Renewable and Sustainable Energy Reviews 91 (2018) 165–179

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

An overview of marine macroalgae as bioresource T

a,b,⁎ c c c d e
K. Sudhakar , R. Mamat , M. Samykano , W.H. Azmi , W.F.W. Ishak , Talal Yusaf
a
Automotive Engineering Centre, Universiti Malaysia Pahang, 26600 Pekan, Pahang, Malaysia
b
Energy Centre, Maulana Azad National Institute of Technology Bhopal, 462003, India
c
Faculty of Mechanical Engineering, Universiti Malaysia Pahang, 26600 Pekan, Pahang, Malaysia
d
Faculty of Bioengineering & Technology, Universiti Malaysia Kelantan, 17600 Jeli, Kelantan, Malaysia
e
School of Mechanical Engineering, University of Southern Queensland, Toowoomba, QLD 4350, Australia

A R T I C LE I N FO A B S T R A C T

Keywords: Environmental, economic and political pressures have driven the interest towards the search of sustainable
Macroalgae feedstock for biofuel production. At present, macroalgae (green, brown and red marine seaweed) is getting
Biofuels growing consideration as an alternative resource for sustainable biomass to produce biofuels, biochemical and
Bioenergy food. The unique chemical composition and wide variation in the availability create various opportunities and
Anaerobic digestion
also challenges for bio-based energy production. Recently, numerous studies have taken place in the exploitation
of seaweed as carbon sources for the bioethanol production. Thus, this paper attempts to highlight the char-
acteristics, processing techniques and potential applications of the seaweed. The present review also focuses on
recent innovative approaches for the sustainable production of bioenergy from seaweed.

1. Introduction renewable energy on an industrial scale have been initiated using solar,
wind, biomass, and so on, but producing biofuels for transportation
The world has realized the effects of greenhouse gas emissions requirements is one of the most promising sources for alternative en-
(GHGs), primarily the CO2 linked to unsustainable energy production ergy [5]. Development of renewable, green, sustainable and efficient
and consumption pattern. Currently, 84% of the primary global energy energy sources for clean electricity and liquid biofuels has become
consumption comes from the fossil fuels such as coal, natural gas, and necessary for sustainable development in recent years [9]. Shifting the
oil [1]. It is estimated that the world energy demand will continue to production of fossil fuels based chemicals to renewable raw materials
increase by 36% (from the current 12,300 Mtoe to 16,700 Mtoe) by the has received more considerable interest due to the concerns regarding
year 2035 [2]. The transportation sector accounts for about 30% of the the effects of the continued use of fossil fuels on the climate. Biofuels
world's total energy consumption, and this consumption is expected to have emerged as an alternative energy source in transportation and
rise with the demand for transportation of goods and people [1,2]. Also, aviation sector to replace conventional gasoline based fuels [10]. Macro
the transportation sector accounts for about 80% increase in world fuel and microalgae represent as the most promising bio-feedstock for re-
consumption over the 2006–2030 period [3,4]. newable fuel production [11–14]. Both microalgae and microalgae re-
It is reported that exceeding the threshold limit (about 450 ppm) of quire sunlight [15], water, nutrients and carbon dioxide to produce
CO2 atmospheric concentration would provide no further chance of energy. The rationale for producing biofuel from algae feedstock is
reversing the global warming and environmental impact [5,6]. These driven by the land-food-fuel-nexus and indirect land use change. There
imply that the utilization of conventional fossil fuels must be stopped are considerable numbers of scientific investigations available on mi-
before the exhaustion of the fuel reserves and the environment. The croalgae biofuel production. However, there are fewer review and ex-
prolonged and intensive use of fossil fuels, the declining of the oil re- perimental studies reported on biofuel production from macroalgae.
serves, and the impacts to the environment has prompted the search for The academic, biological, environmental, and economic significance of
more efficient and cleaner technologies [5,7]. It is in urgent need for seaweeds specifically macroalgae is not widely valued and discussed.
the world to look for new sources of energy and to develop alternative Till date, most academic papers focused on anaerobic digestion of
fuels which are renewable and inexhaustible. Clean and sustainable seaweed; very few have dealt with other approaches for seaweed-based
energy is considered as a strategic option to decrease the CO2 atmo- biofuel production. As such, this review aims to synthesize the litera-
spheric emissions, improving energy self-sufficiency; energy security, ture and provides an essential perspective on the production of sus-
and economic stability of the nation [8]. Although efforts to produce tainable biofuel from seaweed. These study also aims to provide a better

⁎
Corresponding author at: Automotive Engineering Centre, Universiti Malaysia Pahang, 26600 Pekan, Pahang, Malaysia.

https://doi.org/10.1016/j.rser.2018.03.100
Received 27 May 2017; Received in revised form 25 November 2017; Accepted 31 March 2018
1364-0321/ © 2018 Elsevier Ltd. All rights reserved.
K. Sudhakar et al. Renewable and Sustainable Energy Reviews 91 (2018) 165–179

understanding of the marine biorefining approach for sustainable pro- 1G biofuels [21]. Techno-economic and sustainability aspects of in-
duction and consumption of seaweed. However, considering that fossil dustrial-scale 2G biofuels are still not been well established [22].
diesel is the most used fraction in the transportation sector, this paper
throws some light on biodiesel produced from macroalgae. 2.1.3. Third generation (3G) biofuels
This review study serves three (3) primary purpose: Third generation biofuels refers to the bio-oil made from low-input
and non-food microbial feedstock within the realm of algae [23]. They
1. To identify the main seaweed producing countries and describing often derived from high-yield microalgae and macroalgae biomass. 3G
the potential technologies of seaweed cultivation across the globe. biofuels seem to be the most promising innovation to address the cri-
2. To describe the chemical composition and characteristics of sea- tical environmental problems such as CO2 sequestration and waste-
weed focussing on innovative approaches of using different com- water treatment. Algae offer the potential of higher lipid productivity
pounds for biofuel production. using waste or salt water in the areas that not presently used for agri-
3. To investigate and identify the various technologies for producing cultural food production [24]. 3G biomass has the significant merits of
biofuels from marine seaweed. not competing with the land, low lignin content, less energy input and
reduced food-fuel competition [25]. They are engineered explicitly
2. Biofuels: classification and perspectives through molecular biology techniques to improve the biomass conver-
sion to biofuels [26,27]. However, state of the art and the current
2.1. Classification of biofuels technology prohibits the diffusion and exploitation of algae for bio-
diesel production [28].
Biofuels typically categorized by source, type, and generation. They
are broadly divided either as primary biofuels (firewood, agro-residues, 2.1.4. Fourth generation (4G) biofuels
organic material) that are utilized directly in unprocessed form or as a Fourth generation biofuel or next-generation biofuels proceeds one
secondary biofuel (charcoal, ethanol, biodiesel, bio-oil, biogas) that step further to produce ultra-clean carbon-negative biofuels along with
processed from biomass. They are generally in solid (wood, charcoal), carbon sequestration. 4G biofuels are expected to be carbon negative
gaseous (biogas) and liquid form (bio-oil, ethanol, biodiesel) [16]. both at the level of the raw material and process technology [29].
Biofuels are further classified into first, second, third and fourth gen- Table 1 highlights the merits and demerits of a different generation of
erations based on the biomass feedstocks and the processing technology biofuels.
[17]. The classification of biofuels is illustrated in Fig. 1.
A variety of biomass sources (energy crops, food, short-rotation
crops, agricultural waste) could be exploited to generate biofuels. 2.2. Perception of biofuels
However, the energy output significantly depends on the specific type
of biomass used for the conversion process. The share percentage of biodiesel production has been increased in
countries such as Spain, United Kingdom, Argentina, Austria, Colombia
and Indonesia, while has decreased in other top countries such as the
2.1.1. First generation (1G) biofuels USA, Italy, and Belgium [24,26,28]. Among the liquid fuels used for
First generation biofuels or conventional biofuels are derived from transportation, biofuel has contributed 1.8% globally while fossil fuels
the food crops. These fuels are produced through relatively well-es- are making up 92% of the global use. In fact, biofuel can be an excellent
tablished and straightforward processes like fermentation, transester- opportunity for the government to reduce their fuel imports and de-
ification and anaerobic digestion [17]. The production of the 1G bio- crease the environmental impact caused by the conventional fuels.
fuels from plants such as soybean, corn, maize, sugar cane has a Fig. 2 shows the benefit of the biofuels. The continued increase in the
substantial impact on food prices which is not sustainable in the long oil prices, high dependency on the fossil fuels and the rapid growth of
run. The 1G biofuels constitute the most common and widely used GHG emissions drives the need and production of biofuels. Consider-
original biofuels in the world [17]. able attention has been paid to promote the use of liquid biofuels in the
transportation sector and to make it sustainable in the long run. To
2.1.2. Second generation (2G) biofuels date, biofuels are mostly produced using agriculture and food feedstock
Second generation biofuels or advanced biofuels are produced from which poses a significant problem in the refining technologies.
a wide range of non-edible plant biomass, agro-residues and lig- The environmental effects of biofuels represented the most con-
nocellulosic feedstocks [18]. These generation biofuels use non-food troversial factors and been debated in numerous studies [29–32]. Most
crops such as cellulosic biomass which represents an excellent oppor- recent analysis of second-generation biofuels [31,33,34] shows a posi-
tunity to overcome the “food versus fuel” disadvantage of 1G biofuels. tive benefit on net GHG emissions. The fundamental question is whe-
Biofuels produced from this generation uses technologies such as a ther the use of biofuels reduces the land requirement and greenhouse
thermochemical, biochemical, and enzymatic process to produce the gas emissions by limiting the use of conventional fuels [30]. The impact
bioethanol, syngas, and pyrolysis oil-based fuels [19]. 2G biofuels of biofuels on GHG emissions depends on the type of technology,
overpass the environmental and social impact. However, its low net feedstock, energy used, and mode of transportation [35]. Secondly, vast
energy yield, feedstock transportation difficulties, high downstream areas of land are needed to produce an adequate amount of biofuels to
processing costs, moderate reduction of the Greenhouse gas (GHG) substitute a significant quantity of fossil fuels. Also, the intrinsic hy-
limits their use [20]. Conversion of cellulose raw material to sustainable groscopic characteristics and stability issues make it difficult to trans-
biofuel poses competitive, technical and cost challenges compared to port and to store. The presence of specific fatty acid methyl esters tends

Fig. 1. Classification of biofuels.

Biofuels

Source Type Generattion

Prim
mary Seco
ondary Solid Liquid Gaeous First S
Second Third Fourth

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Table 1
Pros and cons of biofuels generations.
Generation Sources Pros Cons

First generation biofuels Corn, Cane, Maize, Soybean, Sunflower, Palm, Rapeseed Straightforward and well-established Food vs. Fuel issues.
Oils. technology.
Ethanol. Scalable and cost-competitive process. Lowland use efficiency.
Biodiesel. Low yield and limited availability of arable
land.
Net energy negative.
Second generation biofuels Non-food energy crops like Jatropha, Neem, Castor, Non-food biomass and grow on marginal Industrial scale is an issue.
Lignocellulose, Switchgrass. land.
Straw and waste sources. Environmental sustainability. High capital cost.
Less controversial. Not widely available for use.
Less GHG emissions.
Third generation biofuels Energy crops for bio-alcohol. High biomass yield. Low energy output.
Hydrogen from algae. Less energy input. Pilot-scale yet to be commercialized.
Oil from macro and microalgae. Widespread availability.
Carbon neutral.
Fourth generation biofuels Solar fuels. Aimed to be carbon negative. Laboratory scale/conceptual stage.
Artificial Photosynthesis.
Genetically modified algae.
Flue gasses.

impact and market potential compared towards four biofuels genera-

tions are illustrated in Table 2.
Renewable
energy 3. Seaweed: classification and composition
source
Water surface (Oceans and Seas) covers 72% of the earth's surface.
As such, oceans play a fundamental role in maintaining the planet's
atmosphere, temperature and the natural sequestration of CO2.
Better use
Less Seawater dissolves approximately 60 times more CO2 than the atmo-
of land Benefits of environmen sphere and three-thousand times more than sedimentary rocks. Also,
with little Biofuels tal impact over 96% of all water on earth is seawater. Photosynthetic efficiency
value
(PE) of marine micro & macroalgae are significantly higher than ter-
restrial plants [36].

3.1. Macroalgae vs. microalgae

Agricultural
development
Algae are the only primary producers in the oceans - an area that
covers 72% of the earth's surface. Algae is also the source of fossil
carbon found in crude oil and natural gas [37]. Aquatic and photo-
Fig. 2. Benefits of biofuels. synthetic plant-like organisms are commonly referred as algae. They
have simple reproductive structures and do not have advanced struc-
Table 2 tures like roots, stems, leaves, vascular tissue. They usually microscopic
The role of critical environmental innovation towards biofuels generation. in nature and distributed in the ocean water, fresh water, and waste-
water.
Reduction in Current
Algae available in a diverse group of organisms, containing several
environmental risks Market
potential hundreds of thousands of known species, differing in size, morphology,
physiology, life cycle, and occurrence. An alga ranges from micrometers
First generation Low High Negative Medium to several tens of meters size. The smallest unicellular which not visible
Second Moderate medium Medium Medium
to the naked eye is called microalgae and the larger ones perceived
generation
Third generation High low Medium/low Low without the aid of microscope is called macroalgae. Microalgae have
Fourth High low Medium/Low Low many different species with varying compositions and may grow in salt,
generation fresh or greywater [38,39].
Microalgae live widely as single cells or colonies without any spe-
cialization [40]. The four dominant group of microalgae is the Ba-
to give poor cold flow properties which are inherent in oxygenated cillariophyceae (diatoms), Cyanophyceae (cyanobacteria or blue-green
biofuels; moving towards non-oxygenated biofuels to overcome the is- algae), Chlorophyceae (the green algae), and the Chrysophyceae
sues of corrosion. The economic feasibility of biofuels usage in trans- (golden algae). Despite the fact that algae growth is more natural and
portation sector depends mainly on the technological innovations and more controllable, their microscopic size makes subsequent harvesting
the political impulse regarding subsidies and incentives. The tendency more difficult [41]. Microalgae are photosynthetically more efficient
towards a new generation of biofuels is primarily aimed to balance the than terrestrial plants, and they are very effective in capturing of CO2
environmental and ecological sustainability. The environmentally cri- from the atmosphere, industrial flue gasses and soluble carbonates
tical innovation is defined as the type of innovation able to cause a (NaHCO3 and Na2CO3). It takes roughly two tons of CO2 to produce one
substantial reduction in environmental risks. The contribution of bio- ton of microalgae biomass. Microalgae have short harvesting cycle
fuels innovation based on the significant technical advance, social (1–10 days) owing to higher growth rate and doubling time, so the

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Table 3
Distinction between macro [48] and microalgae [39].
Macroalgae (Seaweeds or sea plants) Microalgae Similarity

Many different species and fewer pests/invasive species Easier growth control. No fertilizers needed
Lower ash and moreover, fewer salt content Fast growing
No food or fuel debate
Can use Industrial Wastewater No need for grinding
No added water required Easier to genetically manipulate
No land required Better for landlocked countries
Simpler to cultivate and easy to harvest Higher HHV & lipid content
Mostly carbohydrate & some protein – Carbohydrate, Lipids & protein

biomass and oil yield is higher compared with other plants (Table 3) Thallus: The simple or more advanced body like structure is known
[42–44]. as a thallus. All sections of the thallus can photosynthesize.
Marine algae are one of the important primary producers (photo- Lamina or Blades: The main photosynthetic leaf-like flattened por-
synthetic). They are referred by a generic term “seaweeds” or informal tions which absorb sunlight.
term macroalgae [45]. Seaweeds or Macroalgae are the large primary Floats: Gas-filled bladders or floats is an organ between the blade
producers of the sea. While some thought to be the precursors of plants, and stipe. Floats may contain carbon monoxide or pneumatocysts. It
algae do not have the same structures as plants (roots, stems, and is used to keep the blades near the water's surface where more light
leaves). Though more intricate than the unicellular algae, seaweeds still is available for photosynthesis.
lack the complex structures found in plants. Seaweed is a large, diverse Stipe: Stipe is a stem-like structure found in some macroalgae spe-
group of amazing aquatic plants like species. Seaweed is becoming es- cies. The stipe can be long and tough to provide support. It acts as an
sential in aquaculture as it does not compete with other crops for land attachment for the blades. It carries sugars from the blades to the
and freshwater [46]. Furthermore, seaweeds have rapid growth rates, rest of the plant.
high biomass yield, and high polysaccharide content. It possesses all Holdfast: A specialized root-like structure that holds the plant to the
essential qualities for biofuels production. Sugar kelp is one of the bottom surface or rocks. It does not penetrate through the sand or
promising species of marine algae which can be a source of biofuels if mud neither aid in gathering nutrients.
sustainably produced and used [47]. Frond: Referred as combined part of the blade and stipe.
Microalgae grow in any water habitat, whereas most macroalgae
species can be found in the marine environment. Algae due to its di- 3.3. Classifications of the seaweed
versity use different components of light spectra and the diversity of
algae species are attributed to the presence of specific light-capturing Marine macroalgae are mostly benthic organisms that are divided
pigments. Kelp forests created by large brown algae have very high into three major groups according to their photosynthetic pigments.
productivity to even above 3000 gCm−2year−1. Seaweeds are the The distribution of seaweeds depends on various environmental factors
dominant autotrophic biomass, and it provides food and shelter for and most importantly the quality and quantity of sunlight. Several
associated fauna [49]. species of seaweed reproduced asexually by means of vegetative
growth. In this process, an alga reproduces new individuals that are
genetically identical to the parent algae. Approximately 10,000 species
3.2. General structure and characteristics of seaweed exist in nature. Jard et al. [50] classified seaweeds into
three broad categories: green, red and brown seaweeds. The various
Seaweed is available in the diverse group with common structure, classifications of seaweed are listed in Table 4.
only difference they do not have actual leaves, stems, and roots. A ty-
pical seaweed structure is shown in Fig. 3 [48]. Seaweed is multi- 3.4. Compositions of the seaweed
cellular eukaryotic aquatic plants (approx. 9000 species) exhibiting
differentiated cell structure and function and is commonly more to- The seaweed is significantly different from terrestrial plants.
wards plant-like. The specific characteristics of each seaweed family are Compared to terrestrial biomass, macroalgae contain high contents of
compiled and shown in Table 4 [45–48]. They have simple re- water (90% fresh wt.), Carbohydrates (25–50% dry wt), protein
productive structures with the absence of vascular tissue. In their nat- (7–15% dry wt.) and low lipid contents (1–5% dry wt). Table 5 shows
ural setting, macroalgae grow on rocky substrates although in some the composition of macroalgae along with its constituents.
cases they are attached to sand particles. They form a stable, multi- The growth cycle of seaweed is shown in Fig. 4. The average bio-
layered vegetation capturing of available photons from sunlight. mass yield and the trace element present in the seaweed are as follow
[54,55].

○ Yield (20 t per hectare per year).

○ Dry matter (6–39%).
○ High carbohydrate fraction (up to 60%; but only 30–40% hexoses,
C-6).
○ Low lipid levels (up to 4.5%).
○ Nutrients proteins and amino acids (17–44%).
○ Bioactive components: fucoidan, fucoxanthin, laminarin (β−1,3
glucan), mannitol, alginic acids, high-M alginate, Pigments, anti-
oxidants, vitamins, and minerals.
○ Polyphenols.

Fig. 3. A typical seaweed structures (small kelp plant) with its main parts.

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Table 4
Classification of seaweed [51–53].
Type Characteristics Occurrence Photosynthesis Role and Importance Species
Pigments

Green algae (Chlorophyta) • Multicellular • 700–7000 species • Chlorophylls A and B, Primary producers
• Simple thallus • Occurs in Bays, carotenoids • Halimeda
• Relative to green Estuaries, Tide Pools • Store excess energy as • Ulva lactuca
plants starch • Codium tomentosum
• Filamentous spongy • Cellulose in cell walls
fingers or paper-thin
sheets.
• Some coralline

Brown algae (Phaeophyta) • Olive green to dark • Around 1500 species • Contain chlorophyll A • Kelp forest provide habitat for
brown color • Temperate and polar and C and fucoxanthin countless species of fish, marine
• Can grow up to 100 m location • Cell wall made of mammals, birds and
• Most complex thallus • North America and align and pectin invertebrates
• Leathery and can Europe • Saccharina latissima;
withstand exposure to • Gulf of Mexico. –Himanthalia elongate;
air • mid-Atlantic • Laminaria digitata; Fucusser-ratus;
• Rocky shores • Ascophyllum nodosum;
• Prefer shallow and • Undaria pinnatifida;
cold waters • Saccorhiza polyschides; Sargassum
muticum.
• Kelps, Sargasso weed
• Nereocystis
• Macrocystis
Red Seaweed • Grow as filaments, • 4000 species • Chlorophyll A and • Some are corraline (produce
sheets of cells. • Most abundant and phycobilins calcium carbonate
• Parasites of other most widespread • calcium carbonate • Gracilaria verrucosa,
algae • Live in deep cold within their cell walls • Palmaria palmate
waters or warm,
shallow waters
• Asparagopsis armata.

Table 5
Composition of seaweeds [48,52,53].
Components Composition

Carbohydrates Brown Seaweed; 30–50% dry weight

Red Seaweed; 30–60% dry weight
Green Seaweed; 25–50% dry weight
Proteins Brown Seaweed; 3–15% dry weight
Red Seaweed; 10–47% dry weight
Green Seaweed; 9–26% dry weight
Minerals 7–38%
Lipids 1–3%
Water 80–90%

4. Seaweed supply chain

Fig. 4. Growth cycle of seaweed.
The majority of the seaweed species are essential sources for com-
mercial foods, feeds, high-value pharmaceutical, nutraceuticals and macroalgae biomass. The supply chain for biofuel production from
other bioactive products [39,44,56]. Also, there is growing interest to seaweed is summarized in Fig. 5. Large-scale production of seaweed for
produce different types of biofuels including biohydrogen, methane via biofuel production mainly depends on the composition of seaweed,
thermal gasification or anaerobic digestion; bioethanol by fermenta- percentage of carbohydrate and ease of conversion. A seaweed species
tion; bio-oil by pyrolysis and biodiesel by transesterifications of

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•Nattrually-occurring seaweed d Table 6

•Culltured seaweeed (aquacultture) Environmental factor for the growth of seaweed.
•Haatchery
ntal)
•Prroduction sysstem (verticaal & Horrizon Location Grow in tropical regions.
On coral reefs, rocky and in sandy bottoms of marine waters in
intertidal or subtidal zones.
• Mechanical
M Water quality Clear, constant motion for continuous nutrient flow.
• Manual
M Salinity 28–34 ppt, relatively salty, purely marine.
Depth at least 30 cm during low tide.
Temperature 27–30 °C.
Current 5–10 m per minute.
Land Quality Substratum - Sandy/rocky.
• Trruck/wagonn
Fauna The presence of natural seeds and other vegetation, e.g.,
• Loose/baled
seagrass or sargassum.
Climatic Factor Reef areas to protect the farm from the typhoon, strong waves,
and tsunami.
• Reemoval of foreign
f objeects
• Dewatering/d drying
• Siize reductioon/grinding
• Desalination growth and harvesting and therefore enables higher efficiency and
productivity than natural growth. Macroalgae can be cultured in la-
goons or sheltered bays to obtain the nutrients directly from the sea-
• Feermentation
n
• Anaerobic
A digestion water. Rock-based farming, fixed off-bottom (post and line) and long
• Hydrothermaal liquefaction lines are the traditional methods of cultivation of seaweed (Table 7).
Large brown kelps are usually preferred for biomass production.
• Fooods
Whereas, the smaller species are favored for high-value components
• Feeeds [60–66].
• Biiochemicalss
• Biiofuels 4.2. Harvesting of seaweed

Harvesting macroalgae have been a long tradition in many coastal

Fig. 5. Conceptual supply chain to produce valuable products from seaweed. lands [67]. The two types of harvesting techniques are:

with high carbohydrate content, low ash, low water, low cellulose • Manual (Hand)
content will be preferable for biofuel production. The first stage in the • Mechanical (Dredge, moving boat, mesh conveyor)
supply chain of seaweed for biofuel is the biomass generation via cul-
tivation. Next, the harvesting usually performed using manual or me- Harvesting is typically carried out three times in a year. Intense
chanical methods. Biomass pretreatment includes filtering, dewatering, mechanical harvesting leads to adverse consequences on marine eco-
and drying. Downstream processing techniques can be varied according systems and considerably diminishes the growth of macroalgae species
to the utilization of the seaweed. The absence of lignin in seaweed [68]. However, in some other areas, removal of proliferated macroalgae
makes it easier to convert into a biofuel than land-based plants [57]. growth is beneficial as a mean of removing of excessive nutrients from
Seaweed with a low content of polyphenols is best suited for bio- the environment. The economic feasibility of harvesting macroalgae
methane production. Polyphenols inhibit the growth of methanogenic blooms has not been successful worldwide [64].
bacteria and considered as a limiting factor in anaerobic digestion.
The only viable technology for producing renewable energy (biogas) 4.3. Pretreatment of seaweed
from macroalgae is through anaerobic digestion. Biodiesel and bioe-
thanol are the main promising options for the future sustainability of Continuous, year-round production of seaweed improves the eco-
transportation sector. The most commonly argued approach of algae nomic viability of a large-scale production plant [69]. The harvesting of
exploitation is to obtain biodiesel rather than other biofuels [34,39,58]. biomass takes place in a period of 2–5 months when the composition is
Till date, the oil yield from macroalgae is less profitable compared to at its optimum. These imply that the seaweed biomass has to be stored
microalgae [44]. and preserved. L. hyperborea harvested for alginate production in
Norway (approx. 150,000 t annually) is preserved with formaldehyde,
which is not a viable option for later biochemical conversion. Other
4.1. Cultivation of seaweed preservation methods applicable for several thousand tons have not
been described. The drying of seaweed is carried in the open sun by
Seaweed cultivation and harvesting are rather straightforward, and spreading uniformly on the nearby rock or shore. Drying time is mostly
a significant amount of biomass could be obtained due to its size within 24 h and the final moisture content of dried seaweed ranges
compared to microalgae [54]. Macroalgal biomass for downstream between 10% and 15%. Drying could be applied to small biomass vo-
processing is obtained from three primary sources: direct harvesting of lumes intended for high-cost products but will be too expensive for
seaweed from the marine environment, a collection of dead seaweed high-volume low-cost products [70]. Seaweed is dried to remove
from shore (wrack), and culturing selected seaweed species. Seaweed moisture from 90% to 10% (wet basis) on an average 10 kg of seaweed
can be directly cultivated in an open sea. A part of seaweed production will produce 1 kg dried biomass. Physical, chemical and enzymatic
comes from harvesting of beach cast seaweed and natural population. pretreatment methods are used to loosen the cell wall for further ex-
The major environmental factors for the growth of seaweed are listed in traction procedure [69,71–75].
Table 6
The various methods of cultivation of seaweed are offshore, onshore 4.4. Conversion to food, feed, biochemical and biofuels
and integrated seaweed cultivation. Offshore cultivation of macroalgae
involves direct culturing in seawater through the use of anchored ropes. Seaweeds have been used as a source of fertilizer in the agriculture
It can also be combined with onshore aquacultures and offshore wind industry. It has also been used as a source of alginates in the food in-
farm sites [59]. Offshore cultivation allows controlled conditions of dustry. There is a myriad of potential pathways and numerous seaweed

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Table 7
Cultivation method of seaweed.
Fixed off-bottom long line Floating Raft Rock-based farming

Substrate or seedlings are tied to the rope of 10–20 m Floats or wooden rafts are used to suspend substrate Seaweed explants are attached to a rock density of 25 per m2
length. in the sea surface. with an elastic band.
Both offshore shallow waters and onshore cultivation. Enables deeper waters farming sites. Sites need to be protected from sea menace.
More intensive maintenance and necessity of boats. Labor intensive and complex to install. Labor saving and simple method.

Fig. 6. The process of energy extraction from seaweed.

Fig. 7. Key process stages of biogas production from seaweed.

species to produce bio-energy. A range of methods for producing • Combustion

bioenergy from macroalgae exists. The extraction of energy from sea- • Fermentation (Bioethanol)
weed biomass can be categorized into two categories based on the re- • Anaerobic digestion (Biogas/methane)
quirement of drying before processing (Fig. 6). The biofuel production • Biorefining approach
from dry seaweed biomass involves either direct combustion, pyrolysis,
gasification or transesterification [76]. Hydrothermal treatments, en- The potential application of macroalgae for biofuel production has
zyme hydrolysis, fermentation to bioethanol/biohydrogen/biobutanol been reviewed [80] and shown that the seaweed biofuel conversion
and anaerobic digestion are the energy production methods from wet processes developed to date are at the laboratory or pilot-scale opera-
biomass [7,77–79]. Well-developed technologies include: tions. The use of seaweed for the biofuel production is still in extensive

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research and development stage. Seaweed accumulates high amounts of

non-glucose-based sugars, such as mannitol and cell wall poly-
saccharides and lower amounts of glucose-based polysaccharides.
Therefore, the industrial production of bioethanol from macroalgae
requires fermentation of both glucose- and non-glucose-based sugars
[81].

4.4.1. Anaerobic digestion

The practical feasibility of seaweed as a feedstock for the anaerobic
digestion (AD) process has been successfully demonstrated in many
studies. However, the long-term AD process may be problematic due to
sand deposition in digesters and salinity [82–84]. Numerous para-
meters such as the cultivation method, the type of species, seaweed
yield per hectare, harvesting time play a significant role in the anae-
robic digestion process. The energy and material balance, the carbon
balance, the cost of the harvesting biomass, the cost of the producing
biogas from seaweed have not been assessed [77,78,85]. However,
there are very few seaweed digesters at commercial scale. The typical
anaerobic digestion process of seaweed biomass is shown in Fig. 7.

4.4.2. Fermentation
Macroalgae are ideal candidates for bioethanol production owing to
the high content of carbohydrates which can be easily fermented to
produce biofuels [69,86]. Separate hydrolysis and fermentation (SHF)
and simultaneous saccharification and fermentation (SSF) are the cur-
rently used methods for bioethanol production from seaweed
[11,23,87]. The steps involved in the fermentation process are shown in
Fig. 8. In the case of SHF, seaweed biomass is first hydrolyzed, and then
it is subjected to bacterial or yeast fermentation in separate units
[11,23,68,81,88]. However, in the case of SSF, both the hydrolysis and
fermentation is carried out simultaneously in a single process
[67,73,81,89,90].

4.4.3. Chemical extraction and transesterification

A conventional solvent extraction method is typically used to ex-
tract the oil (Fig. 9). The oil is extracted from the seaweed by the Bligh-
Dyer method and hexane-acetone extraction method. The yield of oil
from Bligh Dyer method is very less and it is often difficult to separate
Fig. 8. Experimental pathway for bioethanol production from seaweed.
the oil from the biomass. The steps involved in hexane-acetone ex-
traction are mentioned below:
transesterification but also simultaneous esterification and transester-
• Extraction of wet biomass by shaking with 720 ml chloroform/me- ification are also possible. These enable efficient conversion of free FAs
into biodiesel. In traditional transesterification process, free FAs cause
thanol mixture 2:1 (v/v) at 37 °C for 18–24 h.
• Filtration of extract through 47 µm diameter Whatman glass mi- soap formation (saponification) reducing the biodiesel yield. Macro-
crofibre filters. algae have high moisture content, which causes several problems in
• The addition of chloroform (10 ml) and distilled water (10 ml) se- biodiesel production [94].
quentially to the filtrate and shaking for 10 min.
• Filtration of the solution under vacuum through a 25 mm diameter 4.4.4. Direct combustion
Whatman glass filter microfiber. The use of macroalgal biomass for direct combustion has also been
• Washing the filtrate with 30 ml of 5% sodium chloride solution. studied by many researchers [95–98]. In general, it is not recommended
• Separation of a unipolar upper phase containing strong non-polar to use feedstock with high ash, moisture, alkali metal (Na, K) and ha-
compounds and the lower layer of chloroform. logen content for direct combustion [95,99]. The minimum and the
• Filtration and removal of traces of water by treating with anhydrous maximum value of the higher heating value of Macroalgal biomass
sodium sulfate reported in the literature range from 4.35 to 20.1 MJ/Kg. The higher
• Centrifugation to facilitate phase separation (If needed). heating value (HHV) of macroalgal biomass is much lower than that of
• TMSH derivatization to get the FAME [56]. Rotary evaporation of the terrestrial energy crops (14–20 MJ/kg). The combustion efficiency
the TL extract at 40 °C [91]. of seaweed biomass for the generation of heat is very low and are
• The extracted oil from the seaweed biomass can be tested for fatty usually between 15% and 30%. However, the use of seaweed biomass
acid profile analysis (using GCMS). for direct combustion process is not recommended due to the risk of
corrosion, fouling and particulate emissions. The combustion of waste
Alternatively, Soxhlet extraction technique using chloroform or residues is economically viable, although technical problems like ash
chloroform/hexane mixture can also be used. handling and flue gas emissions (NOx and SO2) remains.
The most desired lipid fraction of macroalgal oil is the neutral lipids
(NL) due to their high content of triacylglycerols (TAGs) [92]. TAGs are 4.4.5. Pyrolysis
rich in fatty acids (FAs), and 99% biodiesel yield is possible [93]. The most preferred method for bio-oil extraction in tropical and
Conversion of FAs to biodiesel is performed traditionally by subtropical regions is pyrolysis. Dried seaweed biomass can be easily

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Fig. 9. Oil extraction from seaweed [56].

5. Recent approaches in seaweed processing

5.1. Seaweed production through an offshore wind farm

Prospects of seaweed cultivation and harvesting around offshore

wind turbines for the generation of biofuels, bioenergy, fish and animal
feed are being explored [107]. Seaweed and wind turbines are poten-
tially a right combination for both wind power and bioethanol (from
seaweed) production (Fig. 12). Additional simple infrastructure is
needed in wind farms to enable them to double up as seaweed farms.
The following are the features for such farms:

• Seaweed farms are recruitment area for fish juveniles.

• Nutrients from fish farms may increase the seaweed production.
Fig. 10. Pathway of bio-oil production from seaweed. • Share facilities and infrastructure (floating stage, boats, harbors).
The survival, growth rate and the ecological effects of offshore
converted into bio-oil and solid residue (char) via pyrolytic cracking. cultivation of seaweed required to be studied. It is also expected that
Pyrolysis is the thermal decomposition in the complete absence of an the offshore wind power plants might bring benefits to marine species,
oxidizing agent (air or oxygen), or with a limited supply, so the com- including new habitat for various sea creatures [110].
bustion or gasification do not occur to an appreciable extent [100,101].
Seaweed biomass is first mechanically milled and further dried to use as 5.2. Integrating with mariculture
feed for pyrolysis conversion [102,103] (Fig. 10).
Mariculture is the technology of rearing of aquatic organisms under
controlled or semi-controlled conditions [109]. Besides increased in-
4.4.6. Gasification land production from freshwater fish aquaculture, which is traditionally
The large-scale gasification of biomass has been successfully de- an integral part of agriculture production, a significant proportion of
monstrated. However, it is still relatively expensive in comparison to the expansion is also anticipated to take place along the coasts of both
energy from fossil fuel [104,105]. Gasification is capable of producing developing and developed countries [111]. Seaweeds have several uses,
syngas and hydrogen at a competitive market price. Few demonstration gaining momentum as a new experimental system for biological re-
gasification plants exist in some countries, yet more extensive pene- search and also as a part of integrated aquaculture systems [112].
tration in the industrial market depends on integration into the seaweed The various benefits of mariculture are listed below:
biofuel chain [106]. Fig. 11 illustrates the gasification process of sea-
weed. The pros and cons of various biofuel production from seaweed
are compared and presented in Table 8.
• Seaweeds farms act as nutrient sinks and increase the primary
productivity.
• The farms act as habitat for certain fish and shellfish.
Fig. 11. Gasification of seaweed.

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Table 8
Merits, demerits, and the main products of different processing techniques [7,16,26,43,85].
No Processing options products Advantages Disadvantages
Biological process

1 Anaerobic digestion Biogas Matured technology, drying not required High Nitrogen and Sodium inhibition
2 Fermentation Bioethanol High carbohydrates contents Low efficiency, mixed sugars
Chemical process
3 Chemical extraction and transesterification Biodiesel No dewatering Poor yield
4 Direct chemical treatment Value added chemicals
Thermochemical
5 Direct combustion Heat
6 Pyrolysis Bio-oil & char No caustic chemicals requiredFast rate High temperature and energy consumption
7 Gasification Syngas & Hydrogen

• Seaweed farming provides sustainable lively-hoods. combined with extraction of high-value compounds. Organic residues
• In many cases, women are involved in the seaweed farming. can be fermented to biogas and cover part of the energy demands of the
• Older individuals are engaged in tying and drying of seaweeds. process, while the inorganic residues (minerals) can be utilized as fer-
• A sustainable and lucrative business which prevents migration. tilizers [114]. The integrated seaweed biorefinery approach is illu-
• Since seaweeds are cash crops, it gives instant money to the farmers. strated in Fig. 13. This strategy involves sequentially the cultivation and
• In many island nations, these seaweeds have become the crops with harvesting of seaweed, pretreatment process, extraction of bioactive
highest export earnings. compounds, extracting biochemicals and biofuels through various
processes (fermentation, pyrolysis, HTL). Integrated biorefining ap-
proach for the production of high-value biochemicals, bioproducts,
5.3. Integrating nanotechnology for pre-treatment of seaweed
biofuels, and various cost reduction strategies to convert biomass to
biofuels are identified in this work [115].
Nanotechnology is an emerging field and is a widely applied tech-
nology due to their specific surface area that several hundred times
more than their equal weight of the macroscale materials. The nano-
5.5. Hydrothermal liquefaction
particle is an efficient carrier of biomolecules due to their large surface
area to volume ratio. Cellulase is one of the best alternatives for che-
Hydrothermal liquefaction (HTL) is presently considered to be a
mical and physical pretreatment of the seaweed biomass.
promising alternative and energy efficient technology for conversion of
Immobilization of the cellulase using nanoparticles is a new area of
seaweed into biofuels and chemicals [116,117]. Seaweed with a high
bioenergy research [113]. Immobilization of the cellulase enzymes on
moisture content between 80% and 85% can be quickly reduced into
magnetic nanoparticles to hydrolyze seaweed biomass for ethanol
bioactive compounds and fuel using hydrothermal conversion or li-
production reduces the consumption of hydrolyzing enzymes. Research
quefaction [118]. The hydrothermal process is the most favored option
oriented towards the biological synthesis of magnetic nanoparticles is
when the sun or air drying is problematic due to high moisture contents
very much needed.
owing to cold and temperate sea climates. The HTL also known as
thermochemical conversion process takes place in water under sub-
5.4. Integrated biorefining approach critical conditions, where the water behaves as solvent, reactant, and
catalyst (Fig. 14). These are done to avoid the latent heat of vaporiza-
Biorefining is a new and novel processing technique to produce a tion at high pressure or temperature. The kinetic pathways during HTL
broad spectrum of bioenergy (biofuels, power, and heat) and bio-based involve de-polymerization, decomposition of monomers by cleavage,
products (food, feed, chemicals,) [7]. A seaweed-based biorefinery ap- dehydration, decarboxylation and deamination, and recombination of
proach is the integration of various bioprocessing technologies for the reactive fragments. Recent studies on hydrothermal liquefaction
complete utilization of biomass to produce multiple products (food, (HTL) of seaweed biomass have demonstrated the production of higher
feed, biochemicals, and biofuels) cost-effectively and sustainably. Pro- calorific value products [119–121]. The process can produce liquid bio-
duction of biofuels or bulk chemicals, or isolation of protein, should be crude and char from the non-lipid fraction of seaweed biomass [116].

Fig. 12. Offshore wind farm and macroalgae cultivation [108,109].

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K. Sudhakar et al. Renewable and Sustainable Energy Reviews 91 (2018) 165–179

Fig. 13. Integrated energy production from macroalgae [7].

diversification and product quality optimization are the focus area

needed to assess the technical potential of seaweed. Long-term invest-
ments are required to undertake the pilot scale studies in macroalgae
processing techniques. Seaweed may play a significant role in biofuel
and biochemical production in next 10–15 years.

6. Economic importance and environment impact of seaweed

cultivation

6.1. Economic importance

Fig. 14. Hydrothermal liquefaction of macroalgae. Seaweed usage has been traced back to the Neolithic period and
actual record reveals its use as food source in China about 1700 years
The HTL product yields vary according to the composition and physical ago. Humans have made use of macroalgae for centuries and the overall
properties of the seaweed biomass feedstock, solvent, the process con- demand for seaweed-based products are continuously increasing.
ditions, and the presence of catalysts. HTL process exhibits several Seaweed is a resourceful product that can be used for direct human
challenges for the commercialization, including pressurized feeding of consumption or processed into fertilizers, biofuel, cosmetics, and
slurries, corrosion and salt precipitation. The upgraded oil product is in medicines [126,127]. Large-scale seaweed production is already the
the diesel fuel range while chemicals can be extracted both from the primary source of income for the coastal communities, covering parts of
water phase. Cost-effective microwave assisted hydrothermal liquefac- Malaysia, Indonesia, and the Philippines (Fig. 16). These areas are rich
tion is the latest novel processing route of algae biomass and provides a in marine biodiversity and seaweeds are growing in its natural state due
no enzymatic route for depolymerization of biomass into sugars, which to the conducive local environment. Seaweed contains high-value bio-
can be used for the biological production of fuels and chemicals logical derivatives with potential commercial application in pharma-
[118–121]. ceutical, biomedical, cosmetic, aquacultural, fertilizer, and nu-
traceutical industries. Seaweed is also extensively utilized as
ingredients in food additives (polysaccharide gels (hydrocolloids),
5.6. Combined hydrothermal liquefaction and pyrolysis polysaccharides and biologically active materials) [128], pet food,
feeds, human and animal food preparations owing to its high contents
The most recent techniques used for the conversion of macroalgae of polyunsaturated fatty acids (PUFAs), carbohydrates, vitamins, mi-
feedstock into biofuels are pyrolysis and hydrothermal liquefaction nerals, and dietary fibers [129]. The growth of the seaweed has been
(HTL) as shown in Fig. 15. Hydrothermal processing is developed as an restricted due to various issues such as technological constraints, socio-
alternative technique to process wet biomass which is not possible in political (land grabbing), increase in land rates and environmental
case of direct combustion [122]. The hydrothermal conversion pro- problems.
cesses provide the high temperature and pressure conditions required to Seaweed production is dominants in Asian countries such as China
process the wet organic biomass into higher energy density cleaner (62.8%), Indonesia (13.7%), Philippines (10.6%), Korea (North and
fuels similar to a lignite coal (green coal), petroleum (bio-crude) or South; 8%), Japan (2.9%), Malaysia (0.9%). The rest of the world
natural gas (syngas). Experiments in hydrothermal processing have contributes only (1.1%) of global production (Fig. 17). The annual
proved the potential for upgrading wet biomass, through carbonization, global seaweed production accounts for about 5.5–6 billion USD. The
liquefaction, and gasification to produce products with a far higher global farmed and captured marine algae production (33 countries) in
energy density than the original biomass. Microwave pyrolysis or ex- 2012 is 23.8 million and 1.1 million wet tons respectively. About 7.5 – 8
traction creates an ideal or optimum environment to convert seaweed million tons per annum of wet seaweed are harvested from farmed and
biomass to biofuels for the aviation sector [123–125]. naturally growing seaweed crops. The global harvest and market po-
Integrated biorefinery based biomass production, species tential of seaweed is roughly 26 million tons. Only a few Asian

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Fig. 15. Pyrolysis and hydrothermal liquefaction of macroalgae.

countries are dominant, and they account for the 96.27% of the total
farmed algae production (Table 9) [130]. The major problems faced by
seaweed industry include overexploitation of marine seaweed, scarcity
of high-quality seaweed biomass, shortage of skilled labor, lack of im-
proved technology and a lack of information on new sources.
The tropical seaweeds in commercial products include the
Eucheuma, Caulerpa Kappaphycus and Gracilaria [131]. Laminaria
(kombu), Undaria (wakame) and Porphyra (Nori) are sold at $ 2800/dry
ton, US$ 6900/dry ton and US$ 16,800/dry ton respectively [126]. The
market potential of seaweed is shown in Fig. 18. Several countries in-
cluding China, Indonesia, Japan and the Republic of Korea uses sea-
weed as a staple food. It is most likely that the future seaweed industry
adapts multiple biorefineries concepts where food products are ex-
tracted with energy as a by-product.
Fig. 17. Global production of seaweed.

6.2. Environmental impact

from the carbon fuel burning power plant can feed into open or closed
6.2.1. CO2 mitigation algae systems, to accelerate algae growth and carbon reduction [132].
With the concern over global warming, new concepts for the com- Seaweed is the excellent candidate to remove CO2 from the atmosphere
plete and efficient capture of CO2 are being explored. The CO2 released due to its higher photosynthetic efficiency and fast growth rate [133].

Fig. 16. Worldwide distribution of seaweed.

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Table 9
Industrial products from seaweeds [126,127].
Food Industry Fertilizer Industry Pharmaceutical Industry

Algin: Excellent source for producing potash Filler in pharmaceuticals and cosmetics.
An extract of brown algae (phycocolloid) is used as an emulsifier and potassium nitrate.
in dairy products such as ice cream, cheese, and baked goods.
Carrageenan: Produce agar and products. Alginic acid:
Harvested from red algae used as an emulsifier. Garden fertilizers, and in animal feeds Shampoos, paints, cosmetic, antacids, shaving cream, and paint
Thickening agent in milk products such as yogurt and milkshakes.
Agar: Seaweed liquid fertilizer and manure Carrageenan:
Second extract from red algae. have sales value of several million Aquafresh toothpaste, Sensodyne toothpaste, silver polish,
Culturing microbes for the healthcare industry. dollars swimming pool filter powder, flea powders, garden pest control
Thickener in foods, and to protect canned meats.
Formation of jellies.
Media to grow molds and bacteria.
Phycocolloids: Solid charcoal residue (biochar) is used Bioplastic production.
Food processor for their ability to form viscous suspensions. as biomanure and biofertilizer Dyes and colorant production.
Dairy and meat industry Chemical feedstock production.
Pharmaceutical ingredients.
Irish Moss: Phycobiliproteins:
Stiffening agent in instant puddings, sauces, and ice cream. Fluorescent pigments used as biomedical reagent
Fining agent for beer brewers

treatment process.
✓ Development of catalytic novel separation processes to operate in
aqueous phase.
✓ Development of integrated biochemical and thermochemical con-
version processes operating at 80% water to produce high-quality
biofuels from seaweed.
✓ Techno-economic feasibility and optimization studies of the overall
conversion processes from macroalgae feedstock to biofuel.
✓ Improvement in current framework for implementation of value-
added bio-based products.
✓ Improvement in cooperation between major stakeholders in stra-
tegic and policy planning at various levels (Regional, National &
International).
✓ The impact of seaweed cultivation on aquatic biodiversity and social
acceptability need to be addressed.
✓ For the production of biofuels, seaweeds have to be cultivated in
Fig. 18. Market potential of seaweed. large-scale, and the processes for extraction required to be studied in
detail to attain nations’ economic needs.
One on of dry seaweed can approximately absorb 960 kg of CO2 during
the cultivation. It also has other environmental benefits such as redu- 8. Conclusion
cing eutrophication, global warming potential, and acidification. Sea-
weed can also be used for nitrogen, phosphorus and potassium fixation This paper has assessed the potential of seaweed as an alternative
[134]. sustainable feedstock.

6.2.2. Wastewater treatment & pollution control ✓ Marine seaweed is a promising feedstock for bioenergy production
High nutrient content and pollutants in the wastewater can be due to its extensive geographical distribution and advantages over
treated using macroalgae; thus converting the waste into valuable the terrestrial plant.
commodities [135]. Seaweed cultivation is currently researched for ✓ Seaweed has a crucial role in providing some of the essential pro-
uranium/plutonium sequestration and also for purifying fertilizer ducts required for human society in the coming decades.
runoff. By cultivating macroalgae (seaweed) in the industrial effluent ✓ Seaweed can create a healthy and profitable business for the coastal
ponds, the pollution can be alleviated [136]. fishing communities with a diversified production of biochemical,
bioethanol, biogas and fertilizers.
7. Concluding remarks and future directions ✓ Major innovations in the conversion process and integrated bior-
efinery approach is the key factor for sustainable utilization of
The following technological advancements are required to establish seaweed in future
a sustainable and efficient utilization of seaweed. ✓ However, with its enormous potential and unique chemical com-
position, macroalgae has a good market potential and probably will
✓ Increased understanding of the morphology, genetics, and bio- make a substantial contribution towards a sustainable en-
chemistry of the seaweeds is needed. vironmentally benign alternative feedstock for energy production.
✓ Optimizing the composition of dominant seaweed species to pro-
duce high-quality biomass based on the different sea regions.
Acknowledgement
✓ Screening and discovery of other seaweed species to develop new
products and processes for the benefit of the humanity.
Universiti Malaysia Pahang fully supports the facilities and re-
✓ Development of high energy dry matter with minimum pre-
sources for this research. The authors would like to acknowledge the

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