Environment International, Vol. 4, pp. 239-244, 1980 Printed in the USA. All rights reserved.

0160-4120/80/090239416502.00/0 Copyright1981 Pergamon Press Ltd.

TRACE METAL LEVELS IN TREE BARKS AS INDICATORS OF ATMOSPHERIC POLLUTION

O. Osibanjo and S. O. Ajayi Department of Chemistry University of Ibadan Ibadan, Nigeria

(Received 6 April 1980; Accepted 22 September 1980)

Barks of six species of trees were sampled at thirty-nine different locations in Ibadan, Nigeria and were analysed for the trace metals lead, cadmium, cobalt, copper, zinc, manganese, and iron. Lead levels in barks from areas with relatively high traffic density were generally higher than lead levels in barks from a r e a s with low traffic density. The lead level recorded in the high traffic density areas, 40-140 p.g/g, is low compared to values reported for barks of trees along busy roads in developed countries. For the other metals, no correlation with traffic density was observed.

Introduction Results of environmental studies within the last t w o decades or so have implicated atmospheric pollutants ranging from trace metallic elements and gases such as sulphur dioxide as being responsible for certain diseases in man, animals, and vegetation (Lawther, 1965; Williamson, 1973). Trace levels of some toxic metals including lead and cadmium have been shown to be health hazards when ingested by m a n through inhalation or along the food chain. The combustion of fossil fuels and automotive exhaust emission in certain areas are the primary sources of the atmospheric metallic burden (Williamson, 1973). Biological monitors such as h u m a n blood and skeletal tissues and vegetation have been used to monitor levels of atmospheric metallic concentrations (Valkovic et al., 1974). It has been shown (Clyde, 1971) that vegetation is an important sink for atmospheric pollutants and the use of vegetation monitors have been found to be simple and cheap. However, trees are preferable to grasses, shrubs, mosses, and food crops because they are widely distributed and remain in a fixed position over considerable periods of time, enabling the analysis of trends over time intervals. Most of the studies on atmospheric pollution monitoring in this direction have been carried out mainly in the developed countries of Europe and the U.S.A., where levels of metals in tree barks and tree rings have been correlated (Barnes et al., 1971) to the actual levels present in the atmosphere. There is need for comparative data from developing countries, where pollution problems 239

are beginning to reach a disturbing magnitude in certain cases. In developing countries, atmospheric pollution is localised to towns and cities resulting from dust and suspended particulate matter in the air during road and highway construction operations, burning of fossil fuels for multifarious purposes, and automobile exhaust emissions. In Nigeria, automobile exhaust would account for about 80% of the air pollution problems in the urban areas; the remaining 20% being contributed from industrial sources, the burning of refuse and forest, and civil engineering activities. The level of lead in Nigeria's super grade gasoline is 600-800 mg Pb per litre which is higher than the permissible levels of lead in gasoline in the U.K. and U.S.A. (Crighton, 1974). About 15%-30% of the emitted lead from automobiles is airborne (Quinche et al., 1969) and it is not uncommon to find people plucking and eating raw fruits, or food hawkers displaying their stuff openly and unwrapped alongside a heavy traffic road. To the best of our knowledge, no measurement of heavy metals in vegetation, as indicators of air pollution, has previously been reported in Nigeria. This paper gives the results of a study carried out over a dry season period in Ibadan, the third largest city in Africa, on the levels of trace heavy metals of tree barks as a measurement of local metallic pollution. The choice of metals determined, that is, Pb, Cd, Co, Cu, Zn, Mn, and Fe was based on environmental considerations,

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O. Osibanjo and S. O. Ajayi uniform size with a laboratory mill (the mill was thoroughly cleaned and dried before and after each grinding to avoid contamination).

Sampling and Sample Description

Six species of trees, with different bark features (degree of roughness) as shown in Table 1, were sampled from thirty-nine various locations in I b a d a n (Fig. 1) to represent areas of different traffic density. The sampling points designated SI-$39, included locations of high traffic density ($1-S6,S14-S22), medium traffic d e n s i t y (S7-S13,S27-$36,S38-S39), lOW density residential a r e a s ( S 2 3 - S 2 6 ) . Sampling points S I - S 4 represent different locations within the city's main shopping centre. The University Botanical Garden ($37) serves as the pollution free reference point, being remote from traffic flow. Trees of about the same age, situated close to the highway (about 5 m) were selected and the barks carefully removed with a stainless steel pen knife at an average height of about 2.0 m above the ground (Barnes, 1976). The bark samples were kept in paper envelopes and then placed in polythene bags. Each tree was sampled at least twice. The samples were dried in the oven at 60C for about 3 h. Then they were pulverised to

Experimental
About 2 to 3 g of each sample was accurately weighed into properly cleaned vitrosil crucibles and ashed at 450-500 C. The ash was dissolved in 5 ml of 20% hydrochloric acid, and then mixed with water in a 100 ml volumetric flask. The samples were analysed by atomic absorption spectrophotometry using a PerkinElmer Model 305B instrument operated as per the instrument's handbook. Air-acetylene flame was used and the instrument was calibrated using mixed calibration standard solutions prepared as required, by stepwise dilution from stock standard solutions prepared from the pure metal or analytical grade chloride or nitrate of the metals. Stock solutions were 1% in HCI or H N O 3, but calibration standards were always 1% in HC1.

Table 1. Description of tree species, barks, and locations; key to Fig. 1

Botanical name

Tree Species Common name

Bark features

Tree location
SI

Site description
U T C technical

$2
S3

Samanea saman

Rain trees

Rough but porous and thick

$4 S5 S6 S7 S8
Sto
S I1 812

Cocoa House Bank Road, Dugbe Railway station Adamasingba Adamasingba Agodi
Aerodrome Oduduwa Road,

Si3 839 St4 Sis $22 $24

S2s
Casuarina

U.I. OduduwaRoad, U.I. Niger Road, U.I. Niger Road, U.I. Independence, Hall, U.I.
Molete

Whistling
pine

Rough, porous, slightly thick but

brittle and

$32 $34
S37

loose
St9 $2o

Oke-Ado ElizabethRoad Bodija Admissions's Office Geology Dept., U.I. BalewaHall, U,I. Botanical Garden, U.I.
Sango

$25
Delonix regia

Flamboyant tree Slightly smooth, thin layers

327 S2s

ElizabethRoad Bodija U.I. gate

Oduduwa Road,

S31 $35

U.I. Niger Road, U.I. Botanical Garden, U.I.

Trace metal levelsin tree barks Table 1. Continued. Tree Species Botanical Common name name Bark features Tree location
SI6

241

Site description Salvation Army Road Mokola Awolowo Av. Bodija Niser Car Park, U.I. Niger Road/ Zoo Garden Road junction U.I. Botanical Garden, U.I. Elizabeth Rd/ Parliament Rd. junction Elizabeth Rd. close to Baptist church Awolowo Av, Bodija Botanical Garden, U.I. Opposite U.I. gate

Si7 $26
Terminalia catappa

Indian almond Rough, hard tree (local name: and slightly bread fruit tree) thick

$30
$33

$36 SIS

Azadirachta

Dogo yaro

Rough, hard and thick

S21

$23 S3s
Tabe buia rosea

Rough, hard but tough to peel off

S9

'qD61X ' .. 22

L.21

,B

" "

APata

--,,,,o,,oo
3 4 35

383671

--Ceme~ry

Cemetry

13

--

E7 o

'<

UNIVENSITY

30
13291231

\
|
I

32 3334 39

I i I

Fig. 1. Sketch of part of Ibadan showing location of samples.

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Results and Discussion

O. Osibanjo and S. O. Ajayi barks. For example in Table 3, the values of lead obtained were rain tree 140 # g / g , Indian almond tree 89.5 # g / g , and dogo yaro 64.4 # g / g . This observation can be related to the nature of the barks, since rough barks are known to accumulate metals more than smooth barks (Barnes et al., 1976). Residential areas such as Bodija and Agodi normally have low traffic volume, thus having lower concentrations of lead and other metals than areas of high traffic density already mentioned in the foregoing paragraph. In Bodija, for example, Table 4, the lead levels recorded were flamboyant tree 65.5 /~g/g, Indian almond 92.0/~g/g, and dogo yaro 31.4 # g / g , but are higher than the values obtained from locations within the university campus, e.g., Oduduwa Road (Sll), Niger Car Park ($30), and Niger R o a d ($12, $13), where the traffic load is usually light. In all cases, samples collected from the Botanical Garden, where the traffic is almost nil, have the least values (Table 4). The type of tree also appears to affect the metal concentrations of barks in areas of low traffic density. However, for a family of tree species within the same traffic density

Organometallic compounds such as tetraethyl lead and zinc dialkyl dithiophosphate are often added to gasoline and lubricating oils. Hence, the concentration of lead should be highest, compared to other metals, in the tree barks if the metals accumulated in the barks have been derived from atmospheric pollution caused by auto-exhaust emission. The results for lead show a marked variation of concentration with traffic volume for all species of trees (Tables 2-4). Tree barks in areas of relatively higher traffic volume such as the Dugbe City Centre ($1) , (S5,S6) , Molete (S14), Oke-Ado (S15), Mokola (Si7), and Sango ($19) generally have the highest values for each plant species (Tables 2 and 3). In Table 2, S 1, $4, S 5, S 6 are areas of high traffic density; S 7, S s, areas of low density; S 7, S 8, areas of low traffic density, while locations within the university campus, Sio-$13 and $39 have the lowest traffic density. In areas of similar traffic density, the type of tree appears to have significant influence on the concentration of lead in the tree

Table 2. Variation in lead concentration with traffic density for bark from rain trees. Sample SI S4 $5 S6 S7 Ss Si0 Sll Sl2 Si3 $39 Location UTC Technical, Dugbe Railway station, Dugbe Adamasingba Adamasingba Agodi Aerodrome Road Oduduwa Road, university campus Oduduwa Road, university campus Niger Road, university campus Niger Road, university campus Independence Hall, university campus /xg Pb/g sample dry weight 140.0 102.0 110.2 85.8 35.6 39.5 16.2 24.1 16.7 18.5 14.8

Table 3. Concentration of lead, zinc, and copper at commercial/city (high traffic density) sites. Tree species Rain tree Rain tree Pine tree Pine tree Flamboyant tree Flamboyant tree Indian almond tree Indian almond
tree

Tree location UTC Technical ($1) Adamasingba ($5) Molete ($14) Oke-Ado ($15) Sango (Si9) Elizabeth Road (S2t) Salvation Army Road (Sic 0 Mokola (SiT) Elizabeth Road ($21) Elizabeth Road (Sis)

Concentration,/~g/g sample dry weight Pb 140.0 110.2 34.6 44.7 121.0 100.3 89.5 902.0 64.4 39.5 Zn 60.8 31.7 8.2 13.3 102.7 60.4 20.0 100.7 55.6 17.1 Cu 8.2 16.3 4.7 6.4 15.5 13.1 20.4 21.9 5.4 7.1

Dogo yaro Dogo yaro

Trace metal levels in tree barks Table 4. Concentration of lead, zinc, and copper at residential (low traffic density) sites and the Botanical Garden. Tree species
Rain trees

243

Tree location Pb Agodi ($7) Oduduwa Rd. U.I. (Sll) Niger Rd. U.I. (Sl3) Bodija ($24) Students Admissions Office, U.I. (S2s) Behind Geology Dept. U.I. ($32) Botanical Garden ($37) U.I. gate ($9) Oduduwa Rd. U.I. (St0) U.I. gate ($27) Bodija ($25) Niger Road ($31) Botanical Garden ($25) Bodija ($26) Niser car park ($30) Niger Road ($33) Botanical Garden ($36)
Bodija ($23)

Concentration,/Lg/g sample dry weight Zn 22.6 11.1 7.0 24.5 22.4 35.3 31.4 35.5 14.8 20.1 Cu 6.8 5.1 5.8 7.8 10.0 9.9 16.7 19.8 18.8 15.1 35.6 24.1 18.5 28.2 22.8 16.8 14.3 36.8 25.0 33.7 65.5 35.5 18.7 92.0 31.2 39.4 24.1 31.4 12.6

Rain trees Rain trees Pine tree Pine tree Pine tree Pine tree Tabebuia rose Flamboyant tree Flamboyant tree Flamboyant tree Flamboyant tree Flamboyant tree Indian almond Indian almond Indian almond Indian almond Dogo yaro Dogo yaro

Botanical Garden (S3s)

traffic v o l u m e a r e a s are used for m e d i c i n a l purposes. F r o m our s t u d y the r a n g e o f values of l e a d in tree b a r k s f r o m high traffic d e n s i t y a r e a s in I b a d a n is 4 0 - 1 4 0 / ~ g / g , except for the high v a l u e of 9 0 2 . 2 / ~ g / g o b t a i n e d at l o c a t i o n $17. I n c o m p a r i s o n to values rep o r t e d elsewhere, e.g., C a n a d a 100-3000 #g P b / g ( C a n o n a n d Bowles, 1962), F r a n c e 5 0 - 1 0 0 /tg P b / g (Quinche et al., 1969), a n d Britain 100-700 /~g P b / g (Barnes et al., 1976) o u r results m a y n o t c a u s e imm e d i a t e e n v i r o n m e n t a l p o l l u t i o n c o n c e r n now. But the localised effects m a y s o o n e r b e serious, especially for children, if the p r e s e n t p h e n o m e n a l rate of increase in traffic v o l u m e continues. T h e r e is no definite c o r r e l a t i o n b e t w e e n the levels of the o t h e r metals, Cd, Co, Cu, Zn, M n , a n d F e in the tree b a r k s a n d traffic density. But the m e t a l levels are in g o o d a g r e e m e n t with the soil a b u n d a n c e r a t i o of these elements ( T a b l e 5). T h e a v e r a g e soil a b u n d a n c e of the metals is in the o r d e r F e > > M n > > Z n > C u > C o > Cd, the s a m e t r e n d as o b t a i n e d in this s t u d y for the levels of the metals in the b a r k s of trees. This implies that tree b a r k s are useful m o n i t o r s of the soil metallic Table 5. Average concentration of cadmium, cobalt, copper, zinc, b u r d e n . The v a r i a b l e p l a n t n u t r i e n t r e q u i r e m e n t s a n d manganese, and iron in barks of different tree species around Ibadan. n u t r i e n t a b s o r p t i o n capacities of p l a n t s f r o m soils m a y Concentration/tg/g samples dry weight p r o b a b l y explain w h y c e r t a i n tree species c o n t a i n Tree species Cd Co Cu Zn Mn Fe 986.8 " higher m e t a l levels t h a n others, e x c l u d i n g a t m o s p h e r i c Rain tree 2.95 4.84 10.4 43.0 77.5 Pine tree 2.85 5.05 5.5 9.9 61.0 507.3 p o l l u t i o n sources. Flamboyant tree 3.60 6.68 11.3 49.1 160.6 1259.0 Indian almond tree 3.6 5.3 19.5 50.5 146.0 2288.0 Dogo yaro tree 2.3 4.1 10.8 30.9 62.1 635.0 Soil average abun0.15 23.0 70.0 132.0 100.0 500.0 Acknowledgements--We acknowledge the assistance received from dance (various Mr. Percy Onianwa during the collection and analyses of the samsources) pies. area, o t h e r factors such as w i n d d i r e c t i o n a n d the influence of a d j o i n i n g traffic m a y b e i m p o r t a n t . F o r example, E l i z a b e t h R o a d , s a m p l e l o c a t i o n S21, is close to a r o u n d a b o u t while $18 is n e a r b y a r o a d j u n c t i o n . Hence, d o g o y a r o h a s P b values of 64.4 /~g/g at S21 a n d 39.5 # g / g at Sts, respectively ( T a b l e 3). T h e I n d i a n a l m o n d tree c o n t a i n s higher values of l e a d a n d o t h e r m e t a l s (Tables 3 a n d 5) t h a n o t h e r trees in v a r i o u s l o c a t i o n s i n c l u d i n g the B o t a n i c a l G a r d e n ( T a b l e 4). T h e b a r k of this tree l o c a t e d at M o k o l a ($17) gave a consistently high l e a d v a l u e of 9 0 2 / ~ g / g despite r e p e a t e d s a m p l i n g a n d analysis. A l t h o u g h the tree is l o c a t e d n e a r the M o k o l a r o a d j u n c t i o n , a very b u s y traffic spot, a n d n o t far f r o m a gasoline service station, n o e x p l a n a t i o n c a n be given as yet for the u n u s u a l l y high result. D o g o y a r o tree b a r k a n d leaves are tradit i o n a l l y s o a k e d in w a t e r a n d the c o n c o c t i o n m a d e thereof, used for m a l a r i a cure. T h e r e c o u l d be further risk to h e a l t h w h e n b a r k s of d o g o y a r o trees f r o m high

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O. Osibanjo and S. O. Ajayi

References
Barnes, D., Hammadah, M. A., and Ottaway, J. M. (1976) The lead, copper and zinc contents of tree rings and bark, a measurement of local metallic pollution, Sci. Total Enviro~ 5, 63. Cannon, H. L. and Bowles, J. M. (1962) Contamination of vegetation by tetraethyl lead, Science 137, 765-6. Clyde, A. H. (1971) Vegetation: A sink for atmospheric pollutants, J. Air Pollut. Control Assoc. 21, 341. Crighton, I. S. (1974) Motor oil additives, Chert Ind 4, 126. Lawther, P. J. (1965) Air pollution and illness, Discovery J. Sci. 25, 14. Quinche, J. P., Zuber, R., and Bovay, E. (1969) Lead pollution of highway roadside vegetation, Phytopathol. Z. 66, 259-274. Valkovic, V., Rendic, D., and Biegert, E. K. (1979) Trace element concentration in tree rings as indicators of environmental pollution, Environ. Int. 2, 27. WiUiamson, S. J. (1973) Fundamentals of Air Pollution, AddisonWesley, Reading, MA.