c Ê
 


    

 ¹Subhash Hathurusingha, Pramod Shrestha, Nanjappa Ashwath

 Centre for Plant and Water Science, CQ University, Bruce Highway, Rockhampton
 4701, Australia

 ¹s.hathurusingha@cqu.edu.au, +61749232110.

Ô 

 

 

c ºatty acid profiles (ºAP) of kernel oil extracted from four central Queensland weed species
cc were studied. Oils were extracted by standard n-hexane double extraction and were analysed
c by gas chromatography using the official method of American oil chemist¶s society. Kernel
c
oils of ‰

 sp.  sp  
 

 seemed to have suitable ºAP for
c biodiesel production. However, the potential of u
  was difficult to
c comprehend due to its relatively lower oil content, higher acid value, very high amount of
c unsaturated fatty acids and low cetane numbers.

cÔ 
c 



c Ê
 

 
  



 

c 



 åver increasing demand for energy and steep decline in fossil fuels have embarked

developing and developed countries in an agitated position. This issue has become intensified
 to an extent where edible crops and arable lands are compromised. Scientist are now
 exploring potential feedstock that apparently having low or zero economic value and are
 resilient enough to tolerate marginal environmental conditions.

Ô One such group are environmental weeds. u
‰ (Papaveraceaeè‰

sp

 (Rutaceae)  sp ‘ Ochnaceae) and 

 (Arecaceae) are classified as

c
 weeds in Australia. u
 ‰ is a coarse erect herb which extrudes a milky sap

 and has prickly stems and leaves (Stone and Benjamin, 1970). ‘ Ît bears oblong/ellipsoid

c capsules that are 3-4cm long, having numerous seeds (Wagner   1999). 



 is a large palm that grows 20 m in height, with trunk up to 0.6 m wide. Ît yields


ovoid fruit, 2.5±3 cm long, 1±2 cm wide and turns yellow to orange when ripe (Weeds

 Australia, 2010).

  sp. is a small trees or shrub that grows up to 2-7 m in height and 6-16 cm in diameter,

 the species is deciduous and bears drupes (10-12 × 6-7 mm), base slightly curved ,apex

Ô obtuse and turns from green to black when ripe (ºlora of China, 2007). ‰

 sp. is an

 evergreen small tree or shrub that reaches 12 m in height. Ît bears ellipsoid fruit, 0.8±2 cm

 long, containing 1 or 2 hairy seeds. Ît turns red when ripe (Weeds Australia, 2010).

 They possess favourable characteristics such as profuse fruiting, resilience and high kernel oil
c content (>18%) (Ashwath et al., unpublished). Due to their inherent competitiveness, large
 establishments of these species should have strict control mechanisms to avoid them from

escaping the plantation. Main advantage of weeds is that it requires zero to very little
 maintenance. Weeds are resistant to pests and diseases. They are also extremely efficient in
 utilizing available soil nutrients.

 ºatty acid profiles (ºAP) of these selected weeds have never been reported in scientific
Ô literature. This paper describes physicochemical properties of oils from selected weed species
 found in central Queensland, Australia with special reference to their ºAP. ºAP is extremely
 important in evaluating the potential of any biodiesel feed stock as chemical composition of
 oil directly effects the quality of resultant biodiesel (Ramos et al., 2009).

c 

 




 


 ‰ ‰


 Seed collection was carried out in October 2009. They were collected
Ô from................................and were immediately transported to the lab. Seeds were soaked in
 water, air dried, deshelled and oven dried at 40 ºC. Dried kernels were then grounded and oils
 were extracted using standard n-hexane double extraction at 25 ºC. Kinematic viscosity at 40
 ºC was measured using Cannon ºenske Opaque capillary viscometer by ASTM D445 method.
c Density and acid value were measured by ASTM D1250 and ASTM D664 methods. Oils
 were methylated by the official method of the American Oil Chemist¶s Society (AOCS).

Methylated oils were then injected (1.5 µl) to HP 6890 series GC equipped with a 150 psi
 inlet manifold and a flame ionization detector (ºÎD) and fatty acids were separated using HP
 ÎNNOwax 30 m x 0.25 mm x 0.25 µm. Oven temperature was set to remain at 150 ºC for 1
 minute and then increase to 230 ºC at 2.9 ºC/min rate and then to remain at 230 ºC for 1
Ô minute. Detector temperature was programmed to 260 ºC. Split ratio was set at 20/1. Air flow
 was programmed at 450 ml/min and carrier gas (H2) flow and N2 make up flow was set at 40
 ml/min and 45 ml/min respectively. Analyses were performed in duplicate and fatty acid
Ô methyl esters were identified by comparison of retention times with authentic standards
Ôc (SUPå CO 18918 ºAMå standard mix) and quantified by AOCS official reference method.
Ô

Ô
Saponification Number (SN) and Îodine Value (ÎV) of oils were calculated using fatty acid
Ô methyl ester compositions of oil with the help of åqs. (1) and (2), respectively (Kalayasiri et
Ô al., 1996):

Ô SN = ™ [(560 x Ai)/ MWi], (1)

ÔÔ ÎV = ™ [(254 x D x Ai)/ MWi], (2)

Ô Where, Ai is the percentage, D is the number of double bonds and MWi is the molecular
Ô mass of each fatty acid. Cetane number (CN) of ºAMås was calculated from åq. (3)
 (Krisnangkura, 1986)

c

 CN = 46.3 + 5458 /SN ± 0.225 x ÎV (3)


 


 Majority of the selected weed species had appreciable kernel oil content (Table 1) and based
 on the intensity of fruiting, the form, the size and spacing, these plant species have a potential
 to produce commercial oil yield. Kernel oils of most of the species except u

Ô  have recorded lower acid values. Oils having lower acid values are ideal sources
 for making biodiesel since they can be converted to methyl esters using standard protocols
 (Canakci and Van Gerpen, 2001). However modified transesterification protocols can be used
 to overcome that issue (Sahoo et al., 2007). În terms of viscosity, all selected weed species
c have recorded controllable values. Kernel oils of all other weed species, except ‰

 sp.
 had acceptable density. Density and viscosity if oil is substantially reduced during the

conversion of triglycerides and free fatty acids into their corresponding methyl esters
 (Peterson et al., 1986).

 (Însert Table 1 here).


Ô ºatty acid composition of the feedstock directly influences the quality of resultant biodiesel
 (Ramos et al., 2009). Kernel oils of all weed species had relatively suitable fatty profiles for
 them to be used as sources for biodiesel (Table 2).‘Kernel oils from 

and
c  sp. recorded higher amount of saturated fatty acids and in contrast, kernel oils from
cc u
  and ‰

 sp. recorded higher amount of unsaturated fatty acids.
c Saturated fatty acids crystallize at higher temperatures (Cankci and Van Gerpen, 2001) and
c
oils having very high amount of saturated fatty acids have higher cloud points. This
c indicates that 

 and  sp. may not be suitable candidates for
c biodiesel feed stock in countries having cooler climate. However, higher amount of short to
c medium chain saturated fatty acids result in better ignition characteristics (Knothe, 2005).
cÔ
c Unsaturated fatty acids are important to maintain oil and the resultant biodiesel in liquid form
c (Azam et al., 2005) but if they exceed a certain limit can cause formation of peroxide
cc polymers at higher temperatures. În that context, the potential of u
 
ccc becomes doubtful due to its very high unsaturated fatty acid content (82.6%).
cc
cc
(Însert Table 2 here).

cc ºatty acid methyl esters (ºAMå) of selected weed species had higher (>200) saponification
cc values (Table 3). Saponification number (SN) represents the number of milligrams of
cc potassium hydroxide or sodium hydroxide required to saponify 1g of fat under the conditions
ccÔ specified. Ît provides a measure of the average molecular weight (or chain length) of all the
cc fatty acids present (Knothe 2006).

cc ong chain fatty acids found in fats generally have low saponification value because they
c have a relatively fewer number of carboxylic functional groups per unit mass of the fat as
cc compared to short chain fatty acids. Higher saponification numbers in ºAMå of selected
c weed species may be due to relatively higher percentage of short to medium chain fatty acids.

c
(Însert Table 3 here).

c All selected weed species except u
  recorded cetane numbers higher than
c ASTM (American standard for testing materials) standard values. Cetane number (CN) is
c widely used as diesel fuel quality parameter related to the ignition delay time and combustion
cÔ quality. Higher cetane numbers give better ignition properties (Meher et al., 2006). An
c adequate cetane number is required for good engine performance. High cetane numbers help
c ensure good cold start properties and minimize the formation of smoke.

c
 u
  and ‰

 sp. recorded acceptable iodine values but 

c
c
 and  sp. had unacceptably lower iodine values. Îodine value is a measure
c
 of total unsaturation within a mixture of fatty acid. Ît is expressed in grams of iodine which
c

react with 100 g of the respective sample when formally adding iodine to the double bonds
c
 (Knothe et al., 2005). This also supports the previous claim that 

 and
c
  sp. may become solidified at moderate temperatures.

c
 

c
Ô 



c
 Most of the kernel oils extracted from the selected weed species have acceptable
c
 physicochemical properties for them to be used as feed stock for biodiesel. 

c
and  sp. can be recommended as a biodiesel feed stock in countries having
cc tropical climate. Due to relatively lower oil content, higher acid value, very high amount of


c unsaturated fatty acids and low cetane number the potential of u
  as a
c
viable feedtock for biodiesel becomes doubtful.

c 
c 
c
cÔ Azam MM, Waris A, Nahar NM. Prospects and potential of fatty acid methyl esters of some
c non-traditional seed oils for use as biodiesel in Îndia. Biomass and Bioenergy2005; 29: 293-
c 302.
c Canakci, M., Van Gerpen, J. (2001) Biodiesel production from oils and fats with high free
cc fatty acids, 
  uu Vol. 44, pp-1429±1436
c ºlora of China (2007). Vol. 12. pp 361, 362. Science Press, Beijing, China and Missouri
c
Botanical Garden Press, USA.
c 
               
     

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c 
 
 
 c Ô
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c     "  #$
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 c 
 !

c Knothe G, 2005. Dependence of biodiesel fuel properties on the structure of fatty
c acid alkyl esters ºuel Process Technology 2005; 86:1059±1070.
c Knothe, G. (2006) Analyzing biodiesel: standards and other methods, È
u

cc  
, Vol. 83, pp 823±833.

c Meher C, Vidya Sagar D, Naik SN (2006) Technical aspects of biodiesel production by
c
transesterification±a review,   
 , Vol.10, pp 248±268

c Peterson, C. . (1986). Vegetable oil as a diesel fuel: status and research priorities.
c 
  uu , Vol. 29, pp 1413±1422.
c Ramos, MJ, ºernández CM, Casas A, Rodríguez , Pérez A. (2009) Înfluence of fatty acid
cÔ composition of raw materials on biodiesel properties, Ê
 
, 100: 261-268.
c Sahoo, P.K, Das, .M., Babu, M.K.G., Naik, S.N (2006) Biodiesel development from high
c acid value polanga seed oil and performance evaluation in a CÎ engine,  e, Vol. 86, pp 448-
cÔ 454.
cÔc Stone, Benjamin C. 1970. The flora of Guam. Micronesica 6:1-659.


cÔ Wagner, Warren ./Herbst, Derral R./Sohmer, S. H. 1999. Manual of the flowering plants of
cÔ
Hawaii. Revised edition. Bernice P. Bishop Museum special publication. University of
cÔ Hawaii Press/Bishop Museum Press, Honolulu. p1919.
cÔ Weeds Australia (2010) National Weeds Strategy, Australian Weed Committee,
cÔ http://www.weeds.org.au/cgi- bin/weedident.cgi?tpl=plant.tpl&ibra=all&card=T22, accessed
cÔÔ in 27/03/2010
cÔ
cÔ
c
cc
c
c

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cc 

c 

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c 

Ô
c 

c Physicochemical properties of kernel oils

    
   !      " %& 

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 41.6 3.78 3.49 0.06 15.50 0.06 0.94 0.06

‰

 sp. 21.9 0.36 2.14 0.05 19.47 0.03 1.11 0.02
sp 31.2 0.00 6.81 0.03 15.53 0.03 0.87 0.02
u
 18.4 5.40 141.01 0.02 12.01 0.06 0.89 0.07

cÔ *Values are means standard error of three replicates.

c
c

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c
cc
c
c

c
c
c
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c
c



c 'ºatty acid composition of kernel oils*

º   
   



‘ 

‘ 
 ( ‘ ‘ ‘‘


Octanoic acid 8:00 3.7 1.9 - - -

Decanoic acid 10:00 3.0 0.03 - - -
 
auric acid 12:00 28.7 0.7 - - 0.5 0.001

Myristic acid 14:00 11.5 0.1 - - -
   
Palmitic acid 16:00 10.9 0.2 18.9 0.02 51.8 0.002 12.8 0.001

Palmitoleic acid 16:01 - 7.6 0.001 - -
   
Stearic acid 18:00 2.9 0.02 12.0 0.002 3.2 0.003 4.0 0.002
   
Oleic acid 18:01 33.8 0.7 21.4 0.01 31.1 0.003 27.5 0.002
   
inoleic acid 18:02 5.4 0.1 33.1 0.01 14.0 0.003 55.1 0.002

inolenic acid 18:03 - 5.5 0.01 - -

Arachidic acid 22:00 - 1.5 0.01 - -
Saturated ºA N/A 60.8 32.4 54.9 17.4
Unsaturated ºA N/A 39.2 67.6 45.1 82.6


 *Values are means standard error of three replicates.






Ô





c












  ) Saponification number (SN), Îodine value (ÎV) and cetane number (CN) of fatty

Ô acid methyl esters of selected weed species.



  
©  ‰

 

‘ 

‘ 
 ( ‘  ‘


SN N/A 239.9 203.9 209.0 201.8
ÎV 115 40.2 101.8 53.3 124.5
CN 47 60.01 50.15 60.41 45.33



c