Pertanika 6(3), 48-55 (1983)

Heavy Metals in some Malaysian Mosses

LEE CHNOONG KHENG, LOW KUN SHE, AZHAR PHOON1 and PATRICK LOI SUOK TEEChemistry Department, Faculty of Science and Environmental Studies,

Universiti Pertanian Malaysia, Serdang, Selangor, Malaysia,

Keywords: Mosses; heavy metals; background values; correlations.

RINGKASAN

Enam puluh lima jenis sampel lumut dikumpulkan secara rawak dari kawasan Kuala Lumpur dandi sekitarnya. Sampel-sampel ini dianalisiskan untuk Zn, Pb, Cd, Cu, Ni, Fe dan Mn. Kecenderongan ter-tentu diperhatikan untuk perubahan kepekatan Pb lumut-lumut. Perubahan dalam logam lain tidakmengikut kecenderongan yang jelas. Nilai latar belakang bagi logam-logam ini kecuali Fe pada umumnyadapat dibandingkan dengan nilai yang telah dilaporkan. Kajian pertalian antara logam-logam dilakukandan keputusan menunjukkan adanya pertalian yang positif dan penting antara Pb, Cd, Cu, Fe dan Mn.Kesesuaian untuk menggunakan lumut-lumut sebagai penunjuk pencemaran adalah dibincangkan.

SUMMARY

Sixty-five moss samples were collected randomly from areas in and around Kuala Lumpur andanalysed for Zn, Pb, Cdt Cu, Ni, Fe and Mn. A definite trend was observed for the variation of Pb con-centration in mosses. The variations for the other metals were, however, not clearly defined. The back-ground values for these metals were generally comparable to previously reported values except Fe whichwas high. Correlation studies among the metals were performed and the results indicated positive significantcorrelations among Pb, Cd, Cu, Fe and Mn. The suitability of using mosses as pollution indicatorsis discussed

INTRODUCTION

The monitoring of atmospheric pollution isof great importance. Various direct means ofmonitoring heavy metals in the atmosphere areavailable (Hendrikson, 1962). However, most ofthese methods, though yielding accurate andquantitative estimations, are rather expensive andcumbersome. The use of biological materials asmetal indicators, on the other hand, has beenreported to be a relatively cheap, simple andreliable method (Goodman and Roberts, 1971;Little and Martin, 1964). The use of mosses in thisrespect has been reported to be advantageous overthat of vascular plants (Groet, 1976).

Ruhling and Tyler (1968, 1970, 1971) studiedthe distribution of heavy metals in mosses andvascular plants. Holocomium splendens was foundto be a sensitive indicator for heavy metal pollu-tion. Groet (1976) investigated the heavy metallevels in Leucobryum glaucum (Hedw) Angtr.

extr. and other mosses and found that the heavymetal concentrations were generally higher in themore industrialized areas.

Ward et al (1977) studied the concentra-tions of heavy metals in bryophytes. They foundthat near the ore treatment plant, the metalconcentrations were higher in the mosses than intheir substrates, indicating foliar uptake of air-borne contaminants.

Barclay-Estrup and Rinne (1978, 1980)reported that the concentrations of both leadand zinc in two feather mosses were higher in theurban than the rural areas. They found that themetal concentrations in Pleurozium schreberidecreased with increasing distance from the city.

In the study of seventeen moss species,Onianawa and Egumjomi (1983) found thatlead values for mosses from the rural areas of thecountry were significantly lower than those of the

1 Biology Department, Faculty of Science and Environmental Studies, Universiti Pertanian Malaysia.

Key to authors1 names: C.K. Lee, K.S. Low, Azhar Phoon, and P.S.T. Loi.

48

C.K. LEE, K.S. LOW, AZHAR PHOON AND P.S.T. LOI

city. No definite trend was, however, observedfor all the other trace metals analysed.

The distribution of heavy metals in Malaysianmosses has not been investigated. The presentstudy is the first attempt to determine the varia-tions in heavy metals in mosses in the city ofKuala Lumpur as well as some areas nearby, andto assess the suitability of using mosses as pollu-tion indicators.

METHODS AND MATERIALS

Sixty-five samples of mosses consisting of 24species were collected randomly from November1981-December 1981, and from October 1982—February, 1983. The mosses were collected fromareas which include Kuala Lumpur, the capital ofMalaysia, Selangor (Petaling Jaya, Shah Alam,Serdang), Negeri Sembilan (Pasoh Forest Reserve),Perak (Tanjung Malim) and Pahang (GentingHighlands and Cameron Highlands). Fig. 1 showsthe locations of these areas. Depending on thenatural habitat of the mosses collected, associatedsubstrate samples of soil or bark were collectedwherever possible.

ft

3 Ki

p.

To

Ca

X ^^—-^L \ /^PERAK V (_^

. C* i P A H A N G ^ VrOanq V ^ , (

ah Alam \ E L A N G O * 2

ala Lumpur \ L ^

talin<) Jaya V * * * p \

njunq Malim C C" • X^ • 4 NEGRI , v ~

meron Highlands N ^ ^ .

ntinq Highlands V.

1

Fig. 1. Map of part of Peninsular Malaysia showingsampling locations.

On arrival in the laboratory, the mosses weremanually separated from their substrates, washedtill no soil adhesion could be seen, rinsed withdeionised water and dried at 75°C for three days.The substrate materials were similarly treated.The dried samples were ground using a stainlesssteel grinder. One gram of the ground samplewas digested with a 4:1 mixture of concentratednitric and perchloric acids. The residue was re-dissolved in 1% nitric acid and made up to 25 cm3,(Little and Martin, 1972). A blank treated in thesame way was used as a control. Duplicates werecarried out for all the samples.

Analyses of Zn, Pb, Cd, Cu, Ni, Fe and Mnon all the samples were carried out using a sequen-tial inductively coupled plasma emission spectro-meter (Labtest Plasmascan 710-2100).

To check the accuracy of the analysis, deter-minations were made of the metal contentsof NBS standard reference material No. 1571(Orchard leaves). The material, in duplicate, wastreated in the same manner as the moss samples.The obtained concentrations for all metals exceptMn and Fe fell within accpetable limits (Table 1).The low values of Mn and Fe cannot be explainedat this juncture.

RESULTS AND DISCUSSIONS

Variations of heavy metal concentrationsThere are three areas where the mosses were

collected. Area I (Kuala Lumpur) has the highesttraffic density. Area II comprises Petaling Jaya,a satellite town 8 km from Kuala Lumpur; ShahAlam, a new state capital 24 km east of KualaLumpur and a University and Research Complexat Serdang, 20 km south of Kuala Lumpur. AreaIII includes the Pasoh Forest Reserve in NegeriSembilan, Tanjung Malim in Perak and Cameron

TABLE 1Analysis of National Bureau Standards (NBS)

No. 1571 (Orchard leaves)

Metal Zn Pb Cd Cu Ni Fe Mn

Certified value 25 ± 3 45 ± 2.0 0.11 ±0.01 12.0 ± 1.0 1.3 ± 0.2 300 ±20 91 ±4

Observed value1 27 ± 0,3 47 ± 0.2 0.12 ± 0.00 12.1 ± 0.4 1.1 ± 0.3 253.5 ± 0.5 77.3 ± 1.2

1 The values are means and S.D.s of the duplicate analyses.

49

HEAVY METALS IN SOME MALAYSIAN MOSSES

Highlands as well as Genting Highlands in Pahang.The traffic density in these areas is generally inthe order of Kuala Lumpur > Petaling Jaya >Shah Alam > Serdang > Area III. The heavymetal concentrations in mosses in areas I, II andIII are shown in Tables 2, 3 and 4 respectively.

There is a clear distribution pattern for Pb,irrespective of the species type and the age of themosses. With the exception of residential areas,Pb concentration ranged from 131 to 1634 jugg"1

in Kuala Lumpur, The range was 88-308 jug g"1

in Petaling Jaya, 23-98 jug g"1 in Shah Alam,17-69 jug g"1 in Serdang with the exception ofthe sample at the Tennis Court, Universiti PertanianMalaysia, 13-17 /igg"1 in Pasoh Forest Reserve,47-56 jugg'1 in Genting Forest, 17-54 jugg"1 inCameron Highlands and 19-22/igg"1 in TanjungMalim. These values clearly show that there isa definite distribution pattern for Pb in mosses,depending on the traffic density of the areas.

When specific species of the mosses are consi-dered, the same trend is shown. Pb concentrationforHyophilla involuta ranged from 172-1118 jug g"1

in Kuala Lumpur and 54-88 jugg"1 in Selangor.For Barbula indica, it was 412-1315 jug g"1 inKuala Lumpur and 44-93 jugg"1 in other areas.Similar trends in the variation of Pb concentrationhad been reported for Leucobryum glaucum(Groet, 1976) and Pleurozium schreberi andHylocomium splendens (Barclay-Estrup and Rinne,1978). Mosses, thus, appear to be a good indicatorof Pb pollution in the atmosphere.

No clear trend was observed for the variationof Zn, Cd, Ni, Fe and Mn in the mosses. Cugenerally followed the same trend as Pb althoughit was not as well defined. Low and et ai, (1983)demonstrated in a 10-week moss-bag experimentthat the uptake of Zn, Cd, Ni, Fe and Mn initiallyincreased with exposure time, but subsequentlydecreased. Pb and, to a lesser extent Cu, were thetwo metals whose concentrations in the mossesincreased with increasing exposure time. Thiscould be due to the fact that Pb was more effec-tively sorbed by the mosses (Ruhling and Tyler,1970). Lead was reported to form a more stableorganochelate with mosses than the other metals(Mellor and Mallye, 1947, 1948). Mosses, there-fore, could not be used to monitor Zn, Cd, Ni, Feand Mn levels on a long term basis.

Analysis of heavy metals in the substratesgave wide variations. No meaningful deductionscould be drawn from the results.

Background values for metalsOwing to the difficulty of obtaining true

natural values for heavy metals in mosses, samplesfrom remote and unpolluted areas were used toobtain data on 'near natural' or background values(Groet, 1976).

Table 5 lists the background values for themetals in the present study as well as some pre-viously reported values for comparison. Generallythe background values for Zn and Fe were higherin the Malaysian mosses. The background valuesfor Pb was about-equal to that in Canada, SouthScandinavia and New Zealand. It was, however,higher than that in North Scandinavia and Britainand lower than that in the Northeast USA. Thebackground values for Cd and Cu were higherthan those in Britain and Scandinavia but wereabout equal to those of the other countries. TheNi background value was higher than that inCanada and North Scandinavia and about equal tothat in the other countries. For Mn, the back-ground value was lower than that in Canada.The differences in values seem reasonable, takinginto account that various species of mosses werestudied.

Metal CorrelationA positive correlation was obtained for all

metal except that between Ni and Fe (Table 6).Significant correlations were observed for Cd,Pb, Cu, Fe and Mn. Zn correlates significantlywith Cd and Mn only. Ni correlates with Pb only.Rinne and Barclay (1980) reported significantpositive correlations among Cd, Cu, Fe, Ni, Pband Zn in Pleurozium schreberi. Groet (1976)observed significant positive correlations amongCr, Cu, Ni and Zn in Leucobryum glaucum;however, Cd correlated with Zn only. Ruhling andTyler (1969) intercorrelated Cu, Zn, Ni and Pbin Hypnum cuppressiforme and reported positivecorrelations between Cu and Ni (0.61), Cu and Zn(0.36), Cu and Pb (0.49), but a lower correlationbetween Zn and Pb (0.29).

Correlation of heavy metals may bo affectedby emission sources (Groet, 1976), metrologicalconditions as well as the age and the speciesof the mosses (Grodzinska, 1978). In the presentcorrelation study, all the mosses, irrespective oftheir age and species, were considered. This mayexplain some of the anomalies observed.

CONCLUSION

From the data gathered in this study itappears that Malaysian mosses are good indicatorsfor Pb pollution in the atmosphere. However, the

50

TABLE 2Concentration of heavy metals (jug g"1 dry weight) in mosses in Kuala Lumpur

SampleNumber

Kl

K2

K3K4

K5

K6

K7

K8

K9

K10

K l l

K12

K13

K14

K15

K16

K17

K18

K19

K30

K 2 1 ;•*-

K22 ':;'K23 pK24 'K25

K26

Location

Jalan AmpangJalan AmpangJalan PekelilingJalan BrickfieldJalan BrickfieldJalan BrickfieldSt, Mary CathedralJalan BelandaJalan KuchingCourt HillCourt HillGeneral HospitalLake Garden :

Jalan BrickfieldResidential (city centre) v -Edinburgh Circle > \Jalan Raja MudaJalan Tunku Abdul Rahman (T.A.R)Road Junction of Jalan T.A.R.,

Jalan Raja Laut.Residential (outside city)Jalan PekelilingResidential (outside city)Jalan DutaJalan BrickfieldJalan Sungai BesiJalan Pekeliling

Species

Hyophilla involuta

• • • •

Meiothecium microcarpum Harv.) Mitt.

Meiothecium sp.Berbula indica

Barbula sp.Calymperes dozyanumCalyperes sp.

Isopterygium minutirameum (CM.) Jaeg.Syrrhopodon sp.Bryum coronatum Schwaerr.Splachnobryum oorschotii (Lac.) C Mall.

Zn

382.3370.6629.0648.3550.1311.4371.7305.9139.4158.4197.6619.0

88.5257,9634.0673.0

10081881504.0

38.9726.6479.0227.2241.1757.0

' 896.0

Pb

11181079917.7

1037708.9429.3841.1535.4172.1291.0311.4

468.0131.7142.0215.9

16971315411.9483.5

35.6407.963.4

328.6322.2

588.41634

Cd

5.8

7.3

6.5

4.7

2.9

2.8

4.8

3.2

5.5

3.2

1.2

5.9

1.4

.083.0

3.4

5.2

7.5

4.6

3.*

3.0

1.9

4.0

1.1

7.1

6.6

Cu

62.669.859.877.8

103.141.264.049.541.5

52.633.036.669.521.925.856.943.536.7

9.9

25.39.8

75.744.252.974.5

Ni

20.621.320.915.8

8.6

12.411.717.513.4

_

6.2

5.7

6.1

19.445.643.125.319.756.1

9.7

29.943.819.716.120.919.3

Fe

393094906800589536941445679752868833

-

250356102342518633303410537046104340

84892190

860

66101450

72006750

Mn

257.0174.6114.7148.9122.1107.2201.396.576.2

-

43.3101.440.595.434.625.6

134.4175.3108.2

23.361.349.366.663.399.4

128.2

in

N

IOy4

TABLE 3Concentration of heavy metals (jug g"1 dry weight) in mosses in Selangor

SampleNumber Location Species Zn Pb Cd Cu Ni Fe Mn

Petaling Jaya51 Residential (next to

playground)52 Town53 Playground

Shah Alam54 Adjacent to electronic

engineering factory55 Ladang Sungai Rengam56 As above57 ITM58 ITM59 Adjacent to Highway.

Serdang510 Hydroponic unit, UPM511 Foodtech, UPM.512 Tennis court, UPM513 Coconut unit, UPM514 Oil palm estate, UPM, near S13515 Oil palm estate, 10 m from

highway to Kajang. •)516 Jalan Ladang, UPM J

517 Mardi Guard House518 Mardi Oil palm estate519 Mardi Oil palm estate520 Junction between Serdang/

Belakong521 Same as 20522 Opposite to site 21

Puchong523 Rubber estate524 Rubber estate

Hyophille involuta

Philonotis hastata (Duby) Sijk & Marg.Leucophanes octoblespharoides Brid.

Hyophille involuta

Octoblephan albdtum Hedw.Syrrhopodon cittiatusBabula indicaBabula indicaCalymperes sp.

Meiothecium microcarpum

Barbula indicaIsopterygium albescens (Schwawgr.) Ja

Calymperes delesscittii Besh.Syrrhopodon albovaginatus Schwaegr.Isopterygzium minutirameum

Calymperes sp.

Tazithelium ramicola Broth.Fissidens sylvaticus Girff.

108.7

1914

87.6 2.3 31.3 6.1 2586

65.5 6.9 37.0 20.4 5140

38.9

111.3315.0

308.2102.2

7.24.4

17.47.5

15.320.3

80293700

47.416.4

56.7

314.0619.0678.0548.0795.0

828.0139.0

15111074728.068.6

110.3158.0149.9179.9789.1

152.878.7

139.577.8

24.223.052.792.798.2

17.221.8

208.025.319.140.4

45.321.627.244.869.3

62.559.9

44.646.3

3.15.53.03.97.9

4.40.59.62.82.02.1

3.91.82.32.86.0

2.41.4

2.73.9

9.615.012.015.116.7

10.923.128.619.310.915.8

12.314.955.398.9105.0

19.223.7

23.737.1

14.613.320.011.517.9

10.54.323.66.916.48.1

17.516.117.136.012.4

3.26.1

10.513.8

470027805160698011370

10570851712280237017101290

40001746336256599458

18391343

46007181

16.318.219.265.137.3

78.424.9213.286.848.070.9

71.291.634.035.3106.7

75.722.4

83.636.8

>

>2

i

oento

mC/3

*1TM - InstitutTeknologi Mara.UPM - Universiti Pertanian Malaysia.

TABLE 4Concentration of heavy metals (jig g"1 dry weight) in mosses in Negeri Sembilan, Pahang and Perak

*

SampleNumber

Nl

N2

N3

N4

PI

P2

P3 :

P4 '

?5

P6

P7

P8

P9

P10

P l l

Location

Negeri Sembilan

Forest Reserve

Plot 1

Plot 2

Plot 3

Plot 4

Pahang

Genting Casino

Genting Casino

Genting Forest

Genting Forest

Cameron Highland

Residential Bungalow

Research station

Jungle path

Flower farm

Hill slope ^ 4 ' ;

Tanjong Malim, Peitfe

Oil palm estate ^ *!

Oil palm estate

Species

Syrrhopodon sp.>»

t

Barbula indica (Schwaegr) Brid.Bryum argenteum Hedw.Pyrrhobryum spiniforme (Hedw.) Mitt.Trimegistia sp.

Hyophilla involutaBarbula indica (Schwagr) Brid.Braunfehia sp.Philonofiz tumerianne (Schwaegr) Mitt.Rhacopilum spectabile Reinw and Hornsch.

Calymperes sp.Octoblespharum albidum Hedw.

Zn

179

171

179

176

1521176.5326.1380.5

741.0248.0442.0515.0804.0

626.0589.0

Pb

13.612.615.616.5

648.5624.847.456.1

54.143.917.223.134.3

22.018.8

Cd

1.3

1.3

1.5

1.4

4.4

3.3

0.9

1.9

4.7

5.1

1.7

3.8

3.4

1.8

1.6

Cu

7-320.413.5

7.6

33.186.513.310.4

10.122.1

8.0

14.611.3

7.5

10.4

Ni

4,0

15.619.917.0

12.711.212.918.8

10.119.826.619.317.3

20.314.3

Fe

2000237032302088

46441611390647120

41203940390034704120

37007300

Mn

13.313.547.721.6

104.9106.9

-

-

110.784.6

100.8100.630.9

16.414.8

O

wFH

in

5>N

%

ooz*>zwT>inH.LO

l

Ii

TABLE 5.Comparison of Background Values of Heavy Metals

Species analyzedElement

Zn

Pb

Cd

Cu

Ni

Fe

Mn

Serdang (1) Forest Reserve (1) Canada (2) Southern Northern North

range) (range) rangeScandinavia (3) Scandinavia (3) Eastern USA (4) Britain (5) New Zealand (6)

range range meanmean ± SD mean ± SD

Isoptergium Sypohopodon Pleurozium Hylocomium Hylocomium Leucobryum Hypnum Hypnumalbescens sp. schreberi splendens splendens gloucum cupressiforme cupressiforme

68.6-728.0

19.1-45.3

3.0- 3.9

10.9-19.3

8.1-16.4

1290-12280

48.0-213.3

171-179

12.6-16.5

1.3-1.5

7.3-20.4

4.0-19.9

2000-3300

13.3-47.7

65-71

29-31

0.5-0.6

6.6-8.8

2.0-3.4

690-940

290-320

80-110

40-150

0.8-1.5

8-12

3-8

1000

30-40

5-10

0-1

5

1.5-2.0

500

6.2

131.0

V 0.89

9.6

9.4

91 ± 17

5.8 ±8

1.4 ±0.4

13 ± 2

8.3 ±1.7

17.2

10.6

0.4

10.1

+

±

±

±

3

2

0

.3

.0

.21

2.4

I2O

00

O

References : (1) Results of present study(2) Rinne and Barclay-Estrup, 1980.(3) Ruhling and Tyler, 1973.

(4) Groet, 1976.(5) Goodman and Roberts, 1971.(6) Ward et al., 1977.

C.K. LEE, K.S. LOW, AZHAR PHOON AND P.S.T. LOI

TABLE 6Correlations between metals in mosses

Elementsn

Zn

Cd

Pb

Cu

Ni

Fe

Level of significance

*P<0.05 * * P < 0

Cd65

0.51**

.001

Pb65

0.18

0.40**

Cu64

0.04

0.27*

0.53**

Ni64

0.21

0.17

0.26*

0.02

Fe64

0.15

0.49**

0.16

0.31*

-0.06

Mn62

0.27*

0.55**

0.55**

0.49**

0.05

0.28*

use of mosses as indicators for other metalsrequires a more detailed study of the displacementpatterns among the metals.

REFERENCES

BARCLAY-ESTRUP; P. and RlNNE, R.J.K., (1978):Lead and zinc accumulation in two feather mossesin north western Ontario, Canada. Oikos, 30:106-108.

GOODMAN, G.T. and ROBERTS, T.M., (1971): Plantsand soils as indicators of metals in the air. Nattfre,231: 287-292.

GRODZINSKA, K., (1978): Mosses as bioindicators ofheavy metal pollution in Polish National Parks.Water, Air and Soil Pollution, 9: 83-97.

GROET, S.S., (1976): Regional and local variations inheavy metal concentrations of bryophytes in thenorth eastern United States.-O/fcos, 27: 445-456.

HENDRIKSON, E.R., (1962): Air Sampling. Air Pollu-tion, 1. New York. Academic Press. 389-433.

LITTLE, P. and MARTIN, M.H., (1972): A survey ofzinc, lead and cadmium in soil and natural vegetationaround a smelting complex. Environ. Pollnt, 6:1-19.

LOW, K.S., LEE, C.K., and LOI, P.S.T., (1983): Un-published Results.

MELLOR, D.P. and MALEY, L., (1947): Stability con-stants of internal complexes. Nature: 159, 370.

MELLOR, D.P. and MALEY, L., (1948): Order of stabili-ty of metal complexes. Nature: 161: 436-437.

ONIANWA, P.C and EGUNYOMI, A, (1983): Tracemetal levels in some Nigerian mosses used as indica-tors of atmospheric pollution. Environ. Poll 5:71-81.

RINNE, R.J.K. and BARCLAY-ESTRUP, P, (1980):Heavy metals in a feather moss, Pleurozium schreberi,and in soils in NW Ontario, Canada. Oikos; 34,59-67.

RUHLING, A. and TYLER, G. (1968): An ecologicalapproach to the lead problem. Bot. Notiser, 121:321-342.

RUHLING, A. and TYLER, G., 1969): Ecology of heavymetals - a regional and historical study. Bot. Notiser,122:248-259.

RUHLING, A. and TYLER, G., (1970): Sorption andretention of heavy metals in the woodland mossHylocomium (Hedw.) Br. et. Sch. Oikos, 21: 92-97.

RUHLING, A. and TYLER, G., (1971): Regional dif-ferences in the deposition of heavy metals overScandinavia. / Appl. EcoL, 82: 497-507.

WARD, N.I. BROOKS, R.R. and R O B E R T S , E. (1977):Heavy metals in some New Zealand bryophytes.Bryologist, 80: 304-312.

(Received 2 June 1983)

55