposition in Topsoil, Road Side Dust and Application of Doedonea viscose as Biomonitor

in Tripoli Area, Libya.

Almathnani, A.M. Alshergawi, M.I. Elssaidi, M.A. Kahled, B.Y. Inamul Haq

Environmental Science Departmental, Faculty of Engineering & TechnologySebha University, Brack-Libya

ABSTRACT

Present paper deals with the monitoring and assessment of heavy metals in soil, road side dust and particulate matter (PM) deposits on plant leaves around Tripoli areas/ roads (Zawya, Khums, Sawani, Tarhuna) at different sites (0, 2, 5, 10 & 20 km) on each road. Plant, Doedonea viscosa, specie of Doedonea shrub, widely distributed in Libya was used for monitoring of heavy metals in PM deposition or accumulated on leave. The heavy metal monitored during the study period includes Zn, Cu, Pb & Cd. The level of Zn and Cu in Environmental samples such as soil, road side dust and in plant. unwashed leaves were much higher than the level of Pb & Cd. The metal concentration order in these samples were Zn > Cu > Pb > Cd. Metal concentration trend variation was also discussed in relation with traffic density and other sources of fugitive emission around different sites on each roads/areas. A comparative evaluation in variation of heavy metals was also made with other data reported in other countries. Preliminary data provides some insight to undertake expensive survey using Doedonea viscosa, as biomonitor and low cost tool for monitoring of trace toxic inorganic and organic atmospheric air emission in urban and industrial area of Libya for preparation of environmental map for taking necessary environmental production measures.

Key words:Biomonitor, Doedonea shrub, Air, Soil, Pollution, Deposition, Traffic, Heavy metals, Zinc, Lead, Copper, Cadmium, Tripoli, Libya.

INTRODUCTION

Pollution of airborne trace metals is derived through emission from industrial, vehicular and urban activities. Interest on the effects of atmospheric particulates on health and environment has increased many folds in the last one decade on the basis of evidences that this type of pollution proved strong link with respiratory illness (1, 2). It was also reported that metal adsorbed on ambient suspended particulates produce tissue damage in the lungs (3).

1

Page 2: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

In most urban cities, the airborne trace metals are not routinely monitored by High-volume sampler or other mechanical devices owing to their high cost and technical difficulties to cover large geographical areas. Due to these problems and also release of toxic trace metals are increasing alarmingly by rapid industrialization and increased traffic density in the urban Environment (4, 5), more attention are being paid to plants as bioindicator of trace metals in atmosphere (6). Such biomonitors, are an effective monitoring tools for trace toxic pollutants, are extensively being used for sampling & monitoring of large geographical regions for preparation of environmental map on atmospheric airborne trace toxic contaminants (7-9). Data on ambient trace metal deposition will help decision makers for planning and adoption of environmental protection measures against the increasing level of potentially toxic/hazardous trace metals in ambient environment.

Various authors have used botanical materials such as lichens, fungi, tree bark, tree rings and leaves of higher plants as bioindicator. Lower plants especially mosses, algae and lichens, in view of their higher capacity for metal accumulation were used more frequently for biomonitoring of metal in urban environmental (10-16). In Europe mosses have been employed in National & multi-national surveys of atmospheric metal deposition (17). Considering the effectiveness of the findings, such survey was further expanded in most of the European countries (18). Survey of heavy metals deposition employing moss was also studied in mountainous territories of Italy (19).

Leaves of higher plants have also been extensively used for biomonitoring of heavy metals (20 & 21). The most frequently used higher plants were chosen among the genera Capsella and Poa (10), Pinus (22), Queruis (23). Several authors (24-27) found higher plants/tree leaves and bark to be natural biomonitoring surfaces for industrial and urban pollution. Leaves of higher plant like date palm and others have been used to monitor distribution of airborne Pb, Cd, Zn and Cu (22 & 28). The level of Pb, Cd and Zn concentrations in topsoil and washed & unwashed leaves of E. angustifolea, a typical urban tree was tested as a possible biomonitoring in different areas in Turkey (29). Mesquite (Prosopis Juliflora), deciduous tree that withstand drought and extreme temperature in arid ecosystem was used as biomonitor for monitoring of Pb level (in leaves, barks and surrounding soil) in different area in Kuwait (30). The level of heavy metals contamination of surfaces road side soil, plants (Anabases Arbiclata) and air along a major traffic highway in tropical climate of Jordan were monitored (31).

As evident from the literature, various investigators have extensively used lower plants as well as different parts including leaves of higher plants, as bioindicator for monitoring and assessment of airborne heavy metal deposition in urban environment. Since no studies had assessed the level of heavy metals deposition and accumulation in the leaves of Doedonea viscose, a widely distributed plants in Libya (Mediterranean zone & desert climate). The present study was therefore initiated to assess the level of various trace toxic metals such as Zn, Cu, Pb & Cd contamination/depositions in unwashed and washed leaves of Doedonea viscose, surrounding topsoil and road side dust on sites of different roads (Zawya, Khums, Sawani, Tarhuna) in Tripoli zone.

2

Page 3: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

MATERIALS AND METHODS

Plant used: The choice of Doedonea viscose was made because of the their low dimensions

and resistance to Libyan climate, their availability & wide geographical native distribution. This was considered to be an important data in order to use the Doedonea viscose more extensively in urban and rural areas of Libya for monitoring and assessment of environmental pollution.

Doedonea shrub has about 60 number of species which are mainly found in Australia but some of these species are widely distributed in topical and sub-tropical region of many countries (32). The Doedonea viscose has a average height of about 5 meters with dense branch of leaves and trunk diameter of about 10 centimeter. Deciduous leaves are light green underneath and dark green on the top. Leaves are 4-5 centimeter long. Doedonea viscose has rapid growth and is naturally found in a wide range of soil types, being relatively tolerant to sever hot and cold climate prevailing in Libya. Doedonea viscose is commonly planted around residential areas, institutional areas and road side for hedging purposes.

Sampling procedure: Samples were collected during March and April 2006 to avoid washing out of

heavy metal deposits. Topsoil and road side dust samples (the upper 2 cm) of about 1000 gram were collected from 5 different sites and distances (0, 2, 5, 10, 20 Km) near the identified Doedonea viscose on each road Fig. (1) with a stainless steel trowel. The samples were stored in polyethylene bags for analysis separately.

The plants leaves were collected from where the soil samples were collected at different distances on each road Fig. (1). The plant leaves samples were divided into two groups and transported to laboratory in Polyethylene bags. One group of leaves sample was thoroughly washed with distilled water to remove dust particles deposited on leaves surface, and the other group of leaves samples remained unwashed. The washed leaves samples were oven dried at 70 oC/24 hrs for further processing.

Heavy metals determination:The procedure of metals determination in soil and dust samples was followed

according to the reported method (33). The soil dust samples were grounded and sieved. The sieved samples were dried at 70 oC/24 hrs. One gram of soil was treated with 10 ml concentrated nitric acid heated up to dryness and then cooled. This procedure was repeated with another 10 ml concentrated nitric acid followed by 10 ml of 12N HCl. The digested soil and dust samples were then warmed in 20 ml of 2N HCl to redissolve the metal salts. Extracts were filtered using Whitman filter paper No 40 and the volume was then adjusted to 25 ml with 1.5% HNO3.

The procedure used to digest plants leaves and determination of heavy metals was same as reported in literature (34). Metal determination for plant leaves topsoil and road side dust were carried out using flame atomic absorption spectrophotometer.

3

Page 4: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

RESULT & DISCUSSION

Trace metals (Zn, Cu, Pb & Cd) results that analyzed in plant leaves (washed & unwashed), soil and road side dust are given in Table (1) and the concentration variation trends with distance on roads side are shown in Fig. (2). The concentration range of metal in washed and unwashed leaves of Doedonea viscose at different distances are given in Table (2) and metal concentration variation in unwashed and washed leaves at different distance from zero distance is shown in Fig. (3).

Table (1): Range of heavy metals concentrations in topsoil and road side dust around Doedonea viscose shrubs:

Road SampleRange of trace metal concentration (ug/g)Zn Cu Cd Pb

Zawya Topsoil 34.0 - 103.0 21.0 - 42.6 0.1 - 2.0 16.7 - 31.2

Road-side dust 112.0 - 187.0 34.0 - 66.0 29.0 - 41.3 2.9 - 3.8

KhumsTopsoil 45.0 - 87.0 21.0 - 41.0 0.6 - 1.8 0.2 - 16.9

Road-side dust 48.0 - 154.0 21.0 - 41.0 3.0 - 34.8 0.8 - 3.3

Sawani Topsoil 66.0 - 89.0 21.0 - 39.4 2.0 - 18.5 1.8 - 2.7

Road-side dust 111.0 - 228.7 34.1 - 65.2 25.2 - 34.8 3.0 - 7.3

TarhunaTopsoil 52.0 - 87.0 21.0 - 39.0 1.2 - 16.7 0.2 - 2.8

Road-side dust 52.0 - 154.0 27.0 - 38.8 4.0 - 34.8 1.3 - 5.4

Table (2): Heavy metals levels range in washed and unwashed Doedonea viscose leaves:

Road SampleRange of trace metal concentration (ug/g)Zn Cu Cd Pb

Zawya Un-washed 30.0 - 49.6 12.0 - 26.2 0.1 - 2.8 0 - 3.0

Washed 7.8 - 19.0 0.5 - 14.5 0 - 0.1 0 - 0.1

KhumsUn-washed 35.0 - 38.7 12.0 - 33.1 0.1 - 2.2 0 - 0.2

Washed 8.9 - 17.2 6.4 - 10.8 0 - 1.3 0 - 0.1

Sawani Un-washed 31.8 - 38.3 12.2 - 31.2 0.1 - 3.3 0.2 - 1.9

Washed 10.0 - 17.2 3.3 - 10.2 0 - 1.2 0 – 1.2

TarhunaUn-washed 20.0 - 47.9 12.0 - 25.5 0.1 - 2.0 0.1 - 0.5

Washed 7.0 - 20.4 3.0 - 10.2 0 - 0.2 0 - 0.1

Analysis of road side topsoil and dust, and plants leaves revealed high concentration of Zn and Cu compared with Pb and Cd around these areas in Libyan ecosystem i.e., Zawya, Khums, Sawani and Tarhuna roads. 1. Soil contamination:

The range of heavy metals concentrations and their variation in topsoil and road side dust of four different roads at different distances are given in Table (1) and Fig. (2). The concentration order among the above four critically selected heavy metals

4

Page 5: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

in topsoil from four roads around Tripoli were Zn > Cu > Pb > Cd. The same concentration order for these metal were found in road side dust but the concentrations of these metals also much higher than those found in topsoil. The variation trends of each heavy metals are briefly discussed in the following paragraphs:

Zinc: On Zawya road, zinc concentration in topsoil for different sites (distance 0-20 Km) showed a range of 33–103 ug/g. Near zero distance, zinc concentration in topsoil was found at 87 ug/g, decreasing with increasing distance, then increased to max. value 103 ug/g after 20 km, Fig. (2). Zinc concentration in road side dust at zero distance was 154 ug/g and max. 187 ug/g near 2 Km. The value decreased for 5 Km and 4 and increased further up to 151.4 ug/g near 20 Km Fig. (2). Zinc in topsoil and road side dust showed increased value around 20 Km. On Khums road, Zn concentration found decreasing from zero distance, but values for 2 Km, 4 and 5 were not much different, average 52 ug/g, however for 5 Km the Zn concentration was relatively lower than other sites. Incase of road side dust, Zn concentration was found decreasing from zero distance but higher than topsoil Fig. (2). On Sawani road, the Zn concentration in topsoil found varying with distance and lowest at 66.75 ug/g around 20 Km. The Zn concentration for road side dust showed max. value around 5 Km (229 ug/g) and the lowest near 20 Km (111.48 ug/g).

On Tarhuna road Zn concentration for topsoil and road side dust show Cd same variation trend, highest value found at 10 Km (62.3 ug/g for topsoil and 98.9 ug/g road side dust). It is concluded from the above finding that, in general, Zn concentration in topsoil and road side dust on different road sites showed the following order. Sawani Rd. > Tarhuna Rd. > Khums Rd. > Zawya Rd.

Studies conducted elsewhere on metal depositions from particulate matter on road side topsoil exhibited much higher value of Zinc in Hong Kong, 633 ug/g (33), Lancaster, 300-530 ug/g (35), Ecuador 509 ug/g (36), North Wales, 1143 ug/g (37), London, 513 ug/g (38), Banglore, India 808 ug/g (43). However Zn concentration found in our study is comprisable with other reported values in Nigeria, 163 ug/g (39), Auckland, 180 ug/g (40), Birmingham, 205 ug/g (41),.

In this study, since no major industries exists, the primary source of zinc may be attributed to Zn emission into the atmosphere as a result of wear from tires of automobiles and use of Zn additives (Zinc dithiophosphates) in engine lubricating oil. The findings may be divided from two points of views i.e., heavy and low traffic road area. The elevated level of zinc on different sites of Asian road as compared to other roads were found to be maximum partly attributed to the high movement of traffic and fugitive emission due to number of job works like auto workshop, car painting etc. The concentration of Zn on other road was not so high, may be due to less traffic and fugitive emission as the same observed and substantiated by the lower value of Zn in topsoil and road side dust. The other distinct features found was comparatively higher value of Zn concentration around 2 & 5 Km and around 20 Km on Zawya Rd. Fig. (2) which is due to the fact that diversion of vehicle during peak hours following the routes for Tunis through Zawya; Khums; Sawani & Tarhuna roads. The high intra road traffic density and fugitive emission contributed by other sources (workshop) may be the possible reason of high zinc level on Sawani Rd. sites as compared to other roads.

5

Page 6: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

Copper: The variation of the copper concentration range in topsoil and road side dust on four different road sites were almost same (topsoil : 21–40 ug/g, road side dust: 35-52 ug/g). On Zawya road., copper concentration on zero distance in topsoil and road side dust were found at 21.6 ug/g and 35.5 ug/g respectively Fig. (2). On this road maximum Cu concentration were found at 35.8 ug/g and 44 ug/g in topsoil and road side dust around 2 Km and 42.57 ug/g & 66.35 ug/g in road side dust around 20 Km. Similar Cu concentration trends Fig. (2) were found for other roads. The Cu concentration range with distance variation on 4 roads are as follows: Sawani Rd. > Khums Rd. > Zawya Rd. > Tarhuna Rd.

The reason for this could be due to the traffic density & fugitive emission which are high on Sawani Rd. as compared to other roads where low traffic movement observed. Comparing our results with other reported studies showed that our values are much less than those found in topsoil in Hong Kong, 120 ug/g (33), Lancaster, max. 199 ug/g (35), Nigeria, 61 ug/g (39),. However it was also found that our results were comparable with other studies. The sources of Cu emissions may be varied besides traffic (wear and tear of motor vehicles parts), the refused and tire burning (found frequently practiced), car painting, automobile workshop along the road side.

Lead: Lead concentration in topsoil and road site dust is given in Table (1). At zero distance, concentration of Pb in topsoil and road site dust were found at 16.73 and 34.87 ug/g. On Zawya road. at 20 Km maximum level of Pb in topsoil and road site dust were at 31.17 and 41.29 ug/g as compared to other roads for the same locations. Comparing values of Pb for each sites on roads with respect to zero distance, the Pb concentration for other sites were much less for all the road sites, than value, however, increased value were found around 2, 5 & 20 Km on Zawya Rd. in topsoil and road side dust. Lead Concentration order road wise for lead as: Zawya Rd. > Khums Rd. > Sawani Rd. > Tarhuna Rd. (Topsoil). Zawya Rd. > Sawani Rd. > Khums Rd. > Tarhuna Rd. (Road side dust).

The above result show that lead concentration in topsoil and road side dust were less than Zn & Cu concentration The concentration of Pb were much higher on Zawya & Sawani Rd. as compared to other two roads Table (1) and Fig. (2). The lead level in street dust and road side topsoil have been extensively studies because of its most concern environmental heavy metal pollution and found to be present at elevated level in ecosystems. On comparing with other studies carried out for Pb level in soil it is found that our results for all the 4 roads sites revealed much less value with those reported in Hong Kong (33), North Wales (37), Ecuador (36), Auckland, 1650 ug/g (40), London, 1354 ug/g (38), USA, 444 ug/g (42), Banglor, India, 345 ug/g (43),. The reason for low level of Pb in topsoil and road site dust as compared to other countries is mainly due to use of unleaded fuel by automobiles in Libya. However, the most probable source of low Pb contamination may be due to particulate emission by normal wear and tear of the engine parts. The high level of Pb in Zawya Rd. and maximum on 20 Km were compared with other road sites could be due to high traffic density and deposition of lead around the site. Such increased concentration on Zawya Rd. on 2 & 5 Km could be due to the diversion of traffic through the peak hours from zero distance area.

6

Page 7: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

The ratio of Pb:Zn in soil is found to be less than unity which indicates that soil Pb pollution is not caused by automobile but may be due to some local problems as reported by other studies (36 & 42). The Pb:Zn ratio greater than unity as reported by others (34, 39, 37 & 38) is a clear indication of soil Pb pollution caused by automobile which is not the case in present study.

Cadmium: The Cd concentration range Table (1) along all the road’s topsoil and road side dust were 0.7-2.8 and 0.8-7.3 ug/g respectively. Cd concentration variation with distance on four different roads is shown in Fig. (2). Cadmium concentration in topsoil and road side dust on different roads sites were very low than the other 3 metals. The order of Cd concentration in topsoil and road side dust on different roads as Sawani Rd. > Zawya Rd. > Khums Rd. > Tarhuna Rd.

Cadmium concentration around zero distance ( zero distance) in topsoil and road side dust were found to be at 1.79 and 3.29 ug/g respectively. On around 2 & 5 Km on Zawya and Sawani Rd., Cd value increased from zero distances Fig. (2) for both topsoil and road side dust However it is not the case for the other roads. On 20 Km, for all the roads, high value were observed with respect to other 2, 5 & 10 Km. The low and high values of Cd in soil sample found in our study were compared with values reported in others. Low Cd in topsoil as found in our study is not much different than those reported values in Hong Kong, 1.1 ug/g (33), Ecuador, 0.36 ug/g (36), Nigeria, 1.3 ug/g (39), Auckland, 0.4 ug/g (40), Birmingham, 0.7 ug/g (41), USA, 0.89 ug/g (42). The elevated level of Cd found in our study on some of the road side dust range 3-7.3 ug/g. Such high level of Cd were also reported by other workers for Lancaster, 5.2 ug/g (35), North Wales, 6.8 ug/g (37) and London, 4.2 ug/g (38), Banglor, India 7.74 ug/g (43), for road side soil / dust. The sources of Cd in the urban areas are much less well defined than those of Pb and other metals but metal plating and tire rubber were considered the likely sources of Cd. Cd is also found in lubricating oil as part of many additives. It was reported that the Cd level in the car tires is in the range of 20-90 ug/g as Cd contamination in vulcanization process (40). The higher concentration of Cd on Sawani Rd. therefore could be related to the movement of high traffic and release of Cd and its deposition on topsoil/road side dust by mechanical abrasion of tire due to high speed traffic and poor road condition and also emission from engine lubricating oil. 2. Plant Contamination:

The concentration range of different metal studied in washed and unwashed leaves is given in Table (2) and their variation trend in Fig. (3). Variation of different metal concentration in washed and unwashed leaves of Doedonea viscose are briefly discussed below.

Zinc: Heavy metal concentration in Table (2) shows that the order of metal concentration in unwashed leaves is as follows: Zn > Cu > Pb > Cd. similar order was found in case of washed leaves but values wear less than unwashed leaves. The same concentration order were found in topsoil and road side dust The variation of metals (Zn, Cu, Pb & Cd) in unwashed and washed leaves for different road sites Fig. (3).

7

Page 8: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

The variation trend for Zn metal depositions on leaves (washed and unwashed) for all the roads exhibited max. concentration of Zn around 2 Km Fig. (3) from zero distance value (37.57 & 17.42 ug/g in unwashed & washed leave). The zinc concentration in unwashed and washed leaves at 20 Km on Zawya Rd. were 49.56 & 17.23 ug/g and same for Khums Rd. were 38.71 & 13.73 ug/g which were higher from the value of 2 to 10 Km. On other two roads, i.e., Sawani and Turhuna Rd. the trend for zinc deposition were different. The concentration were found decreasing from around 2 & 5 Km and lowest on 20 Km, i.e., 31.75 ug/g on Sawani Rd and 33.24 ug/g on Turhuna Rd. for unwashed leave. The trend were also the same for the washed leave, except on Sawani Rd. at 20 Km.

Considering all the roads and sites, the concentration in unwashed leaves range were 20-49.56 and 7-20 ug/g in washed leave. Our value is much less than those reported elsewhere in unwashed and washed leaves plants around road site in urban area's (83.5 ug/g in road side and 69.15 in Urban areas) in Turkey (29). The sources of Zn emission in ambient area is the same as mention in the soil section. 2 and 20 Km in general, show more concentration attributed due to high traffic density and aerial deposition of heavy metals and other job works around these sites.

Copper: Concentration of copper accumulation trend in unwashed and washed leaves were almost the same as found in the case of Zn. However the level of Cu in unwashed and washed leaves were much less than Zn concentration. On Zawya road the maximum concentration of copper was found around 2 Km (26.23 ug/g) and around 20 Km (21.75 ug/g) with respect to other two 5 & 10 Km and zero distances value (12.17 ug/g) in unwashed leave. The same trends where found in unwashed leaves for Khums Rd. (max. at 28.49 and 33.15 ug/g on 2 & 20 Km. In case of washed leaves the same variation trend were observed Fig. (3). The maximum value found in washed leaves at 14.5 and 9.24 ug/g around 2 & 10 Km on Zawya Rd. and at 10.83 and 9.83 ug/g respectively. On Khums Rd. around 2, 10 & 20 Km. On As Sawani Rd., maximum value in unwashed leaves were 31.2 at around 2 km and lower than this was found on other sites including zero distance value 12.17 ug/g in unwashed leaves. Cu concentration in washed leaves on zero distance was 10.23 ug/g and increased further around 20 Km Tarhuna Rd. showed maximum value at around 2 Km at 19.36 ug/g against the zero distance value, highest at 10 & 20 Km i.e., 25.5 ug/g and 22.13 ug/g in unwashed leave. In case of washed leaves high value was recorded at 20 Km, i.e., 10.02 ug/g (As Sawani Rd. and 9.27 at Tarhuna Rd. and all the site showed low value Fig. (3). Among all the roads sites, Khums Rd. show maximum deposition (unwashed leave) of copper next to zinc Fig. (3). The high value of copper in leaves on almost all the roads around 2 & 20 Km was due to high traffic density and other job works. This could be related to Cu vehicular emission around these sites by motor parts wear and brushing of bearing metals, frequent refuse burning and auto workshops activity along the road side which results in more deposition of particulate matters containing Cu on leaves. The Cu concentration order in different around different road side is as follows: Khums Rd. > Sawani Rd. > Zawya Rd. > Tarhuna Rd.

Lead: concentration of lead on 2 & 20 Km showed maximum value in unwashed leaves at 0.32 and 2.77 ug/g on Zawya Rd. and 2.17 and 0.75 ug/g on Khums Rd. as

8

Page 9: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

compared with zero distance value 0.155 ug/g. Similar results were almost found in case of other two roads. Pb in washed leaves showed low concentration this shows that uptake of Pb by leaves is almost negligible when compared with other metals. These values were much less than data reported in other studies (29) for road side washed leaves. As Sawani and Tarhuna Rd. also showed the same trend. Similar Pb concentration variation with distance on road side topsoil were found. Source of Pb emission deposition on leaves around 2 & 20 Km which showed mix. Value, is related to traffic density and use of unleaded fuel and other fugitive emission on different road sites as discussed in soil section. The Pb concentration order on different road sites found to be as follows: Zawya Rd. > Khums Rd. > Tarhuna Rd. > Sawani Rd.

Cadmium: Cadmium concentration in unwashed leaves on all roads sites range from traces to 1.85 ug/g and in washed leaves trace to 0.2 ug/g; Table (2). These values were higher compared with results of other study (29) conducted for metal deposition on plant leaves surface (unwashed) from urban road side areas in Turkey. But our values for washed leaves were much lower compared with the reported value 0.66 ug/g. The high level of Cd where found in unwashed leaves 1.85 ug/g for Sawani Rd. around 10 km distance from zero distance 0.22 ug/g. The washed leaves showed negligible concentration which is an indication that Cd uptake by leaves is negligible as the case with Pb. The sources of Cd emission are mentioned in soil section.

Heavy metals such as copper and zinc are essential for plant nutrition and requires for the activities for various type of enzymes and therefore the uptake of copper and zinc by the Doedonea viscose from the deposition of particulate matter containing these metals appears to be more. However the variation pattern uptake of heavy metals depends on plant species and climatic conditions. On the other hand cadmium and lead do not have any known physiological function in plants and can be toxic and therefore their uptake by the plant leaves is negligible.

Preliminary data gathered during the study, provide useful information to undertake an extensive survey covering large geographical areas (rural & urban) in Libya using Doedonea viscose as biomonitor for atmospheric trace inorganic and organic pollutants and to prepare area wise environmental maps for different level of Hazardous Air Pollutants (HAP) identified by USEPA for taking necessary environmental protection measures.

REFERENCES

1. Dockery, D.W., Pope, C.A. Annual Reviews of Public Health 15,107-132,1994.2. Pope, C.A., Bates, D.A., Raizenne, M.E. Environmental Health Perspectives

103, 472-479.1995.3. Drehert, K.L. Jaskot.R.H., Lehmann, J.R, Richards, J.H., McGee J.K., Ghio,

A.J., Costa, D.L. Journal of Toxicology & Environmental Health 50, 285-305, 1997.

9

Page 10: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

4. Cadle, S.H., Mulawa, P.A., Ball.J., Donase C., Weibel, A. Sagebiel, J.C. Knapp, K.T. Snow, R. Environmental Sci. & Technology, 31,3405-3412, 1997.

5. Janssen N.A.H., Van Mansom D.F.M., Vender Jagt, K., Harssema, H. Hoek, G. Atmospheric Environment 31, 1185-1193,1997.

6. Bargagli, R., Heavy metals in Terrestrial Plants. Springer Verlag, Berlin. 1998.7. Bringhigma, L., Papini, A, Mosti, S., Cornia, A. Bocchini, P. and Galletti, G.

Rev. Biol. Trop. 50 (2) 577-584, 2002.8. Monaci, F., Bargagli, R. Water, Air and Soil pollution 100, 89-98,1997.9. Market, B.A., Breure, A.M., and Zechmeister, H.G. (Eds). Strategies and

Principles for Bioindication / Biomonitoring for the Environment Elsevier, Oxford. pp. 3-39; 2003.

10. Aksoy, A., Hale, W.H. and Dixon, J.M. Sci. total Environ. 226, 177-186, 1999.11. Ceburnis,D., Ruhling, A.; Kvietkus, K. Environ. Monitoring and assessment, 47,

135-152, 1997.12. Zeichmeister, H.G., Hohenwallner, D., Riss, A. Hanus-Illnar A., Sci. total

Environ., 301, 55-65, 2003.13. Schintu, M., Cogoni, A., Durante, L., Cantaluppi, C., Contu, A. Chemosphere

60, 610-618, 2005.14. Ogunfowokan, A.O., Asubiojo, O.I., Adeniyi, A.A., Oluyemi, E.A. Journal of

applied Sciences, 4 (3) ; 380-383,2004.15. Makholm, M.M., and Mlandenoff, D.J. Environ. Monit. Assess. 104 (1-3), 1-18,

2005.16. Nimis, P.L., Scheidegger, C., Nolseley, P. (Eds):Air Pollution Monitoring with

Lichens. Kluwer Academic, DoRd.recht, p. 408, 2002.17. Ruhling. A, Steinnes, E, Berg, T. NoRd.ic, 1-47, 1996.18. Buse, A., Norris, D., Harmens, H., 2000/2001 Survey Report, centre for ecology

& hydrology, Bangor UK. p. 45, 2003.19. Gedol, R., Brag Zawyaa, L., Marchesini, R., Alber, R. Envir.Poll. 108, 201-208,

2000.20. Djingova, R., Kuleff, I. Market B., Monitoring of Heavy metal Pollution by

Plants as Biomonitor in Terrestrial Environment. VCH publisher, Weinheim, 435-460, 1993.

21. Aksoy, A. and Oztiirk, M. Sci. Total Environ. 205, 145-150, (1997). 22. Schultz, H., Popp, p., Huhn, G., Stark, H.J. and Schurmann. Sci. total Environ.

232; 49-58, 1999.23. Alfani, A and Baldantoni, D; Environ. Pollut. 109, 119-129, 2000.24. Al-Shayeb, S.M., Al-Rajhi, M.A. and SeawaRd., M.R.D. Sci. total Enviorn. 168,

1-10, 1995.25. Shams, Z.I. and Ali Beg, M.A. The Environmentalist 20, 63-67, 2000.26. Pacheco, A.M.G., Freitas, M.C. and Reis, M.A. Methods in Physics Research A.

505, 425-429. 2003.

10

Page 11: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

27. Santitoro, A., Aprile, G.g. Baldantoni, D., Bartoli, G. and Alfani, A. Environ. Monit. Assess 98, 59-67, 2004.

28. Aksoy.A., Qzturk. M. Phoenix dactylifera L. J. Trace and Microprobe Tech. 14, 605-614 1996.

29. Aksoy, A. and Sahin, U. B.Tr. J. of Botany 23, 83-97, 1999.30. Bu-olayan, A.H. and Thomas, B.V. J. Sci. Eng. 29 (1), 65-73, 2002.31. Jaradat, Q.M., Momani, K.A. Turk. J. Chem. 23, 209-220, 1999.32. JAfari, A., Gadi, E.L. Al-Faateh University, Tripoli, 1983.33. Ho, Y.B. and Tai, K.M. Environ. Pollut. 49, 37-51, 1988.34. Otte, M.L., Bestebroer, S.J., Van der Linden, J.M., Rozema, J., Broeknan, R.A.

Environ. Pollut. 72, 175-189, 1991.35. Farrison, R.M., Laxen, D.P. and Wilson,. SJ. Environ. Sci. Technol. 15, 1379-

1383, 1980.36. Hewitt, C.N., and Candy, G.B. Environ. Pollut. 63, 120-136, 1990.37. Davies, B.D., Elwood P.C., Gallacher, J. and Gnnver, R.C. Environ. Pllut. 9,

255-265, 1985.38. CulbaRd., E.B., Thornton, I., Watt, J., Wheat Ley, M., Moorcroft, S. and

Thompson, M.E.J. Environ. Qual. 17, 286-94, 1988.39. Ndiokwere, C.L. Environ. Pollut 7, 35-42, 1984.40. Ward.,N.I., Brooks, R.R., Roberts, E. and Boswell, C. Environ. Sci. Technol.,

11, 917-20, 1977.41. Davies, B.E., Urban Ecology, 6, 285-94, 1984.42. Carey, A.E. Gowan, J.A., Froe hand, T.J. Tai, H. and Wiersman, G. pesticides

Monit. J. 10, 150-4, 1980.43. Central pollution control Board., New Delhi, India. Survey Report, Municipal

wastes & Composting, 2003-04.

11

Page 12: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

Fig. (1): Map showing roads and sampling sites

12

Page 13: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

Site :AZ ZAWIYAH Road

0

20

40

60

80

100

120

140

160

180

200

0 5 10 15 20 25

Site distance (Km) on :AZ ZAWIYAH Road

Co

nc

(ug

/g)

Siol Zn

Dust Zn

Siol Cu

Dust Cu

Site :AZ ZAWIYAH Road

0

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25

Site distance (Km) on :AZ ZAWIYAH Road

Co

nc

(ug

/g)

Siol Pb

Dust Pb

Siol Cd

Dust Cd

Fig. (2a). Variation of heavy metal in topsoil and road side dustLeft side: Zn & Cu; Right side: Pb & Cd, Zawya.

Site :AL KHUMS Road

0

20

40

60

80

100

120

140

160

180

0 5 10 15 20 25

Site distance (Km) on AL KHUMS Road

Co

nc

(ug

/g)

Siol Zn

Dust Zn

Siol Cu

Dust Cu

Site :AL KHUMS Road

0

5

10

15

20

25

30

35

40

0 5 10 15 20 25

Site distance (Km) on AL KHUMS Road

Co

nc

(ug

/g)

Siol Pb

Dust Pb

Siol Cd

Dust Cd

Fig. (2b). Variation of heavy metal in topsoil and road side dustLeft side: Zn & Cu; Right side: Pb & Cd, Khums.

13

Page 14: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

Site : AS SAWANI Road

0

50

100

150

200

250

0 5 10 15 20 25

Site distance(Km)on AS SAWANI Road

Co

nc(

ug

/g)

Siol Zn

Dust Zn

Siol Cu

Dust Cu

0

5

10

15

20

25

30

35

40

0 5 10 15 20 25

Site distance(Km)on AS SAWANI Road

Co

nc(

ug

/g)

Siol Pb

Dust Pb

Siol Cd

Dust Cd

Site : AS SAWANI Road

Fig. (2c). Variation of heavy metal in topsoil and road side dustLeft side: Zn & Cu; Right side: Pb & Cd, Sawani.

Site:TARHONA Road

0

20

40

60

80

100

120

140

160

180

0 5 10 15 20 25

Site distance(Km)on TARHONA Road

Co

nc(

ug

/g)

Siol Zn

Dust Zn

Siol Cu

Dust Cu

Site:TARHONA Road

0

5

10

15

20

25

30

35

40

0 5 10 15 20 25

Site distance(Km)on TARHONA Road

Co

nc(

ug

/g)

Siol Pb

Dust Pb

Siol Cd

Dust Cd

Fig. (2d). Variation of heavy metal in topsoil and road side dust:Left side: Zn & Cu; Right side: Pb & Cd, Tarhuna.

14

Page 15: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

Site : AZ ZAWIYAH RoadPlant specie :Dodonaea viscoaa

0

10

20

30

40

50

60

0 5 10 15 20 25

Site distance (Km) on AZ ZAWIYAH Road

Co

nc

(u

g/g

)

Zn unwashed

Zn washed

Cu unwashed

Cu washed

Site : AZ ZAWIYAH RoadPlant specie :Dodonaea viscoaa

0

0.5

1

1.5

2

2.5

3

0 5 10 15 20 25

Site distance (Km) on AZ ZAWIYAH Road

Con

c (u

g/g)

Cd unwashed

Cd washed

Pb unwashed

Pb washed

Fig. (3a). Variation of heavy metal in plant leaves (washed & unwashed)Left side: Zn & Cu; Right side: Pb & Cd, Zawya.

Site : AL KHUMS RoadPlant specie :Dodonaea viscoaa

0

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25

Site distance (Km) on AL KHUMS Road

Co

nc

(u

g/g

)

Zn unwashed

Zn washed

Cu unwashed

Cu washed

Site : AL KHUMS RoadPlant specie :Dodonaea viscoaa

0

0.5

1

1.5

2

2.5

0 5 10 15 20 25

Site distance (Km) on AL KHUMS Road

Co

nc

(u

g/g

)

Cd unwashed

Cd washed

Pb unwashed

Pb washed

Fig. (3b). Variation of heavy metal in plant leaves (washed & unwashed)Left side: Zn & Cu; Right side: Pb & Cd, Khums.

15

Page 16: Heavy Metals Deposition in Topsoil, Road Side Dust and Application of Doedonea Viscose as Bio Monitor

Site:AS SAWANI RoadPlant specie:Dodonaea viscosa

0

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25

Site distance(Km)on AS SAWANI Road

Co

nc(

ug

/g)

Zn unw ashed

Zn w ashed

Cu unw ashed

Cu w ashed

Site:AS SAWANI RoadPlant specie:Dodonaea viscosa

0

0.5

1

1.5

2

2.5

3

3.5

4

0 5 10 15 20 25

Site distance(Km)on AS SAWANI Road

Co

nc(

ug

/g)

Cd unw ashed

Cd w ashed

Pb unw ashed

Pb w ashed

Fig. (3c). Variation of heavy metal in plant leaves (washed & unwashed)Left side: Zn & Cu; Right side: Pb & Cd, Sawani.

Site:TARHONA RoadPlant specie:Dodonaea viscosa

0

10

20

30

40

50

60

0 5 10 15 20 25

Site distance(Km)on TARHONA Road

Co

nc(

ug

/g)

Zn unw ashed

Zn w ashed

Cu unw ashed

Cu w ashed

Site:TARHONA RoadPlant specie:Dodonaea viscosa

0

0.5

1

1.5

2

2.5

0 5 10 15 20 25

Site distance(Km)on TARHONA Road

Co

nc(

ug

/g)

Cd unw ashed

Cd w ashed

Pb unw ashed

Pb w ashed

Fig. (3d). Variation of heavy metal in plant leaves (washed & unwashed)Left side: Zn & Cu; Right side: Pb & Cd, Tarhuna.

16