Co2 Fixation

58 2011 Society of Chemical Industry and John Wiley & Sons, Ltd | Greenhouse Gas Sci Technol.
ol. 1:5871 (2011); DOI: 10.1002/ghg3

Review
Correspondence to: Angela Dibenedetto, Department of Chemistry and CIRCC, University of Bari, Campus Universitario 70126 Bari, Italy.
E-mail: a.dibenedetto@chimica.uniba.it
Received October 21, 2010; revised December 21, 2010; accepted December 21, 2010
Published online at Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/ghg3.006
The potential of aquatic biomass for
CO
2
-enhanced xation and energy
production
Angela Dibenedetto, University of Bari, Italy
Abstract: In this review, the use of micro- and macroalgae to x CO
2
and produce energy is discussed.
The xation of CO
2
into aquatic biomass is an option which has recently come under intensive investi-
gation as it can be utilized to stimulate the growth of seaweed or microalgae. Aquatic biomass has
long been cultivated and used at industrial level as a source of chemicals (agar, alginate, carragenans,
and fucerellans) or as food for humans or animal feed. Recent interest in its use as a source of biofuels
is due to the need to shift from rst-generation biofuels (biodiesel and bioethanol produced from edible
biomass) to non-food sources that may grow without the use of arable land. Aquatic biomass can be
grown in salty water or fresh wastewater (municipalities or process water) or else in bioreactors to
produce different fuels such as bio-oil, biodiesel, bioalcohol, biohydrogen. Biogas can be produced
from residual biomass after liquid fuel extraction. Microalgae are attracting much attention as they are
photosynthetic renewable resources, with high lipid content and faster growth rate than terrestrial
plants; they can grow in saline waters which are not suited for agriculture. While the lipid content of
microalgae on a dry cellular weight basis usually varies between 20 and 40%, a lipid content as high
as 85% has been reported for selected microalgal strains. They can be easily manipulated through
physical stress or genetic engineering. They can also produce bioethanol. The barrier to their exploita-
tion is the high cost (up to 5000 US$/t) of growth and processing. Seaweeds produce less biofuel per
t-dry weight, but their growing and processing costs are much lower. In perspective, aquatic biomass
can become an interesting and ubiquitous source of energy.
2011 Society of Chemical Industry and John Wiley & Sons, Ltd.
Keywords: biofuels; biomethanol; bio-oil; carbon dioxide xation into aquatic biomass; macroalgae;
microalgae
Introduction
I
t is now clear that the progressively increasing
emission of CO
2
into the atmosphere may afect the
climate; overwhelming scientifc evidence supports
this. Burning coal, natural gas, and oil is the main
origin of CO
2
that behaves as a trapping agent for heat
radiating from the Earths surface.
Te need to reduce atmospheric CO
2
is documented
by several global and local agreements
1
which have
pushed the identifcation and development of new
technologies for CO
2
separation, capture, and seques-
tration in geologic formations or chemical, biological,
and technological utilization. Te utilization approach
is of great interest as CO
2
may be converted into
valuable commercial products, contributing, thus, to
Review: The potential of aquatic biomass for CO
2
xation A Dibenedetto
59 2011 Society of Chemical Industry and John Wiley & Sons, Ltd | Greenhouse Gas Sci Technol. 1:5871 (2011); DOI: 10.1002/ghg3
the recycling of carbon and reducing the extraction of
fuels.
An attractive way to reduce the amount of CO
2

emitted could be its utilization as either technological
fuid or Cn- or renewable C1-building block. Recov-
ered CO
2
can be used for producing chemicals,
plastics, and other useful products: numerous reviews
and books have been published on various aspects of
CO
2
utilization.
28
In fact, CO
2
is considered to be a green, or environ-
mentally benign, solvent and a cheap, non-toxic,
non-fammable, and naturally abundant source of
carbon.
9,10
As a technological fuid, CO
2
has been suggested as
a sustainable alternative for organic solvents in
various chemical processes.
11,12
It can be also used in
enhanced oil recovery (EOR), enhanced gas recovery
(EGR), or as a cleaning agent for textiles, a refrigerant,
a food conservative and a preservative. CO
2
is also
used as a chemical in the production of urea (95 Mt/y),
salicylic acid (70 kt/y),
13,14
monomer for polymers (e.g.
polycarbonates), syngas, and fuels (dry reforming of
methane, methanol). Its mineralization by carbon-
ation of silicates is under investigation.
In addition to such applications, the enhanced
fxation of CO
2
into biomass is a challenging option
under intensive investigation. High concentrations of
CO
2
can be used to stimulate the wild growth of
seaweed and microalgae ofshore or in cultures
onshore and also to promote their growth in fresh
wastewater (municipal ef uents or selected process
waters). In this review, the biological fxation of CO
2

into aquatic biomass is discussed.
Biomass, in general, represents an environmentally
and economically viable alternative to fossil fuels,
moving a step toward the zero emission option. As a
matter of fact, the forecast is that biomass may
contribute to the global energy balance with a share of
more than 10% by 2050.
15
Such expansion of the
market would be possible if new biomass for energy
were specifcally grown and used in addition to the
limited amount of terrestrial or residual biomass used
today as an energy source. However, aquatic biomass
may represent a convenient solution; it has a higher
(from three to four times) growth-rate with respect to
terrestrial plants, due to greater photosynthetic
ef ciency. Microalgae have been extensively studied so
far.
16,17
More recently, marine macroalgae have been
considered with increasing attention.
18
CO
2
recovered
from either power plants or industrial fue gases could
be distributed into the algae culture under opportune
conditions, implementing an enhanced recycle of
carbon.
The interest in the exploitation
of aquatic biomass
Aquatic biomass includes macroalgae, microalgae,
and emergents (plants). Tey can grow both in
saltwater or freshwater. Macroalgae, commonly
known as seaweed, are multicellular organisms.
Tey are ofen fast growing and can reach sizes of up
to 60 m in length. Seaweed is mainly utilized for the
production of human food, animal feed, and the
extraction of hydrocolloids.
Microalgae are microscopic organisms. Diatoms are
the dominant life form in phytoplankton and prob-
ably represent the largest group of biomass producers
on Earth. Green algae are especially abundant in
freshwater. Te golden algae are similar to diatoms
and produce oils and carbohydrates. Emergents are
plants that grow partially submerged in bogs and
marshes.
Natural populations of seaweed have been used since
the beginning of civilization for food, feed, and
fertilizers; they were then cultivated and used at
industrial level also as a source of agar, alginate,
carrageenans, and fucerellans. Te main producers
are China, the Philippines, North and South Korea,
Japan, and Indonesia with a world production of
seaweed of several Mt/y.
Te use of algae for energy production became a
topic of discussion as recently as the 1970s afer which
several projects were funded to determine the techni-
cal and economic feasibility of production of energy
from marine biomass, i.e. macroalgae.
19
Te interest in the exploitation of aquatic biomass
for energy production has grown considerably world-
wide as highlighted by large industrial investment
20
in
such areas and by the huge number of international
conferences and workshops organized and aimed at
defning the real potential of aquatic biomass for the
production of fuels. Tis enthusiasm is justifed by the
larger productivity per hectare of aquatic biomass
with respect to the terrestrial biomass (the productiv-
ity of macroalgae under most performant conditions
ranges from 150 to 600 t
fw
(t
fresh weight
) ha
1
y
1
,
compared with the typical value for sugarcane that
ranges from 70 to 170 t
fw
ha
1
y
1
). Te higher amount
of oil produced per ton of dry weight (the lipid
A Dibenedetto Review: The potential of aquatic biomass for CO
2
xation
content of microalgae may largely vary with the
species, typical values in the range of 2040% of dry
weight with exceptional records of 7580%) and by
the fact that aquatic biomass may be grown in saltwa-
ter and freshwater, ofering a large choice of potential
sites where it can be cultured.
Nevertheless, to enlarge commercialization of
biofuels from aquatic biomass, several barriers and
technical challenges must be overcome. In particular,
building large ponds (of several hectares) involves
large investments in terms of capital and operational
(cultivation, harvesting, work-up) costs. Particular
attention should be devoted to start algal strains that
may produce for years.
Microalgae
Microalgae are currently cultivated commercially as
feed for fsh around the world in several dozen
small- to medium-scale production systems, produc-
ing from a few tens of tons to several hundreds of tons
of biomass annually. Te main algae genera currently
cultivated photosynthetically (e.g. with light) for
various nutritional products are Spirulina, Chlorella,
Dunaliella, and Haematococcus (Table 1).
Microalgae can be grown in open ponds or in
photobioreactors. Te culture in open ponds is more
economically favorable,
27
(Table 2; photobioreactors
are much more expensive to build than open ponds)
but raises the issue of land cost and water availability,
appropriate climatic conditions, nutrients cost, and
production. In the open pond option, other cultiva-
tion aspects should be taken into consideration, such
as maintenance of long-term growth of the desired
algae strain without interference by competitors,
grazers, or pathogens. Tese results also indicate how
much the overall production cost depends on the
reactor (open or closed) cost.
28
By using open-pond systems, nutrients can be
provided through run-of water from nearby living
areas or by channelling the water from wastewater
treatment plants. Some source of waste CO
2
could be
ef ciently bubbled into the ponds and captured by the
algae (Fig. 1). Te water is moved by paddle wheels or
rotating structures (raceway systems), and some
Micro-algae Characteristics
Spirulina is a multicellular, lamentous blue-green algae. Various commercial Spirulina production plants are
currently in operation.
2225
Growth rate: 30 g/m
2
day dry weight. Temperature: Optimum between 3537 C.
Very tolerable to pH change.
25
Chlorella sp. is a unicellular organism that can be found in almost any water environment (fresh water and
marine). Growth rate: 26 g/m
2
day dry weight. Temperature: 3537 C (depending on species). pH: Depends
on species.
Dunaliella is a type of halophile microalgae especially found in sea salt elds. Growth rate: 1.65 g/m
2
day
dry weight. Temperature and pH: Depends on species.
Haematococcus pluvialis is a freshwater species of Chlorophyta. It is usually found in temperate regions
around the world.
26
Growth rate: 913 g/m
2
day dry weight.
Table 1. Main strains of microalgae currently cultivated.
Table 2. Capital construction costs for three
different algal production systems.
21
Production systems Costs ($/ha)
Open pond 76 000
Raceways 161 000
Enclosed tubes 348 000
2
mixing can be accomplished by appropriately de-
signed guides.
Tere are two major types of ponds for mass cultiva-
tion of microalgae: horizontal ponds and sloped
cultivations ponds. Among horizontal ponds, the
most preferred are the raceways ponds (Fig. 2a);
circular ponds (Fig. 2b) are very expensive as they
require high-energy consumption and it is dif cult to
obtain turbulence in the center of the pond. Raceway
ponds, usually lined with plastic or cement, are about
2035 cm deep to ensure adequate exposure to
sunlight. Paddlewheels provide motive force and keep
the algae suspended in the water. Te ponds are
supplied with water and nutrients, and mature algae
are continuously removed at one end.
Te slope cultivation pond is designed to create a
turbulent fow while the algal culture passes through a
sloping enclosure. Te main disadvantage of this
method is the cost involved.
30
Methods to cultivate algae have been developed over
the years. Recent developments in algae growth
technology include vertical reactors
31
and bag reac-
tors
32
made of polythene mounted on metal frames,
reducing the land required for cultivation.
Using such bioreactors, microalgae can grow under
light-irradiation and temperature-controlled condi-
tions, with an enhanced fxation of CO
2
that is
bubbled through the culture medium. Algae receive
sunlight either directly through the transparent
container walls or via light fbers or tubes that chan-
nel the light from sunlight collectors.
A number of systems with horizontal and vertical
tubes, bags, or plates are made of either glass or
transparent plastic exposed to the sun either in the
free air or in greenhouses (Fig. 3).
Te production of microalgae in open ponds de-
pends on the climatic conditions. Solar irradiation
and temperature are the most important factors
afecting the farming process and its productivity.
Tese two parameters drive the growing period and,
thus, the economics of the process. Te availability of
land and water are key factors for developing open-
pond cultures. Semi-desert fat lands unsuitable for
tourism, industry, agriculture, or municipal develop-
ment were also selected if, in such areas, biomass
cultivation is strongly afected by the supply of CO
2

and water. In fact, either CO
2
or water becomes a
limiting factor. In an open-pond system, the loss of
water is greater than in closed tubular cultivation or
bag cultivation methods. Te water can be saline
groundwater or local industrial water, draining from
agricultural areas and recycled afer harvesting algae.
CO
2
sources for algae growth can be from CO
2
pipelines, fue gases from power plants, or any other
source rich in CO
2
.
Nutrients (N- and P-compounds, micronutrients)
represent one of the major costs of algal growth. Te
use of wastewater (sewage, fsheries, and some indus-
trial waters) rich in N- and P-nutrients is an economic
option with a double beneft represented by recovery
and utilization of useful inorganic compounds, and
the production of clean water that, fnally, can be
Figure 1. Raceway system.
Source: Lookback Biodiesel from Algae.
29
Figure 2. a) Raceway pond; b) circular pond.
2
xation
reused or discharged into natural basins. Should
nutrients be added to water, the grown biomass will
not produce a zero-emission fuel as the production of
nutrients has a large associated emission of CO
2
.
Terefore, the use of wastewater rich in N- and
P-compounds is a must in such technology. Te direct
use of fue gases as CO
2
providers requires that algae
should be resistant to the pollutants that are usually
present in the fue-gas stream, namely nitrogen- and
sulfur-oxides. Studies have shown that 150 ppm of
NO
2
and 200 ppm of SO
2
do not afect the growth of
some algal species.
33
It must be noted that the resistance to NOx and SOy
is not a common feature of all algal species, and this
may represent a limitation to the direct use of fue
gases. Another point that demands clarifcation is the
optimal concentration of CO
2
in the culture, as CO
2

addition lowers the pH of the medium. Although the
response to the concentration of CO
2
may be diferent
for the various algal species, operating at pH close to 6
may, in general, strongly afect algal growth. However,
one of the key points in culturing microalgae, or algae
in general, is to generate the optimal concentration of
CO
2
in the gas and liquid phase. CO
2
can be supplied
into the algal suspension in the form of fne bubbles.
Te drawback of this methodology is the residence
time in the pond which is not suf cient to allow the
CO
2
to be dissolved.
23
A lot of CO
2
is lost to the
atmosphere and only 1320% of CO
2
is used.
A diferent method of supplying CO
2
is the gas
exchanger; this consists of a plastic frame, which is
covered by transparent sheeting and immersed in the
suspension. CO
2
is fed into the unit and the ex-
changer foated on the surface. CO
2
needs to be in a
concentrated form and 2560% of it is suspended and
used.
23
Although it is a most efective method, it
presents as a drawback the need to use very concen-
trated and pure CO
2
which is trapped under the
transparent plastic frame; in this way, very little CO
2

is lost into the atmosphere.
It has been experimentally calculated that for every
1 g of algal biomass produced, 1.82 g of CO
2
is
utilized (this is on the assumption that algae biomass
consists of ~50% carbon). Terefore, for a 6000 m
2

pond (single algal pond), a total amount of 180 kg
algal biomass (considering an algal growth rate of
30 g/m
2
day) will be produced per day which uses
324360 kg CO
2
per day. If one assumes that a
500 MW coal-fred power plant produces 9 10
6
kg
CO
2
/day, the total amount of CO
2
used per day per
6000 m
2
pond is 0.0036% of total CO
2
.
Tese values depend on the growth rate of the
microalgae and on the pond system used.
34,35
Te
growth rate is dependent on the temperature and
the season (high growth rate in the summer and low
growth rate in the winter). It must be concluded that
although the amount of CO
2
utilized is not very high,
a very valuable product is obtained in high yields.
Microalgae may easily adapt to the culture condi-
tions
36,37
if the several parameters which infuence the
rate of growth and cell composition of micro-
organisms are kept under strict control in order to
guarantee a constant quality of the biomass, a para-
meter particularly important for biomass exploitation.
Another factor which infuences the growth of
microalgae is the irradiation. Both in ponds and in
bioreactors, light availability is of paramount impor-
tance. Shadow or short light-cycles may cause a
slow-down of growth; conversely intense light (as may
occur in desert areas or bioreactors) does not
guarantee fast growth as it may modify the cell
functions.
38,39

Tropical or semi-tropical areas are the most practi-
cal locations for algal culture systems.
22
Before
starting to build a culture system, it is necessary to
consider several aspects including the evaporation
Figure 3. a) Horizontal glass tubes; b) Vertical Algae Reactor; c) Water supported exible lms;
d) Plastic bag.
2
rate which may represent a problem in dry tropical
areas (where the evaporation rate is higher than the
precipitation rate, a high evaporation rate increases
salt concentration and pumping costs due to water
loss).
36
Te precipitation rate can cause dilution and a
loss of nutrients and algal biomass. Humidity must
also be considered as with low relative humidity, high
rates of evaporation occur that can have a cooling
efect on the medium,
30
while with high relative
humidity and no winds an increase of temperature in
the medium may occur (even up to 40 C). Te
availability of water is another consideration as a
location must be chosen where there is a constant and
abundant supply of water for the mass culture pond
systems.
Macroalgae
Macroalgae (seaweed) have quite diferent properties
than microalgae. Teir use for energy production has
received less attention so far. Te big advantage of
macroalgae is their high biomass productivity (faster
growth in dry weight ha
1
y
1
than for most terrestrial
crops). Te productivity of natural basins is in the
range 120 kg m
2
y
1
dry weight (10150 t
dw
ha
1
y
1
)
for a 78 month culture. Either brown algae
(Laminaria, Sargassum) or red algae (Palmaria Pal-
mata, Pleonosporum spp, Porphyra tenera) have been
used. Interestingly, macroalgae are very efective in
nutrients (N, P) uptake from sewage and industrial
wastewater. Te estimated recovery capacity is
16 kg ha
1
d
1
.
40
To this end macroalgae have been
used in Europe for cleaning municipal wastewater
41,42

and in Europe and Japan for the treatment of fshery
ef uents
42,43
and for recycling nutrients. Te use of
macroalgae for cleaning up ef uents from fsheries has
an economic value as macroalgae can reduce the
concentration of nitrogen derivatives such as urea,
amines, ammonia, nitrite, or nitrate to a level that is
not toxic for fsh allowing the reuse of water, thus
reducing the cost of their growth. In Europe, macro-
algae are grown in experimental felds and natural
basins. Tey may be cultivated in three dimensions
rather than in two as on land. Macroalgae can be
grown on nets or lines, and can be seeded onto thin
lightweight lines suspended over a larger horizontal
rope.
44
Te capacity of macroalgae as bioflters or for
nutrient uptake has been tested in the north-western
Mediterranean Sea, along French coasts
45
using Ulva
lactuca or Enteromorpha intestinalis that adapted to
non-natural basins. Also in a colder climate, macroal-
gae grow at an interesting rate. For example, in Den-
mark, the Odjense Fiord produces ca. 10 kt per day of
dry-weight-biomass equivalent to ca. 10 t per year
per ha.
Although macroalgae can grow in both hemi-
spheres, climatic factors may afect the productivity
by reducing either the rate of growth or the growing
season. Te Mediterranean Sea has ideal climatic
conditions for a long growing season, with good solar
irradiation intensity and duration, and with a correct
temperature. Moreover, along the coasts of several EU
countries (Italy, Spain, France, Greece) fsh ponds
exist that may be the ideal location for algae ponds.
As reported earlier, a point that requires careful
evaluation is the infuence of CO
2
concentration on
algae growth. In fact, macroalgae may use either CO
2

or HCO
3
as a source of carbon, making the pH

requirements less strict. In fact, algae that use HCO
3
would prefer basic water, while algae that use CO

2
would grow better in more acidic media, where the
free CO
2
concentration is higher.
Te photosynthesis of macroalgae is saturated
at diferent levels of CO
2
, ranging from 500 to
2000 ppm.
46,47
Tis means that with CO
2
concentra-
tion up to fve times the atmospheric concentration,
under the correct light conditions and nutrient supply
macro algae may grow with the same or better perfor-
mance than they show in natural environments.
48
Concentrations of CO
2
in the gas phase up to 5%
(that means 150 times atmospheric concentration)
have been used and have been shown to be acceptable
for growing macroalgae such as Gracilaria bursapas-
toris, Chaetomorpha linum and Pterocladiella capilla-
cea.
49
Macroalgae (Table 3) require less sophisticated
techniques for growing: coastal farms are the most
used techniques for macroalgae. Te world market of
seaweed is high. Its aquaculture production is around
11.3 million wet tonnes. China is the main producer
(92% of the world seaweed supply).
50
Brown seaweed
represents 63.8% of the production, while red seaweed
represents 36.0% and green seaweed 0.2%. Approxi-
mately one million tonnes of wet seaweed are har-
vested and extracted to produce about 55 000 tones of
hydrocolloids, valued at almost US$ 600 million.
51
Te adaptation from wild conditions to pond culture
is not straightforward. Talli can be cut and used for
starting a new culture. In principle, it is more suitable
to cultivate macroalgae using natural climatic condi-
tions, as the adaptation to diferent climates may not
2
xation
be easy. Te knowledge of physiological conditions is
essential for the defnition of the best operative
parameters (optimized growing conditions).
52
Emergents or aquatic plants
Aquatic plants, also known as hydrophytes, grow in
ponds, shallow lakes, marshes, ditches, reservoirs,
swamps, canals, and sewage lagoons. Less frequently,
they also live in fowing water, in streams, rivers, and
springs. Such macroscopic aquatic fora includes
aquatic angiosperms (fowering plants), pteridophytes
(ferns), and bryophytes. Tey can be divided into four
categories according to the habit of growth: foating
unattached, foating attached, submersed, and emer-
gent. Macrophytes play a key role in nutrient cycling
to and from the sediments, and help stabilize river
and stream banks. Plants are ofen used for water
phytodepuration as they ef ciently use N and P
compounds present in wastewater; some species can
also concentrate heavy metals.
53
Such macrophytes
can be spontaneous, but in some countries they are
grown for several purposes, from water treatment to
nutrition (human and animal) and the production of
materials used in various sectors, including building.
With respect to microalgae and macroalgae, plants
may contain a larger content of cellulosic materials
and require diferent technologies for their treatment
and use for energetic purposes.
Harvesting of aquatic biomass
Diferent kinds of aquatic biomass require harvesting
techniques which difer in cost and energy. While
Chaetomorpha linum is present in unattached form in both estuarine systems and coastal lagoons
subject to eutrophication. It can live all the year and can reach high biomass values, estimated around
3.55 kg
fwt
m
2
.
Ulva laetevirens (as U. rigida C. Agardh) is present in attached and unattached form in estuaries and shallow
eutrophic lagoons. During the growing season it may reach 1520 kg
fwt
m
2
and large free-oating thalli.
Gracilaria bursa-pastoris is one of the few Rhodophyceae able to live in eutrophic coastal lagoons where
in some periods it becomes the dominant species of the drifting bed. It is present in attached and
unattached form in coastal lagoons and both hemispheres.
Pterocladiella capillacea, commonly lives on rocky hard substrata, often on vertical rock-faces, from the
inter-tidal level to about 20 m depth, in wave-exposed areas. This species is widely distributed in the
Mediterranean Sea, but lives in both hemispheres.
Codium vermilaria lives on hard horizontal substrata either in sheltered or lightly wave-exposed areas,
between 0 and 50 m depth, in shady places. This species is distributed in the boreal hemisphere from
North Atlantic Ocean to Mediterranean Sea.
Table 3. Macroalgae.
2
macroalgae and plants require simple operations,
microalgae, due to their size and, sometimes, fragility,
demand sophisticated equipment and handling
operations.
Te choice of harvesting methods depends on a few
factors: (i) type of algae that has to be harvested
(flamentous, unicellular, etc.); (ii) whether harvesting
occurs continuously or discontinuously; (iii) what the
energy demand is per cubic meter of algal suspension;
and (iv) what the investment costs are.
36,39,54
Te technologies mainly used with microalgae are
centrifugation, sedimentation, fltration, screening
and straining, and focculation. Various focculants
have been used, covering a large variety of chemical
structures such as metal compounds,
55
cationic
polymers,
56
and natural polymers such as chitin.
57

Tey have been employed not only at laboratory
scale, but also at industrial scale. Such induced
focculation may be accompanied by a spontaneous
or auto-focculation that can be caused by pH varia-
tion of the culture medium upon CO
2
consumption.
For example, an increase of pH may cause the precipi-
tation of phosphates (essentially Ca-phosphate) which
causes focculation of algae. Aggregation of algae,
produced by organic secreted substances
58
or aggrega-
tion with bacteria,
59
may also occur that facilitates
their sedimentation.
Centrifugation is a very popular technique today,
but still it presents some drawbacks such as the rate of
separation. Most advanced technologies are based on
the use of membranes (tubular, capillary, or hollow-
fber membranes) that are becoming more and more
popular.
60
Te size of the pore decreases in the order
from tubular (515 mm) to capillary (1 mm) to
hollow-fber (0.1 m) and the risk of plugging in-
creases with the decrease of the pore diameter.
Te harvesting of macroalgae and plants requires
more immediate and less sophisticated technologies.
Te technique depends on the fact that the biomass is
grown foating-unattached or foating-attached to a
hard substrate. In the former case, the biomass can be
easily collected using a net (as in fshing); in the latter
case it must be cut from the substrate. Automated or
manual devices can be used for the collection.
61
Aquatic biomass composition
Aquatic biomass contains several pools of chemicals
at diferent concentrations depending on the physical
stresses or genetic manipulation induced on the
organism. Table 4 compares the composition of
microalgae, macroalgae, and grass. Very ofen, despite
being members of the same marine algae species, the
chemical compositions were found to be diferent
according to the harvesting site.
62

In general, microalgae and macroalgae can be used
in diferent sectors:
1. Energy (hydrocarbons, hydrogen, methane,
methanol, etc.).
2. Foods and chemicals (proteins, oils and fats,
sterols, carbohydrates, sugars, alcohols, etc.).
3. Other chemicals (dyes, perfumes, vitamins/
supplements, etc.).
Aquatic biomass can be used as a raw, unprocessed
food as they are rich in carotenoids, chlorophyll,
phycocyanin, amino acids, minerals, and bioactive
compounds.
Besides their nutritional value, these compounds
have applications in the pharmaceutical feld as
immune-stimulating, metabolism increasing, choles-
terol reducing, anti-infammatory, and antioxidant
agents;
63
they are also rich in omega-3 fatty acids,
which have a signifcant therapeutic importance
inherent in the ability to act as an anti-infammatory
to treat heart disease.
Due to the high product-distribution entropy, the
extraction of a single product may have an economic
beneft if the product represents several tens % of the
global dry-mass. If it is present at the level of few units
%, then it should have a high market value for meet-
ing economic criteria. As mentioned above, the ability
of algal organisms to concentrate a type of resource
(proteins, starch, lipids) upon stress may help to
reduce the entropy and to increase the concentration
of a given product in the biomass. Tis issue is
particularly relevant when the use of aquatic biomass
for energy purposes is considered. Due to the cost of
cultivation, producing biomass with a high content of
energy products should be a must.
Table 4. Dry biomass composition (%) (organic
fraction).
Microalgae Macroalgae Grass
Saccharides 525 5080 35
Lipids 2040 824 3
Proteins 2050 727 25
Fibres (lignin) 3350 37
2
xation
Technologies for chemicals
production
Chemicals can be extracted from the biomass by
using a variety of technologies of diferent intensity
(destructive, semi-destructive, and non-destructive).
Tere is a relation between the sofness-hardness of
the technology used and the complexity of the struc-
ture of the chemicals extracted. Sofer technologies
will afect less complex molecular structures that will
be recovered unchanged. Hard technologies will
destroy complex networks and complex molecules.
Biomass is suitable for the production of diferent
products such as: bio-oil, biodiesel, bioalcohol,
biohydrogen, and biogas, all related to the production
of energy.
Extraction technique
Te extraction of chemicals from microalgae and
macroalgae may require diferent technologies due to
the diferent size and quality of the cell membrane of
the algae. Depending on the species strain, the cell
membrane can result to be very hard, so that crushing
of the membrane is recommended prior to the extrac-
tion. Such crushing is quite efective if performed at
low temperature, typically the liquid nitrogen tem-
perature (183 K). Tis will obviously increase the cost
of the extracted oil and lower its net energetic value.
Among the technologies used to produce chemicals
from biomass, pressure and solvent extraction can be
used for the extraction of bio-oil. Te former tech-
nique is not well suited to microalgae.
Extraction by using organic solvents (that may be
toxic to animals and humans) is very ofen used. Tis
may have a drawback due to the retention of solvent
by the algal mass which may represent a risk if the
extract is used as food, but has no consequences when
the extract is used as fuel.
Supercritical carbon dioxide (scCO
2
) may substitute
the organic solvent as it has some unique advantages
and is considered a good candidate for algae treat-
ment because it is a non-toxic and fully green
solvent.
64
Despite the advantages, using scCO
2
to
extract valuable compounds from microalgae is not
the prevailing technology in use today even though
production costs are of the same order of magnitude
as those related to classical processes. In fact, for such
techniques quite anhydrous materials are recom-
mended (water content below 5%), so energy should
be consumed to dry the biomass.
Bench scale scCO
2
experiments on microalgae
have been performed on Botryococcus, Chlorella,
Dunaliella, and Arthrospira from which diferent
types of valuable products have been extracted as
hydrocarbons (up to 85% mass of cell from Botryococ-
cus), paraf nic and natural waxes from Botryococcus
and Chlorella, strong antioxidants (astaxanthin,
-carotene) from Chlorella and Dunaliella, and
linolenic acid from Arthrospira.
Te moderate temperatures and inert nature of CO
2

have been shown to virtually eliminate the degrada-
tion of the product extracted. In addition to the
extract quality, the ability to signifcantly vary the
CO
2
solvation power by changes in pressure and/or
temperature adds operating fexibility to the scCO
2

extraction process that no other extraction method,
including solvent extraction, can claim.
65
For the scCO
2
extraction, the biomass should be
dried, then the cellular wall has to be broken in order
to increase the extraction yield (it is possible to use
liquid nitrogen, or a diferent method).
66
Sometimes
methanol can be added as co-solvent in order to
increase the extraction yield.
Bio-oil content of aquatic biomass
Tere is much interest lately in the use of microalgae
for the production of biodiesel, although this is not
the only producible fuel: biogas can also be produced,
as well as bioethanol or biohydrogen. Te quality and
composition of the biomass will suggest the best
option for the biofuel to be produced. A biomass rich
in lipids will be suitable for the production of bio-oil
and biodiesel, while a biomass rich in sugars will be
better suited to the production of bioethanol. Te
anaerobic fermentation of sugars, proteins, and
organic acids will produce biogas.
Several species of microalgae are very rich in lipids
(up to 7080% dry weight, with a good average
standard of 3040%) and this makes a given species-
strain more or less suitable for bio-oil production. Te
highest values are relevant to particular growing
conditions. In a commercial culture what is of interest
is the productivity of a pond, i.e. production per unit
time.
Table 5 shows, as a comparison, the amount (L) of
oil per hectare per year of diferent types of biomass
including microalgae.
67,68

Macroalgae, in general, present a lower content of
lipids than microalgae, and a larger variability.
69
Te
2
lipid content largely depends on the cultivation
technique and on the time of the year macroalgae are
collected.
70,71
Tese are, thus, key issues to be taken
into consideration in the development of a commer-
cial exploitation of such biomass.
Comparing microalgae and macroalgae, it must be
considered that macroalgae are produced at lower
costs than microalgae. Te energy value of an alga
cannot be stated just on the basis of the specifc
amount of oil produced but also from other very
important parameters, such quality, the possibility of
producing another form of energy from the residue
obtained afer the lipid extraction, etc.
The quality of bio-oil
Although algae biomass can be thermally processed to
aford an oily product, the acidity and composition of
the liquid are such that its direct use is not suited and
complex processing is needed before its use. We
consider here the extraction of lipids. Tey are a
mixture containing more than a single type of fatty-
acid (FA), most frequently the lipid fraction of algae
(both microalgae and macroalgae) contains a large
variety of FAs, with diferent number of unsatura-
tions, as shown in Table 6. Tis is an important issue
for assessing the energetic value of a biomass. Te
number of unsaturations in an FA is important as it
determines the usability of the compound as a fuel. In
fact, the optimal conditions for having a biodiesel
with good combustion properties is the presence of
only one unsaturation in the C-chains.
72
Terefore,
the higher the number of unsaturations, the lower the
quality of the biodiesel. Tis brings us to the conclu-
sion that the biodiesel extracted from aquatic biomass
ofen may need a hydrogenation treatment in order to
reduce its unsaturation number
73
and produce a
better quality fuel.
It has been experimentally demonstrated that the
product-distribution and unsaturation-distribution
can depend on the CO
2
concentration. An increase in
the CO
2
concentration of up to 10% in the gas-phase
has almost doubled the total concentration of FAs
(from 29.1 to 55.5%) and in particular that of FAs 16:0,
18:1, 20:4, and 20:5 in C. linum. In general, it has been
found that the number of unsaturations may increase
with the concentration of CO
2
.
74,75

Bio-oil, such as extracted, can be directly used in
thermal processes or in combustion, but cannot be
used in diesel engines as it presents a Low Heating
Value-(LHV) (812 MJ/kg) and high viscosity. To the
latter use it can be converted into biodiesel through a
transesterifcation reaction (Scheme 1) in order to
increase the LHV to 36 MJ/kg.
Considering biodiesel from an environmental point
of view, it includes several benefts: the reduction of
carbon monoxide (50%) and carbon dioxide (78%)
emissions,
76
the elimination of SO
2
emission as
biodiesel does not include sulphur; and the reduction
of particulate. As biodiesel is non-toxic and biode-
gradable, its use and production is rapidly increasing,
especially in Europe, the United States, and Asia. A
growing number of fuel stations are making biodiesel
Table 5. Yields (L ha
1
y
1
) of various types of
biomass.
Biomass Yield (L ha
1
y
1
)
Corn 170
Soybeans 455 to 475
Safower 785
Sunower 965
Rapeseed 1200
Jatropha 1890
Coconut 2840
Palm 6000
Microalgae 47 250 to 14 2000
Fatty acid Species and percentage of a given compound in the species
Compound
N of Catoms/unsaturated bonds Fucus sp
Nereocystis
luetkeana Ulva lactuca
Enteromorpha
compressa
Padiva
pavonica
Laurencia
obtuse
Saturated C
12
C
20
15.6% 27.03% 15.0% 19.6% 23.4% 30.15
Monounsaturated C
14
C
20
28.55% 15.84% 18.7% 12.3% 25.8% 9%
Polyunsaturated
C
16/2
C
16/4
, C
18/2
C
18/4
, C
20/2
55.86% 57.11% 66.3% 68.1% 50.8% 60.9%
Table 6. Distribution of fatty acids in lipids present in some macroalgae.
2
xation
available to consumers, and a growing number of
large transport feets use some proportion of biodiesel
in their fuel. Table 7 reports some fuel properties of
diferent types of biodiesel.
Production of bioalcohol
Aquatic biomass contain a variable quantity of simple
sugars and starch with a low amount of cellulosic
materials that are suited for the production of
alcohols. Mainly ethanol is obtained by fermentation
of such biomass, but other alcohols such as butanol
can be produced in smaller amounts. Te production
of bioethanol from a biomass alternative to corn is a
leading research theme these days.
Microalgae can be used to produce bioethanol
29
as
they are rich (up to >50% of the dry weight) in starch
and glycogen.
80,81
Similarly, macroalgae can be used for ethanol fermen-
tation by converting their storage material to ferment-
able sugars.
82
Te absence or low presence of lignin
makes the enzymatic hydrolysis of algal cellulose more
simple than in the case of terrestrial cellulosic biomass.
Very interesting is that bioethanol can be obtained
using oleaginous algal residue afer the extraction of
oil which contains yet fermentable sugar.
Bioethanol from algae can be obtained from starch/
cellulose which have to be extracted mechanically
(ultrasound, disintegration, mechanical shear, etc.)
from the cells or by using enzymes. Te starch is then
separated by extraction with water or an organic
solvent and used for fermentation to yield bioethanol.
Te latter process can be carried out in a single step
(using amylase) or a double step (saccharifcation
where the starch is hydrolyzed to simple sugars and
fermentation using suitable yeast strain). At the end,
ethanol needs purifcation to obtain a concentration
>95%.
83
Besides starch, several algae, especially green algae,
can accumulate cellulose as the cell wall carbohydrate,
which can also be used for ethanol production. Like
the cellulosic biomass from other plant sources, the
cellulosic biomass from the algae can also be enzy-
matically hydrolyzed using cellulase enzyme and
converted into simple sugars which can then be easily
fermented to ethanol.
Scheme 1. The conversion of a tryglyceride (lipid or bio-oil) into biodiesel (FAME).
Density
(kg/L)
Ash content
(%)
Flash point
(C)
Pour point
(C)
Cetane
number
Caloric value
(MJ/kg)
Ref
Algae 0.801 0.21 98 14 52 40 77
Peanuts 271 6.7 41.8
78
Soya bean 0.885 178 7 45 33.5
Sunower 0.860 183 49 49
Diesel 0.855 76 16 50 43.8
Biodiesel
from marine
sh oil
103 50.9 41.4 79
Table 7. Fuel characteristics of different bio-oils.
2
Production of biogas
Te anaerobic fermentation of fresh organic materials
is largely used for the production of biogas, a mixture
of methane and CO
2
. Te ef ciency of the process
depends on several parameters and the quality of the
biogas (ratio CH
4
/CO
2
) depends on the feed and the
operative conditions.
84,85
Reactors of diferent types
are used and both mesophilic micro-organisms and
thermophilic bacteria are active.
86
A large application
of such technology is the production of biogas by
fermentation of fresh municipal waste, thus turning
municipal waste into energy (methane) for the
community.
By their composition, algae, or aquatic biomass in
general, are quite suited for conversion into biogas. It
is clear that some kind of biomass may not be ad-
equate for such applications. Literature data indicates
that some species of microalgae are quite good for
biogas production.
87,88
Conclusions
Aquatic biomass, i.e. microalgae, macroalgae, and
plants, have a chemical composition that may vary
according to growing conditions also within the same
strain. To produce energy, the wild type are not
always suitable as they can be sensitive to the culture
conditions, so it is better to use a selected cultivated
strain in order to have an optimal energetic yield.
Aquatic biomass are a source of several compounds
which can be used as chemicals or to produce energy.
In particular the coproduction of chemicals and fuels
can be of great importance in order to make positive
the economic balance. In fact, the cost of fuels derived
from aquatic biomass is not competitive with that of
fossil fuels. Te correct application of the biorefnery
concept may result in the production of fuels at low
cost if high-value chemicals are coproduced. In the
near future aquatic biomass might contribute to the
production of transport fuels in a signifcant volume,
supposing that the right conditions for its growth,
collection, and processing are developed. In any case it
seems that the coproduction of chemicals and fuels is
necessary for proftable exploitation of aquatic biomass.
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Angela Dibenedetto
Angela Dibenedetto is Associate
Professor at the Department of
Chemistry, University of Bari (IT). Her
scientic interests focus on CO
2
utilization in synthetic, coordination
and organometallic chemistry,
catalysis, green chemistry, marine
biomass production by enhanced CO
2
xation, marine
biomass as source of fuels and chemicals applying the
Biorenery concept. She is Director of the Interdepart-
mental Centre on Environmental Methodologies and
TechnologiesMETEA UniBa.

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58 2011 Society of Chemical Industry and John Wiley & Sons, Ltd | Greenhouse Gas Sci Technol.

ol. 1:5871 (2011); DOI: 10.1002/ghg3

as a source of carbon, making the pH

would prefer basic water, while algae that use CO

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