Wednesday, December 19, 2012

IPC2012








Heavy Metals and Arsenic Deposition Around a Palm Oil Mill using Palm Waste as Energy Source[1]

Zaini Hamzah1, Noor Azimah Darus2,4, Ahmad Saat3,*,
Zakaria Tajuddin2
1Faculty of Apied Sciences,
2Faculty of Agrotechnology
3Institute of Science
Universiti Teknologi MARA
40450 Shah Alam, Malaysia.
4Universiti Teknologi MARA
Cawangan Pahang, Kampus Jengka
26400 Jengka, Malaysia.

*Corresponding: ahmad183@salam.uitm.edu.my

 
ABSTRACT
To reduce the dependency on conventional fuel many palm oil mills nowadays used palm waste materials like fiber and shell as their source of fuel. However the emission of fumes and fly ashes from the mills raised some concern on their effect to the environment adjacent to the vicinity of the mills. Especially when these emissions and fly ashes are known to contain heavy metals, which some of them could pose health risk to people living around the mills. A study was carried out on one such mills and it surrounding areas, to determine the heavy metal and As contents in the waste fiber, shells and ashes as well as airborne deposition onto plants and soils. The mill is located in Perak, Malaysia. Debris and soils samples were collected in the north, south, east, and west direction relative to the mill, at distances 0.1, 0.5, 1.0, 2.0 and 3.0 km from the mill. The debris was collected between oil palm frond and trunk of about 3 to 4 years old trees.  The elements (As, Cu, Ni, Co, V, Hg, Zn, and Mn) concentrations in the samples were determined by using Energy Dispersive X-rays Fluorescence (EDXRF) technique. Results showed that except for As, Ni, Zn and Hg, other metals exhibit increment in concentration from fiber and shell to fly ash. Metals and As on debris showed varied distribution trends towards the four direction studied, which imply the effects of wind direction on the area. Generally, northerly concentrations showed higher concentration compared to other directions.  Although the elements might be attributed to both fly ash and application of fertilizers and pesticides, similar distribution trends for metals and As were also observed on soils. Plots of distribution pattern of elements on soil and plants enable the determination of “hot spots” for such elements.
Keywords: palm oil mill, heavy metals, EDXRF



INTRODUCTION
Palm oil industry in Malaysia is a success story. It has becomes an important economy sector, as Malaysian is one of the world’s major palm oil producer. Plantation companies vary considerably in size, from a few hundred hectares to more than 100,000 hectares either smallholder or commercial plantation. In 2009 about 4.49 million hectares of land in Malaysia under oil palm cultivation are producing 17.73 million tonnes of palm oil and 2.13 tonnes of palm kernel oil (MPOC, 2009).
To reduce the dependency on the conventional energy source, many palm oil mills recycled their production waste (fiber and shells) as biofuel to supply energy for the mills’ operation. Unfortunately the emissions in the form of fly ash from the fuel combustion and incineration may contained pollutants that that are deposited into the environment and administered to the ground (Subramaniam et al., 2008). These emissions would not only affect the environment but may also posing threat to human health (Yaccob et al., 1989).
Heavy metals such as cadmium, lead and mercury are common air pollutants and are emitted mainly into the air as a result of diverse industrial and human activities. Nowadays, heavy metal is causing concern due to the potential effects on human health and the possible long-term sustainability of food production in impure areas (Zarcinas et al., 2004). Toxic heavy metals in air, soil and water also provide global problem that are growing threat to humanity (Matlock et al., 2001).
This study focused on the determination of elemental composition palm oil waste and fly ash. This will then be related to the airborne deposition of heavy metals and arsenic in debris and soil samples collected in the study area around the palm oil mill.

MATERIALS AND METHODS
The study was done on the FELDA Nasaruddin Palm Oil Mill, in Bota, Perak located at the mid-western side of Peninsular Malaysia. Debris and soil samples were collected in about 3 km radius oil palm plantation area around the mill, assuming the mill as a single emission point source of the area. The soils and debris samples were collected at  0.1 km, 0.5 km, 1 km, 2 km and 3 km from palm oil mill towards north, south, east and west directions. The mill is using palm oil waste as energy source.
Deposited debris were collected between oil palm frond and trunk of oil palm trees of about three to four years in age, at a height of about one meter from ground. This would contain airborne deposition that has been accumulated over almost similar period time. At the same sampling points soil samples was taken by using hand auger to the depth of 15 cm. In the mill fly ash samples were collected at the final stage where fly ash are being retained in the multi-dust cyclone before emitted to the atmosphere. Raw palm oil fibers and shells were also collected.
All collected samples were oven dried at 60°C for at least 24 hours to remove water content. The dried samples were pulverized by using agate mortar and sieved by using 180 μm sieves. They were then pressed at 15 ton pressure to form pallet of 2 cm diameter and about 2 mm thick, for analysis by using Energy Dispersive X-rays Fluoresence (EDXRF) technique.  The instrument bench top PanAnalytical EDXRF spectrometer Model Minipal 4 was used to quantitatively determine As, Cu, Ni, Co, V, Hg, Zn, and Mn in the samples. Duplicate measurements were carried out. The reliability of the optimized analytical procedure was established by analyzing two certified reference materials, Pine Needle, NIST 1575 a and Lichen, IAEA-336. The recovery for various elements were found to ranged between 80% to 110% (Abdullah et al., 2011)

RESULTS AND DISCUSSION
Table 1 shows the results for elemental concentration in palm shell and fiber and the fly ash after the shell and fiber being incinerated for energy production. In Table 2 the concentration of eight elements studied in the debris and soil samples are presented. In the tables the uncertainty values for the data were estimated based on the peak height of the respective element peak in the fluorescence x-ray spectrum. They were dependent on the elements, however generally they are less than 10% of the quoted concentration values.

Fiber, Shell and Fly Ash
In fiber and shell among all elements manganese showed the highest concentration while mercury and cobalt shows the least.  Similar pattern is observed in fly ash. Copper, vanadium, cobalt and manganese showed an increasing trend of concentration from fiber and shell to fly ash, however arsenic, nickel and mercury displayed an opposite trend. No appreciable changed in concentrations were observed for zinc in fiber, shell and fly ash. Besides organic matter being the main composition, results of the study are consistent with Law et al., (2007) that shows the principal elements of oil palm fiber are copper (Cu), manganese (Mn) and iron. In this study due to experimental constraint iron was not determined. As for elemental concentration of elements in palm waste fly ash, the present study shows lower concentration compared to the values quoted by Nugteren et al., (1999) for refinery fly ash. Much earlier study on palm oil mills in Malaysia by Rashid et al., (1987) showed several elements were found to be much higher concentration in ash samples than our study. This observation might be attributed to the more efficient emission control multi-dust cyclone technology used in FELCRA Nasaruddin palm oil mill boiler. The contribution from the uptake elements in fertilizer and pesticide by oil palm trees and accumulated to the fruit bunches is inevitable.

Debris and Soil
Results in Table 2 showed a general pattern of concentration (ppm) variation in soil of elements at all distance (0.1 km, 0.5 km, 1.0 km, 2.0  km and 3.0 km) in all direction (north, south, east and west) that the higher concentration were manganese, zinc, and vanadium.  Meanwhile mercury and cobalt showed lower concentration. Its worthwhile to mention here that the elemental concentration in soil very much dependent upon the fertilizer application, water runoff and soil structure and also airborne deposited on the soil. In this study area the soil is peaty. The characteristic of peat soil are acidic, poor storage qualities, high water table and deficient in nutrient. High acidity will contributed to the high leaching that causing higher concentration of elements being leach out. As a consequence of this relatively more fertilizer are being applied to the plantation area.
For debris, fluctuations of elemental concentrations according to distance (0.1 km, 0.5 km, 1.0 km, 2.0  km and 3.0 km) and direction depend on the host particulate size of the elements, wind speed and direction, rainfall as well as age of tree that airborne deposition accumulated. Heavy rainfall may result in the runoff of airborne dust that trapped at the oil palm tree. Meanwhile, older trees will increase would accumulate more deposition. Wind direction and speed would bring together more fly ash particulate to certain directions than others. Zinc, manganese and vanadium can be categorized as higher concentration group for airborne deposition and as well as in soil samples. While, mercury, arsenic and cobalt, belongs to the lower concentrations group.
Comparison on average concentration of elements in soil and debris shows that arsenic, copper, nickel and vanadium are always higher in soil than debris. The opposite is observed for manganese and mercury. Average concentrations of zinc and cobalt are identical for both soil and debris. However, statistical study on the correlation of elemental concentrations between elements in soil to the respective element in debris shows no significant correlation. These observations might be explained by the combined effects of soil type, application of fertilizers and pesticides, rainfall as well as wind.
Spatial distributions of elements in debris around the 3.0 km radius about the mill are shown in Figure 1 and Figure 2. Assuming the emission of the palm oil mill is the main point source of these elements, the north and south directions of distribution are dominant for copper, nickel, and manganese, and arsenic. Of the two directions, southerly is more dominant. Cobalt, mercury, and vanadium show easterly distributions. This observation is consistent with the fact that Peninsular Malaysia experiences two monsoons seasons; the north-east monsoon and the south-west monsoon. The resultant effect of annual wind-rose for direction and speed are in these directions.
Based from the distribution according to distance from the mill in Figure 1, except for mercury and zinc, all other elements show highest concentration in debris collected at 1.0 km away either southerly or easterly. The trend of increasing concentration with distance, reaching maximum and then decreasing is consistent with “umbrella effect” as described  by Mohd Zahari et al., (2012) in his study on emission from an oil refinery. Briefly the maximum concentration is 17.05 ppm southerly for arsenic, 103.8 ppm southerly for copper, 24.2 ppm southerly for nickel, 0.86 ppm easterly for cobalt, 168.0 ppm easterly for vanadium and 1464 ppm southerly for manganese. Mercury showed highest concentration (0.10 ppm) at 0.1 km easterly, while zinc showed relatively uniform distributions (averaged about 245 ppm) towards all direction.

CONCLUSION
            The study has shown that although the use of oil palm waste for energy production for palm oil mill operation is economically noble approach, and able to reduce environmental impact of the abundance waste, other side effects need to be considered as well. The fly ash of the burnt waste was found to contain heavy metals and elements that might be harmful if emitted to the environment. No correlation has been found between the concentrations of the studied elements found in soil and airborne debris collected on the oil palm trees. However, accumulations of some toxic elements of anthropogenic origins were found in the airborne debris deposited on the oil palm trees.

ACKNOWLEDGEMENTS
The authors would like to thank Universiti Teknologi MARA, Malaysia for the fund, and facilities to carry out the study.

CITED REFERENCES


Lim J.M.,  J.H. Lee and Y.S. Chung (2005). The Distribution Characteristics Of Trace Elements In Airborne Particulates From An Urban Industrial Complex Area Of Korea Using Instrumental Neutron Activation Analysis. Nuclear Engineering and Technology 37, 503-510

Matlock, M. M., K.R. Henke, D.A. Atwood, (2001). Effectiveness of Commercial Heavy Metal Chelators with New Insights for the Future in Chelate Design. Department of Chemistry, University of Kentucky, pp1-13

Mohd. Yaacob  K.,  Abdul. Rahman and Mohd. Rashid M. Yusof, (1989). Air pollution control in palm oil mill industry in Malaysia. Symposium on environmental perspectives towards the year 2000 and beyond, 1-6

Nugteren W H., J. M. Janssen, and B. Scarlett (1999). Improvement of Environment
Quality of Coal Fly Ash by Applying Forced Leaching. International Ash Utilization Symposium 32. 1-6

Rashid M. Y.M., A. W. Khalid and F. S. Azman (1987). Elemental composition of
palm oil mill boiler fly ash. Asian Environment on Journal of environment science & technology, 1-12

Subramanian. V, Y.M. Ngan Choo and N.M. Nik Sulaiman, (2008). Environmental performance of the milling process of Malaysia Palm Oil using the life cycle assessment approach. American journal of environment sciences 4, 310-315

Zarcinas A.B., C.I. Fauziah, M.J. McLaughlin and G. Cozens (2004). Heavy metals
in soils and crops in southeast Asia. Environmental Geochemistry and Health 26. 343–357

Mohd Zahari Abdullah, Ahmad Saat and Zaini Hamzah, (2011). Optimization of EDXRF Spectrometer to analyze Heavy Metals in Moss Samples. American J. of Engineering and Applied Sciences 4 (3): 355-362.

Mohd Zahari Abdullah, Ahmad Saat and Zaini Hamzah, (2012). Assessment of the impact of petroleum and petrochemical industries to the surrounding areas in Malaysia using mosses as bioindicator supported by multivariate analysis. Environ Monit Asses 184, 3959-3969.

 
Table 1. Elemental contents of shell, fiber and fly ash.
Element
Shell
(ppm)
Fiber
(ppm)
Fly Ash
(ppm)
As
5.08
7.15
4.90
Cu
57.6
166.5
192.4
Mn
117.9
251.4
527.1
Ni
30.3
29.6
9.64
Co
0.19
0.39
0.47
V
11.37
34.87
35.74
Hg
0.02
0.03
0.01
Zn
246.1
250.7
246.6

Table 2. Distributions of various elements concentration (ppm) in debris and soil according to direction and distance from mill.


Arsenic

Copper

Nickel

Cobalt

Direction
Dist.
Debris
Soil
Debris
Soil
Debris
Soil
Debris
Soil
North
0.1km
11.19
11.45
86.46
7.68
10.32
17.82
0.33
0.74

0.5km
6.68
10.62
85.73
29.27
17.14
6.91
0.25
0.61

1.0km
6.79
11.66
29.27
19.76
12.82
11.00
0.25
0.49

2.0km
6.87
10.10
19.63
8.05
4.86
11.45
0.31
0.78

3.0km
5.31
14.95
86.46
18.29
11.68
11.45
0.11
0.28
South
0.1km
6.22
9.87
75.98
8.05
11.68
8.73
0.21
0.26

0.5km
10.18
8.01
16.71
6.10
9.86
6.45
0.51
0.22

1.0km
17.05
13.89
103.78
12.93
24.18
14.86
0.48
0.29

2.0km
9.90
26.06
18.17
31.34
12.59
36.91
0.52
0.25

3.0km
7.49
13.68
88.78
13.66
11.91
19.41
0.25
0.25
East
0.1km
6.37
42.23
53.78
19.02
17.59
24.41
0.15
0.20

0.5km
7.82
6.92
32.56
8.17
11.91
5.32
0.42
0.31

1.0km
10.23
16.81
16.46
12.07
13.73
10.32
0.86
0.45

2.0km
6.92
14.90
41.34
16.1
11.91
6.23
0.19
0.17

3.0km
9.51
13.91
30.98
21.22
9.18
8.50
0.52
0.25
West
0.1km
8.13
13.26
48.17
16.34
18.95
14.64
0.30
0.33

0.5km
7.90
18.29
25.61
13.17
9.41
26.91
0.31
0.40

1.0km
7.15
11.11
22.93
7.32
11.32
10.55
0.56
0.25

2.0km
7.49
10.88
19.39
7.68
10.32
11.68
0.65
0.36

3.0km
7.93
6.99
28.29
10.49
6.00
6.00
0.22
0.11



Zinc

Mercury

Manganese

Vanadium

Direction
Dist.
Debris
Soil
Debris
Soil
Debris
Debris
Debris
Soil
North
0.1km
254.0
245.0
0.03
0.03
962.9
29.44
29.44
4564

0.5km
253.3
244.9
0.03
0.02
653.6
27.48
27.48
1256

1.0km
246.8
244.9
0.05
0.04
111.8
27.27
27.27
363.9

2.0km
246.7
245.1
0.03
0.03
81.4
111.6
111.6
1276

3.0km
252.6
245.0
0.04
0.05
766.1
9.71
9.71
560.8
South
0.1km
250.7
245.2
0.03
0.03
468.9
38.83
38.83
1018

0.5km
245.9
244.9
0.03
0.03
254.6
117.5
117.5
1190

1.0km
253.4
245.4
0.03
0.03
1464
46.09
46.09
1323

2.0km
246.2
248.9
0.02
0.02
271.4
119.3
119.3
3508

3.0km
251.7
245.3
0.02
0.04
698.6
79.04
79.04
907.6
East
0.1km
250.2
245.0
0.10
0.05
142.1
11.55
11.55
929.4

0.5km
245.9
244.7
0.04
0.02
57.1
103.6
103.6
1210

1.0km
245.8
245.3
0.03
0.03
96.8
168.00
168.00
3979

2.0km
250.5
245.2
0.05
0.03
261.1
14.48
14.48
698.6

3.0km
247.9
245.4
0.04
0.04
172.9
77.13
77.13
2183
West
0.1km
246.9
245.1
0.03
0.03
197.9
134.4
134.4
1052

0.5km
246.9
246.0
0.03
0.03
137.9
100.2
100.2
2013

1.0km
246.7
245.0
0.02
0.02
151.8
135.2
135.2
3035

2.0km
246.1
245.1
0.03
0.02
87.9
160.0
160.0
3303

3.0km
246.2
244.9
0.04
0.02
70.7
142.57
142.57
327.6







Figure 1. Spatial distribution arsenic, copper, nickel and cobalt in debris studied in the four directions.





Figure 2. Spatial distribution of vanadium, mercury, zinc and manganese in debris studied in the four directions.





[1] Presented at International Plantation Conference (IPC2012, 19-21 Dec. 2012, Bogor, Indonesia.

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