USC Chemical Engineering Student Research Annual 2010

Calorific Values and Proximate Analysis of Sargassum spp. and Ulva spp.
Carlo S. Alburo, Radzwell H. Conje, Maria Gracelda B. Pino, Engr. Patrick U. Tan*
Department of Chemical Engineering, University of San Carlos, 6000 Cebu City, Philippines *Corresponding Author

Abstract The potential of seaweeds, Sargassum spp. and Ulva spp., as biomass for energy production was investigated based on their calorific values. Further, calorific values were correlated with the proximate analysis, which covers moisture, ash, volatile matter and fixed carbon contents of the seaweeds, using multiple linear regression. The calorific value was measured using bomb calorimetry while the proximate analysis was conducted using gravimetric method. The seaweed samples were taken from three different spots in Mactan Island, namely, Cordova, Buaya, and Maribago. It was found that the calorific values of Sargassum spp. range from 8.50 MJ/kg to 12.94 MJ/kg while Ulva spp. have a mean calorific value of 13.48 MJ/kg on dry basis. This shows that the seaweeds have comparable calorific values with those of the conventional biomass fuels like bagasse, rice husks and corn cobs. Correlation between calorific values and proximate analysis for Sargassum spp.and Ulva spp. was finally established in this study as:

CV MJkg= 13.3832-0.1546 M+0.0164 VM-0.0802 ASH with R2 = 0.80.
Keywords: Calorific Values, Proximate Analysis, Seaweeds, Correlations 1. Introduction 1.1. Seaweeds as Biofuels The Philippines has an abundant supply of biomass resources which include agricultural crops (rice hulls, coconut husk and meat, cocoa, cassava and bagasse), saw mill (forest logs) and furniture residues (sawn timber). These biomass resources readily compete with food production and agricultural land [1]. To avoid this competition with food production, a potentially viable alternative is to use aquatic biomass, such as algae, as the feedstock biofuel and bioenergy production.

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Macroalgae (or seaweeds), as biofuel, have the advantage of higher growth rates compared to terrestrial crops and avoids competing with the agricultural land. Moreover, seaweeds can mitigate greenhouse gas emissions since CO2 from flue gas can be utilized as carbon source in algae growth. Aside from that, wastewater can be used to provide nutrients for seaweed growth [2]. Past attempts in utilizing seaweed as source of fuel started in 1970’s oil crisis. Among the programs started to compensate for the energy crisis, the Giant Kelp Program of United States used the brown seaweed Macrocystis pyrifera as energy crop. However the program was discontinued when it was thought that the crisis was over [3]. But with the serious problems posed by global warming and the rapid depletion of oil reserves today, the use of aquatic biomass energy is now being reconsidered as a means of CO2 mitigation. Processes that are now considered for energy generation from aquatic biomass include direct combustion, anaerobic digestion, fermentation to alcohol, thermal liquefaction, thermal gasification, and pyrolysis [4]. In Germany, studies are ongoing for the closed cycle Solar Oxygen Fuel Turbine (SOFT) in which dried seaweeds (specifically Ulva spp.) are combusted in a fluidized bed boiler in Rankine cycle and the combusted products are returned to the cultivation ponds as algae nutrients source [5]. According to Bruton et al. [6], in France, annual green tides generate about 60,000 tons of wet Ulva spp, (or 8,000 tons dry weight) which have been considered to be utilized for local energy production. Seaweed species suitable for biomass energy should display high productivity in terms of standing crop (total amount algae in a specific area at a given time) and biomass yield. The species should be easily cultivated and harvested. Also, chemical composition of seaweeds should be accounted since it determines the fuel quality and dictates the process of energy production [4]. Seaweeds that are considered as potential energy crops include Macrocystis pyrifera, Laminaria, Sargassum and Ulva [3, 4, 6]. These seaweeds are said to have high productivity and biomass yield (45 tons dry weight annually) [2]. Among the five species mentioned above, Sargassum and Ulva species are chosen in this study because of their local abundance and little economic value. Sargassum is a dominant genus in tropical and subtropical waters in terms of standing crop, percent cover and height. Ulva species are common in the intertidal zones of the Philippines, but, at certain times, could overproliferate, producing blooms or ‘green tide’ in some protected bays. Common Ulva species that proliferate in Cebu province are Ulva lactuca, Ulva fasciata and Ulva reticulata [7]. In Mactan Island (Cebu), central Philippines, at least two species constitute the Ulva population, either as free-living or

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attached form. Ulva lactuca mainly consists of free-living population while the species referred to as Ulva reticulata consists mainly of attached population [7]. Ulva species are frequently found in nutrientrich saline waters, attached to the bottom of the waters [8]. 1.2 The Calorific Values Good knowledge of the heating or calorific value of a fuel is needed for heat rate calculations, and modifying operating parameters. Knowing the ash composition of fuels is needed to control of ash-related conditions such as slagging, fouling, or erosion and management of environmental emissions [9,10]. The calorific value of a material is the amount of heat released by a material during combustion. It is affected by the ash and moisture contents of the biomass. The net calorific value or lower heating value is defined as the heat to be removed from the reaction products to obtain a final temperature equal to the initial temperature of the reactants, assuming that the reaction products remain in gaseous phase, i.e. that the heat of condensation of water is not available. On the other hand, the reference state of the water for the gross calorific value (higher heating value) is liquid state. The ash (inorganic) content of a fuel lowers down the calorific value and may cause major problems at high temperature combustion (melting of ash and clogging of reactors) [9,10]. Weber and Zygarlicke [10] reported that ash-related problems, including slagging, agglomeration, corrosion, and erosion, can cause frequent unscheduled shutdowns, decreasing the availability and reliability of the energy source. The calorific value decreases with increasing moisture content. The presence of moisture in fuel lowers its effective heating value since a portion of the heat of combustion is utilized in evaporating the contained moisture, hence decreasing the calorific value. It is highly desirable, therefore, that the moisture content be kept as low as possible [9]. The fixed carbon also affects the heating value of the fuel in such a way that the higher the fixed carbon, the higher the calorific value of fuel. In general, an increase in the ash content corresponds to a decrease in the fixed carbon content and hence a decrease in heating value [11]. Table 1 shows the heating values of commonly used biomass fuels.

Table 1. Typical characteristics of different biomass fuels used commercially for energy generation Type Fruit Stems[1] Calorific Value (MJ/kg) 5 % moisture 63 % ash -

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Oil-palm husks[3] Oil-palm fibers[3] Bagasse[1] Fibers[1] Phaeophyta[2] Chlorophyta[2] Rhodophyta[2] Rice husks[1] Maize Cobs[1] Coffee husks[1] Cocoa husks[1] Groundnut shells[3] Wood[1] Coconut shell[1] Wheat straw and husk[3] Switch grass[3] Charcoal[1]

7-8 7-8 7.7-8 11 9-11 8-13 4 - 12 14 13-15 16 13-16 16.7 8.4-17 18 17-19 18-20 25-32

55 55 40-60 40 9 10-20 10 7-9 3-10 10-60 8 7-15 8-15 1-10

5 10 1.7-3.8 25-45 24-40 20-79 19 2 0.6 7-14 4-14 0.25-1.7 4 8-9 6 0.5-6

Very few studies have been done to establish the calorific values of seaweeds, much less those of endemic seaweeds in the Philippines. Lamare and Wing [12] reported the calorific values of 28 species in New Zealand. Their report showed that for the macroalgae species, the calorific value varies from species to species depending on the type of storage products that range from high-energy polysaccharide starch to mannitol and glycerol. The constituents that contribute to the calorific value of the seaweeds are carbohydrates, proteins and fats, which are all found to differ from species to species. It was reported that Chlorophyta (green algae), Rhodophyta (red algae) and Phaeophyta (brown algae) have different calorific values with Chlorophyta having the highest mean calorific content and the Rhodophyta having the lowest as shown in Table 1. In a similar study, Littler and Murray [13] reported that Chlorophyta had the highest average ash-free calorific content followed by Rhodophyta and lastly Phaeophyta. 1.3 The Calorific Value Determination The calorific value can be determined using proximate analysis or adiabatic calorimetry [14]. However, obtaining data from bomb calorimetry is usually tedious and expensive. For that reason several correlations are devised to predict the higher heating value from the proximate analysis data. Parikh et al. [15] used 450 different types of biomass and presented the correlation: HHV = 0.3536FC + 0.1559VM – 0.0078ASH [ 1]

where HHV is the higher heating value in MJ/kg, FC is the fixed carbon content, VM is the volatile matter content and ASH is the ash content of the sample content in weight % on dry basis.

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Demirbas [16] calculated the calorific values (higher heating values, HHV) of 16 biomass samples experimentally from both ultimate and proximate analyses. The HHV (MJ kg −1) of the biomass samples as a function of fixed carbon was calculated from the following equation: HHV (MJ/kg) = 0.196(FC) + 14.119 (R2= 0.9997) [2]

Sheng et al. [17] gave new correlation between the HHV and dry ash content of biomass (in weight percent) as follows: HHV (MJ/kg) = 19.914–0.2324 ASH [3]

Lamare and Wing [12] correlated ash and calorific values of seaweeds with an R2 of 0.859 as follows: HHV (MJ/kg) = 19.59 – 0.2106 ASH [4]

The major advantage of these correlations is that they allow the determination of HHV of fuels simply from their proximate analysis and thereby provide a useful tool for modelling of combustion processes. These can also be used in examining old/new data for probable errors when experimental results lie much outside the predicted results of HHV [15]. This study sought to explore the possibility of using locally available seaweeds as biomass fuel by comparing their heating values against those of the conventional biomass outlined in Table 1. The study also sought to establish relation between heating values and moisture contents of sun-dried seaweeds and finally correlations between heating values and the proximate analysis were established for Ulva and Sargassum species.

2.

Materials and Methods

2.1 Sampling

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Algal samples were taken from different areas around Mactan Island. The places chosen were dependent primarily on the abundance of seaweeds in one particular place. Ortiz and Trono [18] reported that 72 species of Sargassum are found in the Philippines. Table 2 gives the standing crop of Sargassum beds in Central Visayas.
Table 2. Standing crop of dominant Sargassum spp. in Central Visayas [18] Site Tongo, Mactan Is. Cordova, Mactan Is. Maribago, Mactan Is. Caubyan Is. Danajon Reef Bilangbilangan Is. Olango Is. Standing Crop (kg wet weight per m2 ) 2.5 3.4 2.7 4.9 6.7 2.6 1.28 Dominant Sargassum species S. siliquosum S. binderi S. polycystum , S. oligocystum S. polycystum S. polycystum S. polycystum, S. oligocystum S. polycystum, S. oligocystum and S. siliquosum

In this study, Sargassum polycystum seaweeds were taken from the shores of Barangay Buagsong, Cordova while Ulva lactuca was taken from Barangay Buaya. Both Sargassum oligocystum and Ulva reticulata were taken from the shores of Maribago. The seaweeds were collected during low tides. One liter of seawater samples was also taken during the collection of the species to determine its DO, pH, temperature and salinity. The seaweeds were collected by thallus (vegetative body of algae). Three thalli were collected for Sargassum polycystum, Sargassum oligocystum and Ulva lactuca. The thalli would serve as the samples of each species. There were three samples for each kind of species. And since Ulva reticulata thrive in continuous mats, this species was obtained by composite sampling. The collection of seaweeds was done by hand. Specimens adhering to the seaweeds were removed using knife and the collected species were wrapped in a newspaper and placed in an ice bucket. Water samples were analyzed within 24 hours after they were collected. pH was determined using the pH meter and the salinity was measured using the hand refractometer. The temperature of the seawater and its dissolved oxygen were measured using the thermometer and DO meter, respectively. The seaweed samples were brought to the University of San Carlos Marine Biology Department for identification. The identification of the species was based on their external morphology, color and shape. Pictures of the macroalgae aided the determination of species. 2.2 Preparation of Specimens for Analyses

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The seaweed samples were cleaned with water and the epiphytes (any plant that grows upon or is attached to the seaweeds) were removed. Excess water from the samples was then removed by gently pressing the algae against tissue paper. All the collected seaweed samples were sun-dried. To determine relationship between calorific value and moisture content during sun-drying of seaweeds, one whole thallus of each species, Sargassum polycystum and Ulva reticulata, was sampled for moisture content and calorific values analyses at different intervals of time for three days. A total of seven samples were taken from the whole thallus of each species during the sun-drying period and each sample had three replicates. Also, fresh samples were oven-dried overnight to be moisture free (assumed 0% moisture) and their corresponding calorific values were determined. After all the seaweeds were sun-dried, they were stored and cut into small pieces for the proximate analyses and calorific value determination. The whole experiment was conducted in two trials, one month apart. 2.3 Proximate Analysis Proximate analysis is an indirect method of measuring the calorific value of a sample. It converts the component weights of proteins, fats and carbohydrates in the sample to their equivalent heating values. Proximate analysis requires the values of the ash content, moisture content, volatile combustible matter content, and the fixed carbon in order to determine the heating value of the sample. The Proximate analysis method used in this study was based on AOAC[19]. 2.4 Calorific Value Determination In adiabatic calorimetry, direct combustion of the samples is done in a temperature-controlled bomb. This jacket is maintained at the temperature of the bomb throughout the combustion process to eliminate the heat-leakage. The calorific value of the sample obtained from calorimetry is said to be more accurate than that obtained from proximate analysis [14]. The calorific value was determined using Parr 1108 Oxygen Bomb Calorimeter based on ISO 1928:1995 [20]. Oxygen was supplied at a gauge pressure of 23 atm.

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2.5 Correlations Multiple linear regression analysis was employed to establish the correlations relating the calorific values of seaweeds with their corresponding proximate analysis data. The methods of least squares minimizing the error squared, was used to evaluate the adjustable parameters for each correlation expression [21]. Calculations were aided using the 4-unknown calculator software [22]. Correlation equations established were compared with those in the literature. 3. Results and Discussion

3.1. Calorific Values of Different Seaweed Species from Different Places (Maribago, Cordova and
Buaya) A preliminary run was done to investigate available seaweed species in Maribago, Cordova and Buaya. Table 3 shows the seawater conditions when the seaweed samples were obtained.
Table 3. Seawater conditions of sampling locations

Parameter T (oC) DO (g/ml) Salinity (%) pH

Maribago 30.8 7.17 29 7.99

Buaya 30 3.14 26 8.31

Cordova 30 3.12 36 8.34

In Maribago, the most abundant species were S. oligocystum and U. reticulata. In Cordova, the most abundant specie was S. polycystum. Figure 1 shows the calorific values of different seaweed species harvested.
Figure 1. Calorific Values of Different Seaweed Species from Maribago, Cordova and Buaya

From the Figure 1, it can be seen that the calorific values of Sargassum spp. range from 8.50 MJ/kg to 12.94 MJ/kg while Ulva spp. have a mean calorific value of 13.48 MJ/kg on dry basis which is in agreement with values reported by Lamare and Wing [12]. The results also show that the local species of Ulva and Sargassum collected in Mactan have comparable calorific values with those of the conventional biomass fuels like bagasse, rice husks and corn cobs as cited in Table 2.

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3.2 . Calorific value as a function of moisture content during sun drying The most serious disadvantage of biomass fuel is that they often have high moisture content which readily inhibits combustion [23]. In general, aquatic biomass contains 80 to 90% water [24]. The best way to recover the lost energy because of high moisture content is through drying of biomass. In the study, samples of Sargassum polycystum and Ulva reticulata were sun-dried to minimize the moisture content. It was observed that when the moisture content was still higher than 40%, the calorific value of the seaweed samples could not be determined by bomb calorimetry since no temperature change is observed during ignition. Figures 2 and 3 below show the relation between moisture content of the seaweed and its calorific value for Sargassum polycystum and Ulva reticulata samples, respectively.

In both figures, it can be clearly seen that at moisture content below 40%, the calorific values have negative linear correlations with moisture content consistently in the two experimental trials done. However, Figure 2 shows that the two experimental trials produced different correlations despite involving the same species. This may be attributed to the morphology of Sargassum species. On the other hand, Figure 3 shows that the two trials produced almost identical correlations. Compared to Sargassum species, Ulva species are more homogenous in form and structure hence may promote uniform drying. It is also seen that at moisture content 15% (or below), the calorific value of seaweeds is at par with those of the conventional biomass fuels. Since the two trials produced two different correlations, only correlation of Figure 3, using linear regression, is thus developed as:
moisture content Figure 2. Calorific Value of Sargassum polycystum versus Figure 3. Calorific Value of Ulva reticulata versus moisture content

CVMJkg=11.20—0.098 M
3.3 Correlation between the calorific values of seaweeds and proximate analysis data

[5]

After two to three days of sun-drying, the moisture content of the seaweeds lowered to 10 to 15% by weight. Essentially all seaweed samples have negligible fixed carbon content (~0%) and have high volatile matter (40-75%) and ash content (15-45%) on dry basis as shown in Table 4 and 5. The combustibles of a solid fuel are the volatile matter and the fixed carbon. Since the fixed carbon content is negligible, the volatile matter is the only contributor to the energy of seaweeds.

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Table 4. Proximate analysis and Calorific values of seaweeds for the 1st trial

TRIAL 1 Species Sargassum oligocystum 1 Sargassum oligocystum 2 Sargassum oligocystum 3 Sargassum polycystum 1 Sargassum polycystum 2 Sargassum polycystum 3 Ulva lactuca 1 Ulva lactuca 2 Ulva reticulata Moisture (kg/kg) 15.34 14.66 12.99 12.79 10.36 11.57 15.46 13.26 9.17 VM (kg/kg) 40.60 42.77 45.59 57.83 53.30 59.50 55.70 59.31 70.54 Ash (kg/kg) 44.00 42.57 41.09 29.37 36.30 28.90 28.24 26.61 20.29 CV(MJ/kg) 8.6273 8.8402 9.1552 10.0125 9.7074 10.1191 9.5692 9.6820 10.5727

Table 5. Proximate analysis and Calorific values of seaweeds for the 2nd trial

TRIAL 2 Species Sargassum oligocystum 1 Sargassum oligocystum 2 Sargassum oligocystum 3 Sargassum oligocystum 4 Sargassum polycystum 1 Sargassum polycystum 2 Sargassum polycystum 3 Sargassum polycystum 4 Ulva lactuca 1 Ulva lactuca 2 Ulva lactuca 3 Ulva reticulata Moisture (kg/kg) 14.91 14.55 15.62 17.27 14.41 14.12 14.23 13.71 14.37 11.87 10.23 10.23 VM (kg/kg) 57.02 49.85 54.68 51.89 46.56 49.61 57.35 49.30 64.31 67.80 69.20 75.03 Ash (kg/kg) 28.25 35.64 30.01 31.03 39.42 36.21 42.31 37.69 21.33 20.36 20.55 15.56 CV(MJ/kg) 9.7883 7.8535 9.79368 8.52993 8.79003 8.9893 8.7221 8.9265 11.1842 11.4925 12.2723 11.6259

Ash content is the remaining incombustible minerals of a fuel. Consequently, the calorific value decreases with increasing ash content. In general, fuels should have ash content less than 5% [9]. But seaweeds in this study have been found to have high ash content which would then restrict the direct combustion of seaweeds as biofuels. Figure 4, 5 and 6 are plots of calorific values against moisture contents, volatile matter contents, and ash contents, respectively, covering all the sampled species of Ulva and Sargassum. It can be seen in Figure 4 that the moisture content has a poor correlation with the calorific value, while volatile matter

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content and ash content each have good correlations with the calorific value (R 2 = 0.739 and R2 = 0.723, respectively).

Figure 4. Calorific value versus moisture content

Figure 5. Calorific value versus volatile matter content

Figure 6. Calorific value versus ash content

By multiple linear regression and single linear regression analyses, moisture, volatile matter and ash contents were correlated with the calorific value as tabulated in Table 6 with their corresponding R2. Constraints in the use of these correlations include 10 to 20% moisture content, 40 to 75% volatile matter and 15 to 45% ash content. To measure how well the correlation fits the data, coefficient of determination (R2) was computed. The highest R2 computed was 0.80. This means that 80% of the variation of the calorific values of the seaweed samples has been explained by the linear regression equation established in the study. The correlation equations established were compared with those from literature as shown in Figures 7 and 8. Figure 7 shows that Lamare and Wing [12] and Sheng et al. [17] have almost the same slope while

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the correlation established in the study differed from the two. It can be seen in Figure 8 that the correlation by Parikh et. al.[15] have the almost the same slope with the one established in the study.
Table 6. Correlation equations In this Study Correlation equation In literature R2
0.76 1 0.72 3

Correlation

CV MJkg= 7.8398+0.0626 VM0.0521 ASH CV MJkg= 13.34-0.115 ASH

CV MJkg= 0.3536FC+0.1559 VM-0.0078 ASH CV MJkg= 19.914-0.2324 ASH CV MJkg= 19.914-0.0.2324 ASH

R2 0.99 7 0.89

Reference Parikh et al. [15]

Sheng et al.[17]

0.85 9

Lamare and Wing [12]

CV MJkg= 13.3832-0.1546 M+0.0164 VM-0.0802 ASH

0.80 2

Figure 7. Comparison with established correlations in literature

Figure 8. Comparison with established correlations in literature

4. Conclusion and Recommendation Seaweeds have potential to be used as solid biofuel since they have comparable calorific values to the conventional biomass like bagasse, rice husks and corn cobs. However, seaweeds have to be dried from about 87% to 15% moisture content in order to obtain calorific values close to those of the conventional biomass (9-12 MJ/kg). Moreover, both Sargassum and Ulva species have high ash content (15 %-45%) which may restrict their use in direct combustion.

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In the case of Ulva reticulata species, there was a highly negative correlation between moisture content and calorific values. The last equation on table 6 can be used to predict calorific values of Ulva and Sargassum species. In the case of sun-drying of Sargassum species, more experiments should be conducted to establish a consistent correlation between moisture contents and calorific values. To improve linearity, more species of Sargassum should be included. Because of the high ash content, studies should be performed on the fluidized bed combustor (i.e. Solar Oxygen Fuel Turbine) which operates using seaweeds as fuels and which allows recycling of ash as nutrient source for seaweed cultivation [25]. 5. References [1] Hoi, W. (2003). Potential of biomass utilization for energy in asia pacific sharing of specific experience of Philippine situation. Forest Reasearch Institute. Kepong, Kuala Lumpur Malaysia. [2] Rasmussen, M. and et. al. 2007. Primary Biomass Production from Marine Algae. University of Aarhus : National Environmental Research Institute; Memorandum for VE-net, 2007. [3] Yokoyama, S., Jonouchi, K., Imou, K. (2007). Energy production from marine biomass: fuel power generation driven by methane produced from seaweed. World Academy. 5: 1131-1151. [4] Chywoneth, D. (2002). Review of biomethane from marine biomass. Fuel. 10:1025-1030 [5] Yantovski, E. (2008). Seaweed Ulva photosynthesis and zero emissions power generation. Proceedings of ECOS 2008. 3: 1117-1130. [6] Bruton, T., Lyons, H., Lerat, Y., Stanley, M. and Rasmussen, M. (2006). A review of the of marine algae as a source of biofuel in Ireland. Sustainable Energy Ireland. 13-24. [7] Trono, G. (1997). Field guide and atlas of the seaweed resources of the Philippines. Bookmark, Inc. 264-A Pablo Ocampo Sr. Ave. [8] Hulsbergen, R. (2006). Predicting Ulva growth in a saline Volkelrak-Zoomlake. Delft University of Technology report. 8-19. [9] Quaak, P., Knoef, H., Stassen, H. (1999). Energy from biomass (A review of combustion and gasification techniques). New York, USA. 2-7. [10] Weber, G. And Zygarlicke, C. (2001). Barrier issues to the utilization of biomass. AAD Document Control, 2:765-770. [11] Unesco. (1988). Engineering schools and endogenous technology development. Paris. [12] Lamare, M. and Wing, S. (2001). Calorific content of New Zealand marine macrophytes. New Zealand Journal of Marine and Freshwater Research. 35:335-341. potential cell

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[13] Littler, M., Murray, S. (1977). Analyses of pathways of energy flow. In: Littler, M. and Murray, S. (Eds.). Influence of domestic wastes on the structure and energetic of intertidal communities near Wilson Cove, San Clemente Island. University of California, Davis: California Water. 47-56. [14] Carefoot, T. (1985). Calorimetry. Press Syndicate of the University of Cambridge. In Handbook of Phycological Methods: Macroalgae. New York, USA. 480-490 [15] Parikh, J., Channiwala, S., and Gosal, G. (2004). A correlation of calculating HHV from proximate analysis of solid fuels. Fuel.10.1018 [16] Demirbas, A. (1996). Calculation of higher heating values of Biomass fuels. Fuel, 10:1016-1020 [17] Sheng, C., and Azevedo, J. (2004). Estimating the HHV of biomass fuels from basic analysis of data. Fuel. 10.1020. [18] Ortiz, A., Trono, G. (2000). Growth and reproductive pattern of intertidal and subtidal Sargassum (Sargassaceae, Fucales) population in Bolinao, Pangasinan. Science Diliman. 12:2:45-50. [19] Williams, S.(2002). Official Methods of Analysis of A.O.A.C. AOAC International. Maryland, USA. [20] Determination of gross calorific value by the bomb calorimetric method, and calculation of net calorific value [21] Walpole, E., Myers, R. And Myers, S.(1998). Probability and Statistics for Engineers and Scientists. Prentice Hall, Inc. New Jersey, USA. [22] http://www.1728.com/unknwn4.htm [23] Henrich, R., Vodegel, G., Kocj, M. (2004). Definition of standard a biomass. RENEW. [24] Hennenberg, K., Fritsche, U., Herrera, R., (2009). Aquatic biomass: sustainable bioenergy from algae? Oko-Institut, Darmstadt, Germany. 6. Acknowledgement The researchers would like to express gratitude to Dr. Anthony Ilano, PhD and the University of San Carlos Marine Biology Department for helping with the identification of the seaweed species and allowing the researchers to use Marine Biology Laboratory for the analyses of the seawater samples.

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