10.1007@s11101 012 9268 y PDF

Phytochem Rev (2012) 11:413–431
DOI 10.1007/s11101-012-9268-y
Supercritical methodologies applied to the production

of biopesticides: a review
L. Martı́n • J. L. Marqués •
A. González-Coloma • A. M. Mainar •
A. M. F. Palavra • J. S. Urieta
Received: 27 July 2012 / Accepted: 23 November 2012 / Published online: 4 December 2012
Springer Science+Business Media Dordrecht 2012
Abstract Supercritical technologies are new, envi- atomization, particle from gas saturated solutions
ronmentally friendly, advanced separation techniques and supercritical solvent impregnation among others.
that have attracted the attention of both industry and The aim of this work is to give a general view of
academy in their aspirations of producing safer supercritical fluids in the field of biopesticides
products with cleaner processes. In the field of production, optimization and formulation, emphasiz-
biopesticides, supercritical fluids are being used in ing in the extraction, fractionation and encapsulation
different stages, from the extraction of active ingre- and highlighting their importance when green, solvent
dients from natural matrices to the encapsulation of free processes have to be designed.
blends during the formulation of the final commercial
pesticide. This review summarizes different supercrit- Keywords Natural pesticides Extraction
ical processes that arise in literature comprising Formulation Fractionation Supercritical fluids
supercritical fluid extraction, supercritical antisolvent
fractionation or extraction, supercritical assisted
Introduction
L. Martı́n A. M. Mainar J. S. Urieta (&)
Group of Applied Thermodynamics and Surfaces
The interest for biopesticides has been growing
(GATHERS).I3A (Aragón Institute of Engineering
Research), Facultad de Ciencias, Universidad de rapidly since the awareness for sustainability, climate
Zaragoza, C/Pedro Cerbuna 12, 50009 Zaragoza, Spain change and organic farming has risen dramatically.
e-mail: [email protected] Biopesticides, according to the United States Envi-
ronmental Protection Agency (USEPA) include natu-
J. L. Marqués
Departamento de Quı́mica Fı́sica I, Facultad de Ciencias rally occurring substances and microorganisms that
Quı́micas, Universidad Complutense de Madrid, Ciudad control pests and pesticidal substances produced by
Universitaria, 28040 Madrid, Spain plants containing added genetic material (US Envi-
ronmental Protection Agency 2012). Economically
A. González-Coloma
CSIC, Instituto de Ciencias Agrarias, C/Serrano 115-bis, speaking, pesticides have a worldwide emerging
28006 Madrid, Spain market (1,600 million dollars in 2008 and 3,300
million dollars in 2014 according to previsions) (The
A. M. F. Palavra
2010 Worldwide Biopesticides Market Summary
Departamento de Engenharia Biologica, IST (Instituto
Superior Tecnico) de la Universidad Técnica de Lisboa, 2011) due to two factors: organic agriculture and its
Torre Sul, Avda. Rovisco Pais 1, Lisbon, Portugal regulations (Isman 2006) grow exponentially every
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414 Phytochem Rev (2012) 11:413–431
year and restrictions for the use of synthetic pesticides (Cagniard de la Tour 1822), however the development of
are increasing rapidly. Biopesticides are forced to supercritical techniques did not start until the 1970s,
comply with the legislation in different fields. Inside when Supercritical Fluid Extraction (SFE) was found to
the European Union, in the Sixth Environment Action be efficient in the removal of lower boiling products from
Programme in matter of organic farming (European the residue of crude oil distillation (Gearhart and Garwin
Commission 2007) the following aspects are priori- 1976) or in the decaffeination of coffee beans (Zosel
tized: crops rotation, locally organized renewable 1981). Since then, several techniques have been applied
resources, adequate species selection and also ade- in different fields including chemical reactions (Aresta
quate products for handling with pests. Among these et al. 2003; Lester et al. 2006; Moreno et al. 2011; Han
products to handle pests, those preferred are: the and Poliakoff 2012), soil decontamination (Librando
derived from organic farming, low solubility fertiliz- et al. 2004; Saldaña et al. 2005; Sunarso and Ismadji
ers and natural products or derived. Synthetic organic 2009), advanced materials fabrication (Reverchon and
pesticides, on the contrary, are known for causing Adami 2006; Pérez et al. 2010; Morre et al. 2011; Zhang
ecological disasters in their industrial production such et al. 2011), preparation of pharmaceutical (Domingo
as the Bhopal accident in 1984 (Lapierre and Moro et al. 1997; Davies et al. 2008; Reverchon et al. 2009;
2002), ecological problems in their massive use such Della Porta et al. 2011; Elizondo et al. 2011) and food
as aquifer contaminations (Diaz-Cruz and Barcelo products (Rubio-Rodriguez et al. 2008; Fernández-
2008) or bioaccumulation (Katagi 2010). Ronco et al. 2011; Bernardo-Gil et al. 2011) or extraction
In this context, the production of biopesticides is of bioactive compounds from natural matrices (Martı́nez
included in the philosophy of Green Chemistry, a 2007; Casas et al. 2009; Langa et al. 2009a, b; Martı́n
current within the Chemistry which seeks safer prod- et al. 2011e).
ucts with cleaner processes, whose twelve principles The process design using supercritical fluids
were enumerated by Anastas and Warner (2000). Some depends highly on the phase equilibrium scenario,
of them can be found in the production of biopesticides strongly sensitive to changes in operating conditions.
such as: the energy and raw materials saving, the Therefore, phase equilibrium engineering plays a key
promotion of safer industries, the non toxicity of the role in the synthesis and design of these processes.
products or the use of renewable raw materials (those This engineering is the systematic application of phase
considered inexhaustible in a human life cycle). equilibrium knowledge to process development,
Among these principles, supercritical fluids, especially including experimental data, data banks, phenomeno-
supercritical CO2 (scCO2), are a paradigm as alterna- logical phase behaviour, thermodynamic analysis and
tive solvents, minimizing the quantities of organic mathematical modeling procedures for phase equilib-
solvents used and complying with sustainability. rium process calculations (Herrero et al. 2010).
A supercritical fluid is by definition an element or Although supercritical fluids have been used in
compound above its critical pressure and temperature. several processes along their history and in several
In a simpler form, behind this definition a fluid with disciplines, the aim of this review is to summarize those
extraordinary properties can be seen. It combines techniques that have been used in the extraction,
physicochemical properties of a gas and of a liquid; it optimization and formulation of biopesticides, which
has the viscosity and diffusivity of the former and the will include: supercritical fluid extraction (SFE),
solving power of the latter. Furthermore, its density, supercritical antisolvent fractionation (SAF), supercrit-
that is to say, its solvating capacity, can be tuned by ical antisolvent (SAS), supercritical solvent impregna-
varying slightly the pressure and temperature condition (SSI), particles from gas saturated solutions
tions (Taylor 1996). Moreover, if the supercritical (PGSS) and supercritical assisted atomization (SAA).
fluid is depressurized enough, it passes to gas,
separating itself from the solute, which precipitates
solvent-free. These characteristics can make a super- Supercritical fluid extraction (SFE)
critical fluid an ideal alternative solvent in Green
Chemistry. The SFE is the most used supercritical technique, and
The first reported observation of the occurrence of a although it is somewhat new in time, it has already
supercritical phase was made by Baron Cagniard in 1822 been deeply studied. Chemical, petrochemical and
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Phytochem Rev (2012) 11:413–431 415
food industries have been developing different pro- after the extraction process by means of a new
cesses related to this technique. Foods as decaffeinated compression, which also diminishes operational costs.
coffee or tea, fruit juices with flavour enhancers or As it has been mentioned before, its solvating capacity
alcoholic drinks whose graduation has been reduced, can be tuned by varying slightly the pressure and
have been obtained industrially by means of this temperature conditions, so step extractions or consec-
technique (Brunner 2005; Ruiz-Rodrı́guez et al. 2012). utive separators allow for a simple fractionation. The
However, the obtention of added value natural prod- principal disadvantage of CO2 is its apolarity, which
ucts by means of this safe and clean technique is the makes the CO2 dissolve mainly apolar compounds. To
application that has to be highlighted among the uses overcome this limitation, a modifier, also called
of SFE. entrainer, (principally alcohols in a range of
SFE has become an alternative method to the 1–10 %) of the supercritical fluid can be added, which
traditional extraction ones such as hydrodistillation lets the mixture dissolve more polar compounds.
and organic solvent extraction, because it avoids the At laboratory scale or pilot plant scale, several
disadvantages of them. Hydrodistillation can cause vegetable species have undergone extraction pro-
hydrolysis and hydrosolubilization or can degrade cesses with supercritical CO2 (scCO2), with different
thermolabile compounds, while the use of organic results and applications (Pereira and Meireles 2009).
solvents in traditional extractions entails the inherent Some factors influence the extraction and they have to
problems of working with these types of solvents be taken into account when carrying out a series of
(generation of Volatile Organic Compounds, sample experiments; so evident as the temperature, the
contamination, expensive removal of the solvent, supercritical pressure, the CO2 flow or the extraction
human toxicity) (Reverchon 1997). The only serious time and some other not as evident as the particle size,
disadvantage of SFE is a high investment cost the packing of the material in the extractor or the water
compared to traditional atmospheric pressure extrac- content of the vegetable matrix.
tion techniques. However, the base process scheme Although SFE is a well known technique (14,023
(extraction plus separation) is relatively cheap and references in scifinder, key words supercritical fluid
very simple to be scaled up to industrial level extraction), the biopesticides obtention with such
(Reverchon and De Marco 2006). technique is not so common (26 references in scifind-
SFE consists in mixing inside a vessel a supercrit- er, key words supercritical fluid extraction ? natural
ical fluid (the solvent) with a matrix where the pesticide, 724 references, keywords supercritical fluid
interesting compounds (the solutes) are. The viscosity, extraction ? pesticide, although the majority of them
diffusivity and solvent power of the supercritical fluid refers to the determination of pesticide residues in
allow the compounds to be solubilized in it. After- soils or food). However, some examples available in
wards, a correct depressurization of the supercritical literature can be seen and will be reviewed in this
phase allows the recovery of the solvent free com- paper.
pounds and the compounds free solvent. Furthermore,
if an adequate configuration is used in the depressur- SFE of pyrethrins
ization, several fractions can be obtained if the
operational conditions of the separators are properly One of the applications of the biopesticide extraction
chosen. with supercritical fluid is the pyrethrins extraction
The most widely used supercritical fluid for from plants of the genre Chrysanthemum. Pyrethrins
extraction is carbon dioxide; economic, inert, non (Fig. 1), the most widely used natural domestic
toxic, environmentally friendly and generally recog- insecticides, are extracted from pyrethrum flowers
nized as safe by United States Food and Drug and are comprised of two groups of active compounds:
Administration and European Food Safety Agency. pyrethrins I, with lethal effect, (including pyrethrin I,
Furthermore, its operational conditions are moderate jasmolin I and cinerin I) and pyrethrins II, with knock
because of the critical temperature and pressure down effect (including pyrethrin II, jasmolin II and
(31.1 C and 7.39 MPa respectively), which avoids cinerin II) which are known for being highly selective
thermal degradation and excessive safety require- on insects (Wolansky and Harrill 2008). They are
ments. At industrial scale, the used CO2 is recycled harmful for fishes, although they are much less
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416 Phytochem Rev (2012) 11:413–431
harmful for mammals and birds than other synthetic 20 C than at 40 C and decreased with a decrease in
insecticides (Yamamoto 1970). They are not persis- pressure. The effect of the particle size was investi-
tent, as they are easily decomposed when exposed to gated, yielding the biggest particles a lower quantity of
sunlight (Casida 1980). Conventionally, pyrethrins are extract with less pyrethrin. The extract obtained from
extracted with organic solvents (hexane, methanol, smaller particles at 40 C, contained more undesired
petroleum ether…) (Ban et al. 2010), but several product, finding that the best selectivity was achieved
authors have already studied the SFE of pyrethrins. at subcritical conditions (operating at 20 C). They
Sims patented the liquid carbon dioxide extraction also established that the seed part of the whole flower
of pyrethrins (Sims 1981), while Otterbach compared contained more crude extract and pyrethrins than the
pyrethrum extract obtained by ultrasonic extraction, flower part, so a pre-treatment of unground flowers by
Soxhlet extraction using hexane, and scCO2 extrac- washing with scCO2 improved the quality of scCO2
tion, and observed that the scCO2 process yielded extract, because a part of the undesired waxes was
better quality extracts in terms of colour and pyrethrin eliminated by the pre-treatment. A simpler procedure
content (Otterbach and Wenclawiak 1999). of eliminating the waxes with hexane and then
Pan et al. (1995) conducted the SFE of dry pyrethrum purifying the obtained extract by means of SFE was
flower powder to obtain pyrethrins in the range of also proposed by Kirimiati et al. (2003a) in a
8.3–2.48 MPa at 40 C. The most effective extraction subsequent paper.
occurred at 8.3 MPa, achieving 140 ± 18 mg of pyre- Marongiu et al. (2009) accomplished the SFE of
thrins I and 55 ± 9 mg of pyrethrins II per 100 g of dry three sardinian chrysanthemum flowers, Chrysanthe-
pyrethrum flower powder. The results showed that mum coronarium L., Chrysanthemum segetum L. and
extraction efficiencies of scCO2 were much better than Chrysanthemum flosculosus L., the last one endemic to
those of n-hexane. During the extraction process, the the region. Their volatile fractions were extracted at
most efficient extraction period was the first 3 h of the 9.0 MPa and 50 C, their compositions compared to the
experiment. ones obtained by hydrodistillation, and their antibacte-
Della Porta and Reverchon (2002), extracting rial and antimycotic activities were contrasted with
pyrethrins from pyrethrum, showed that pyrethrins those of the essential oils obtained by hydrodistillation,
were readily soluble in the scCO2, so they could be and to the SFE extracts of Chrysanthemum cinerariifo-
extracted at 9.0 MPa and 40 C, avoiding high lium, a commercial species rich in pyrethrins. They
pressures that could lead to coextraction of undesired tried to extract pyrethrins at 30.0 MPa and 50 C,
compounds. In fact, they conducted a second extrac- finding that the Sardinian plants did not contain any
tion step at 20.0 MPa and 40 C, showing that pyrethrin, while the commercial pyrethrin rich plant
pyrethrins yield did not increase, compared to that of yielded 1.1 % (w/w), with a pyrethrin I to pyrethrin II
the extraction at 9.0 MPa and only undesired com- ratio of 1.3. Moreover, they found out that some of the
pounds were extracted. extracts had antifungal and antibacterial activity, but
Kiriamiti et al. (2003b) studied the effect of their antimicrobial activity was not selective nor
pressure, temperature, particle size and pre-treatment specific. All the supercritical extracts of the local plants
of raw material upon quality and quantity of pyre- were active on plant pathogens (Botrytis cinerea and
thrum flowers extracts obtained with carbon dioxide. Rhizoctonia), while some of their hydrodistilled
They used both supercritical and subcritical CO2 in the showed no activity. Chrysanthemum cinerariifolium
range of 7.0–25.0 MPa and 20–40 C, relying on supercritical extract, on the contrary showed no activity
Stahl, who saw that there was no decomposition of over those plants pathogens.
pyrethrins in pressurized CO2 if the temperature was
increased from 20 to 40 C (Stahl and Schutz 1980).
They achieved a similar extract to the one obtained by SFE of azadirachtins
hexane Soxhlet extraction, excepting that the ratio of
pyrethrins I to pyrethrins II was lower and with less Other pesticidal compounds obtained by means of SFE
pigments. At 40 C the amount of extract was found to are the azadirachtins, extracted mainly from the seeds
be independent of pressure above 10.0 MPa. Pyrethrin of neem tree, Azadirachta indica. Azadirachtins are
content in the crude extract was shown to be higher at tetranortriterpenoids formed by a group of closely
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Phytochem Rev (2012) 11:413–431 417
related compounds including azadirachtin, salannin, 0.24–1.24 ml/min, finding that the best extraction
gemudin and nimbin. Azadirachtin (Fig. 1) is used as a conditions in their studied range occurred at 35 C,
natural pesticide and is considered as a gold mine, due 23.0 MPa and 1.24 ml/min, obtaining 0.18 mg nimbin
to its feeding deterrency for many insects, its growth per gram of neem seed per hour. In fact, a more
disruptancy for most insects and its very low toxicity extensive study conducted by the same group (Tont-
for vertebrates (Morgan 2009). Among others, it has hubthimthong et al. 2004) reached to the conclusion
shown inhibitory effect on vitellogenin during oogen- that methanol was not found to be an effective
esis of arthropods (Jonsson and Piper 2007), acceler- modifier for extracting nimbin as the marginal
ation of the hatching rate and mortality of Hyalomma increase in extraction yield using methanol as modifier
anatolicum excavatum larvae (Abdel-Shafy and Zayed was not substantial, compared to the added difficulty
2002) and decreased blood-feeding in Dermacentor and cost of handling and separating a toxic modifier.
variabilis (Landau et al. 2009) (Fig. 1). Today’s trend within SFE is to try to obtain
Johnson and Morgan (1997) studied the selective azadirachtins with a higher yield and a higher
extraction of azadirachtins and oil from neem seeds recovery. To that extent, studies of the solubility of
using scCO2 with and without methanol as entrainer. azadirachtin in scCO2 (Ismadji et al. 2011) and models
The extraction with scCO2 for 30 min could not to optimize the SFE of nimbin (Zahedi et al. 2010a, b)
remove nor the totality of the oil, nor the azadirachtins, have been accomplished in order to improve the
while when prolonging the extraction to 150 min, all operational conditions that could increase both the
the nimbin and salannin were extracted, leaving some recovery and the yield. In spite of the difficulties
azadirachtin unextracted. When operating at related to innovation in the pesticides market, several
34.4 MPa with percentages of methanol of 20 %, attempts of commercializing supercritically obtained
most of the azadirachtin was extracted, while an extracts of azadirachtins from neem seeds have been
optimum for extracting nimbin and salannin was carried out, including Essences srl, (Salerno, Italy) and
found at 20.65 MPa and 6 % MeOH. Working at ACRA (Milano, Italy). The latter has tried the
reduced pressures (13.7 MPa) they were also able to sustainable production of a neem based insecticide
extract the whole nimbin and salannin, but 20 % of with the cooperation between third world countries
MeOH was used in this case. and Europe (ACRA 2012).
Ambrosino et al. (1999) used sub and supercritical
CO2 in the range of 20–40 C and several pressures to SFE of rotenone
obtain azadirachtins from raw or previously pressed
neem seed kernels. The highest azadirachtins recovery Rotenone is other natural compound that can be
was obtained with scCO2 at 29.5 MPa and 40 C, extracted by SFE. Rotenone (Fig. 1), whose insecticidal
reaching values of 8,810 mg azadirachtins per kg of potential is known since ancient times, is a molecule that
oil and 2,291 mg azadirachtins per kg of seeds. can be obtained from several tropical plants such as
Tonthubthimthong et al. (2001) studied the selec- Derris elliptica, Lonchocarpus nicou or Tephrosia
tive SFE of nimbin from neem seeds. They worked vogelii. The amazonic tribes threw rotenone rich
in the range of 10.0–26.0 MPa, 35–60 C and extracts into water and fished manually the fishes that
Fig. 1 Pesticidal
compounds obtained from
natural matrices by means of
SFE
Rotenone Azadirachtin Pyrethrin I (R=CH3)

Pyrethrin II (R=CO 2CH3)
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418 Phytochem Rev (2012) 11:413–431
were poisoned, capturing them once they got to the modes of action (Imdorf et al. 1999; Rossini et al. 2007).
surface paralyzed or even dead. Besides being a Essential oils, for instance, show antifungal (Mishra and
piscicide, it is also used as a wide spectrum insecticide Dubey 1994), nematicidal (Pandey et al. 2000),
against pests as the potato beetle (Leptinotarsa decem- antibacterial (Burt 2004), repellent (Nerio et al. 2010)
lineata) or the common fruit fly (Drosophila melano- and insecticidal properties among others (Regnault-
gaster). It was once allowed as pesticide in the organic Roger et al. 2012). Some of the SFE experiments aimed
agriculture by the EU (European Commission 1991) due at the extraction of natural compounds tested as
to its natural origin, its safety to non-target organisms, its biopesticides are gathered in Table 1. In Table 1, 19
low resistance development and its short persistence, studies handling with supercritical extractions of nat-
but it has been restricted (European Commission 2007) ural extracts appear. In these studies, 24 species have
due to the fact that a link between rotenone and undergone SFE in order to obtain bioactive fractions,
Parkinson’s disease has been discovered (Tanner et al. and their activities have been tested over several pest
2011). However, its SFE is a valid example of extracting organisms. The extracts showed diverse compositions
and developing a supercritical insecticide. and the pesticidal actions evaluated were different
Li et al. (2005) and Huang et al. (2006) have obtained (insecticidal, fungicidal, herbicidal, antibacterial…).
rotenone from Tephrosia vogelii. The former worked at The supercritical conditions were as follows: pressures
27.58 MPa -60 C adding methanol as modifier and ranged from 8 to 40 MPa, while the used temperatures
achieved the extraction of 98 % of rotenone compared went from 30 to 80 C, depending on the studied plant.
to that extracted with a chloroform maceration. The Yields varied from 0.40 to 14 %. In 11 of those studies,
latter made a systematic study in the ranges of four different cosolvents (methanol, water, acetone,
22–28 MPa and 30–60 C. The highest rotenone con- ethanol) were used with proportions from 2.4 to 11.8 %,
centration in the extract was obtained at 30 C and being ethanol the most used cosolvent.
24 MPa, while the highest yield of rotenone respecting It has to be noticed, however, that several exper-
to the quantity of dry material was obtained at 60 C and iments to extract volatile and non volatile compounds
22 MPa (4.49 mg rotenone per gram of dry material). with pesticidal properties from natural matrices are not
In order to improve the extraction, 10 % of ethyl acetate gathered in the table, as their pesticidal activities have
was added as modifier at 60 C and 22 MPa, obtaining not been tested in the same research. For instance,
an extract with 7.96 % rotenone and a yield of 5.99 mg some biopesticides that have been approved recently
rotenone per gram of dry material. by the EPA, listed in a review of Cantrell et al.
D’Andrea et al. (2007) proposed the extraction of (Cantrell et al. 2012), include extracts or single
rotenone from the roots of Derris elliptica (Wallich) compounds that have already been obtained by SFE.
Benth. They carried out a study at different pressures The former contain canola oil (Dunford and
(9–44 MPa), temperatures (40–60 C) and CO2 to Temelli 1997; Pederssetti et al. 2011), black and
feed material ratios (10–100 g/g). From all the studied white pepper oil (Ferreira et al. 1999; Perakis et al.
conditions, the most efficient extraction occurred at 2005; Zhiyi et al. 2006; Dou et al. 2010), fish oil
44 MPa, 60 C and a CO2 to feed material of 100 g/g. (Rubio-Rodrı́guez et al. 2012) or catnip oil (Louey
In these optimum conditions, the extract purity and the et al. 2001), while the latter are comprised by indole
rotenone yield were 64.2 and 11.25 % respectively, that could be extracted from Tabernaemontana cath-
while the Soxhlet extraction (methanol:dichlorometh- arinensis (Pereira et al. 2004) or Catharanthus roseus
ane 1:1 (v:v)) accounted for values of 27.7 and 8.36 %. (Verma et al. 2008), L carvone from Lippia alba
(Braga et al. 2005), Carum carvi (Baysal and
SFE of volatile oils Starmans, 1999), or Mentha spicata (Almeida et al.
2012), lysophosphatidylethanolamine from antler vel-
Apart from the aforementioned examples, the SFE of vet (Zhou and Li 2009), methyl eugenol from Anem-
constituents of volatile oils and natural extracts is one of opsis californica leaf oil (Medina et al. 2005), allyl
the most studied fields in the biopesticides develop- isothiocyanate from Wasabia japonica matsum (Li
ment. This is so as the appearance of resistance against et al. 2010), piperine from Piper nigrum (Sankar,
complex natural products is unlikely or very low, 1989) or verbenone from Lavandula viridis (Costa
because they have different components with various et al. 2012).
123
Table 1 Biopesticides extracted by means of supercritical fluid extraction
Vegetable matrix Main compounds obtained Activity Organism T (C) P (MPa) Co-solvent (%) Yield (%) Reference
Armoracia rusticana Isothiocyanates Insecticidal Sitophilus zeamais 45 25 11.8 (H2O) 6.10 Wu et al. (2009)
Rhizopertha dominica
Tribolium ferrugineum
Liposcelis entomophila
Artemisia absinthium Z epoxyocimene, C10H18O2, Antifeedant Spodoptera littoralis 40 9–18 0–2.5 % EtOH n.d Martı́n et al.
absilactone type Phytotoxic Myzus persicae (2011c)
sesquiterpene
Rhopalosiphum padi
Phytochem Rev (2012) 11:413–431
Lactuca sativa
Lolium perenne
Artemisia sieberi Camphene, cineol Fungicidal Anopheles 30–65 10.1–30.4 2.40–11 (MeOH) 1.6–14 Ghasemi et al.
Mosquito repellency (2007)
Chamaecyparis t-cadinol, t-muurolol Antifungal Gloeophyllum trabeum 60 20 No 3.27 Du et al. (2010)
lawsoniana Trametes versicolor
Chamaecyparis Nootkatone, t-cadinol 3.22
nootkatensis
Juniperus virginiana Cedrol 3.29
Citrus sinensis l-limonene, palmitic and Antimicrobial Staphylococcus aureus 40–50 10–30 0–8 EtOH 0.61–3.0 Benelli et al.
oleic acids Escherichia coli (2010)
Coriandrum sativum Linalool Herbicidal Zea mays 40 9 No n.d Santoyo et al.
Santolina 1,8 cineole, cmaphor Triticum durum 40 8 (2006)
chamaecyparissus
Satureja montana Carvacrol, thymol Pisum sativum 40 9
Thymus vulgaris Thymol, p-cymene Lactuca sativa 40 9
Portulaca oleracea
Vicia sativa
Daucus carrota Geranyl acetate, Antibacterial Staphylococcus aureus 40–50 9–10 No 0.91–1.17 Glišić et al. (2007)
b-caryophyllene Fungicidal Enterococcus faecalis
Bacillus subtilis
Bacillus cereus
Listeria monocytogenes
Rhodococcus equi
Escherichia coli
Salmonella enteritidis
Pseudomonas aeruginosa
Candida albicans
419
123
Table 1 continued
420
Vegetable matrix Main compounds obtained Activity Organism T (C) P (MPa) Co-solvent (%) Yield (%) Reference
123
Echinacea angustifolia R-cyclopentadecanone Antifungal Botrytis cinerea 45 30 No n.d Li et al. (2011)
Helianthus annuus n.d Herbicidal Triticum aestivum L 50 38 2.5–4.8 H2O 0.2–1.6 Casas et al. (2008)
Hydrocotyle wilfordi Bis(2-ethylhexyl)-phthalate Toxicity Plutella xylostella 50 35 No 5.32 Hu et al. (2008)
Origanum majorana a-terpinene, p-cymol Antimicrobial Aspergillus niger 50 45 No 3.8 Vági et al. (2005)
Antibacterial Trichoderma viride
Penicillium cyclopium
E. coli
B. cereus
P. fluorescens
Origanum vulgare Carvacrol, trans-sabinene Antimicrobial Staphylococcus aureus 40 15 7 EtOH n.d Santoyo et al.
hydrate, cis-piperitol, Antibacterial Bacillus subtilis (2006)
borneol,
terpinen-4-ol, linalool Antifungal Escherichia coli
Pseudomonas aeruginosa
Candida albicans
Aspergillus niger
Rosmarinus officinalis Alpha-pinene, 1,8-cineole, 60 25 4 EtOH n.d Santoyo et al.
camphor, verbenone, and (2005)
borneol
Persea indica Ryanodol Antifeedant Spodoptera littoralis 40–50 10–20 0–2.5 EtOH 0.40–1.13 Martı́n et al.
(2011b)
Rosmarinus officinalis a -pinene, camphor Antibacterial Geobacillus 40 11.5–40 No 1.02 Ivanovic et al.
stearotermophillus (2012)
Bacillus cereus
Bacillus subtilis var.niger
Enterococcus faecium
Salmonella enteritidis
Escherichia coli
Salvia officinalis a -thujone, camphor 2.13
Thymus vulgaris Thymol, p-cymene 1.23
Satureja hortensis d-terpinene, carvacrol Acute toxicity Musca domestica, 50 12–28 0–4.3 acetone 3–4 Pavela et al. (2008)
Spodoptera littoralis,
Culex quinquefasciatus
Leptinotarsa decemlineata
Satureja hortensis d-terpinene, carvacrol Insecticidal, Leptinotarsa decemlineata 50 12–28 0–4.3 EtOH 3–4 Pavela et al. (2009)
antifeedant
Thymus vulgaris d-terpinene, p-cymene 0–4.3 acetone 1.6–3.3
Phytochem Rev (2012) 11:413–431
Phytochem Rev (2012) 11:413–431 421
Darabi et al. (2011)

Pavela et al. (2010)
Some patents have been already licensed with the
Liang et al. (2012)

topic of SFE of volatile oils showing diverse uses
(Santos and Meireles 2011); there are also different
Reference
patents handling with the SFE of biopesticides, such as

the SFE of cis-abienol from Abies sachalinensis
(Tatsuro and Mitsukatsu 1996). The process takes
Yield (%)
place at 9.8 MPa and 40 C for 60 min, obtaining an

2.5–3.8
extract containing 13.60 % of cis-abienol (compared to

3.75
n.d
the hexane extract, containing just 1.31 %). Another

patent handles with the SFE of Chenopodium ambro-
sioides, process that provides an insecticide synergist
Co-solvent (%)
0–4.3 acetone
formed by its essential oil or its supercritical extract

(Hui et al. 2009). A third patent includes bioinsecticide
derivatives extracted from plants with specific chem-
No
No
otypes of Artemisia absinthium by organic or super-

Plant material, main compounds extracted, action tested, target organism and extraction conditions are included, together with the authors
P (MPa)
critical CO2 extractions (Gonzalez Coloma et al. 2012).

12–28
Apart from EPA approved biopesticides, there is also

15
19
a category of minimum risk pesticides included in the

T (C)
biopesticides category that are exempt from registration

49
80
50
under section 25(b) of the Federal Insecticide, Fungi-

cide and Rodenticide Act (US Environmental Protec-
Tetranychus cinnabarinus
tion Agency 1947) which include oils (hydrodistilled

Shiroodi wheat variety
Spodoptera littoralis
and/or pressed oils) of several species. As the extracts

obtained by SFE are analogous to these oils, research
has already been conducted in order to obtain, by means
Organism
of SFE, extracts with similar properties and composi-

tions to those considered of minimum risk. Among
them, the extraction of oils from seeds (soybean,
Mortality, antifeedancy
Germination inhibitor
cottonseed…) counts already with an SFE official

Contact, systemic
method (Firestone 1998). Other volatile oils (compris-

ing hydrodistilled and pressed oils) have also been
and growth
inhibition
toxicity
obtained by SFE: cinnamon (Zhao and Liang 2006;

Activity
Marongiu et al. 2007; Miao and Deng 2011), clove

(Della Porta et al. 1998; Yazdani et al. 2005; Guan et al.
2007; Darabi et al. 2011), citronella (Wu et al. 1994;
Silva et al. 2011), lemongrass (Carlson et al. 2001;
Main compounds obtained
Eugenol, eugenyl acetate
Rozzi et al. 2002), mint (Barton et al. 1992; Dı́az-

octadecadienoic acid
Camphor, camphene
Maroto et al. 2002; Almeida et al. 2012), peppermint

Squalene, 9,12-
(Goto et al. 1993; Castillo et al. 2003; Sovová et al.

2006), rosemary (Santoyo et al. 2005; Zermane et al.
2010; Garcı́a-Risco et al. 2011a; Ivanovic et al. 2012),
garlic (del Valle et al. 2008), geranium (Peterson et al.
2006; Gomes et al. 2007) or thyme (Pavela et al. 2009;
Tanacetum parthenium
Grosso et al. 2010a, b; Garcı́a-Risco et al. 2011b). In

Syzygium aromaticum
Stellera chamaejasme
Table 1 continued
these minimum risk pesticide category there are also

Vegetable matrix
single compounds that have been extracted from natural

matrices by means of SFE such as eugenol (Geng et al.
2007; Tongwei et al. 2010) or geraniol (Moldão-
Martins et al. 2000; Machmudah et al. 2009).
123
422 Phytochem Rev (2012) 11:413–431
SFE is, by large, the most used supercritical the conditions in which the antidissolution takes place.
technology to obtain biopesticides from natural matri- The liquid solution and the scCO2 have to be miscible in
ces. In fact, it has become an existing alternative to the the working conditions avoiding the insolubility gap,
traditional extraction methods, as it has been described taking into account that the compounds dissolved in the
in the explained examples. Advantages such as the easy organic solution could raise the critical point. An
separation solvent–solute, the tunable density allowing incorrect selection of the working conditions would
a selective fractionation, the fast operation, the mild lead to a two phase behavior that could ruin the process.
operating conditions and its green potential have The supercritical antisolvent processes present
converted this technique into a way in which biopes- several advantages over classical antisolvent liquid
ticides can be obtained. On the other hand, the high techniques such as the easy separation of the super-
operational costs (counterbalanced however in most of critical solvents from precipitating products, their high
the cases by the quality and purity of the extracts) and diffusivity or their miscibility with many organic
the inherent inertia of the productive sector are the solvents, due to the well known characteristics of the
obstacles that have to be avoided in order to further supercritical fluids (Rodrigues et al. 2011).
develop the obtention of biopesticides by means of SFE. SAE/SAF methods have mainly found applications
in the fractionation of compounds from natural
matrices. Some examples can be found in bibliography
Supercritical antisolvent fractionation/extraction such as the fractionation of propolis (Catchpole et al.
(SAF/SAE) 2004), the selective obtention of polyphenols and
anthocyanins from ethanolic solutions of freeze-dried
Apart from being used as extractive agents, supercrit- grape residues (Floris et al. 2010), the refining of
ical fluids can be used as antisolvents in the so called phospholipids from egg yolk (Aro et al. 2009) the
Supercritical Antisolvent Fractionation (SAF) or fractionation of Ginkgo biloba extracts (Zhao et al.
Supercritical Antisolvent Extraction (SAE). Once 2011) or the carnosic acid fractionation from rosemary
again, the mainly used supercritical fluid is CO2, ethanolic oleoresins (Visentı́n et al. 2011).
being used as antisolvent, dissolving the organic SAE/SAF techniques have been used scarcely up to
solvent in which a mixture is contained, sweeping date in the production of biopesticides, so there is still
away undesired compounds and allowing thus the a great research potential in this field. Nonetheless,
enrichment of interesting compounds. Martı́n et al. (2011a) have obtained ryanodol rich
The fractionation with supercritical CO2 uses the extracts parting from ethanolic solutions of Persea
apolar nature of the supercritical solvent to fractionate indica, a macaronesian endemic tree. Ryanodol has
the compounds of interest present in a multicomponent already shown its insecticidal activity (Gonzalez
solution. It consists of the continuous contact between Coloma et al. 1993) in both traditional and SFE
scCO2 and the liquid mixture in a pressurized precip- extracts (Martı́n et al. 2011b). A further enrichment of
itation vessel. A spray of the liquid solution is produced ryanodol by means of SAF has also shown better
in the supercritical medium to enhance the mixing of the insecticidal activities than the extracts obtained either
two fluids and, if the process is performed at optimized by SFE or by Soxhlet extraction.
conditions, the liquid solution can be fractionated by A similar procedure that uses CO2 as antisolvent,
scCO2, precipitating part of the solutes as solid powder but in gas phase under the critical point, is the Gas
at the bottom of the high pressure vessel. CO2 and the Antisolvent, which has also rendered enriched extracts
residual organic mixture can be recovered by decom- in interesting compounds. Phytochemicals like caro-
pression in a separator downstream from the precipi- tene from mango leaves, a-hydroxycitric acid from
tation vessel, operated at a lower pressure. In the kokum, or licochalcone-A from licorice have been
precipitator, the more polar compounds that have not purified by this method (Mukhopadhyay and Patel
been swept away by the CO2 are found, while in the 2009). This last compound is known for showing
separator, the swept compounds by the mixture antimalarial (Chen et al. 1994) and antileishmanial
scCO2 ? organic solvent can be recovered (Reverchon (Chen et al. 1993) activities.
and De Marco 2006). The key of this antisolvent Supercritical Antisolvent processes have been
process is the equilibrium in the extractor vessel, i.e., developed to try to overcome the drawbacks presented
123
Phytochem Rev (2012) 11:413–431 423
by traditional antisolvent methods. Supercritical anti- simple depressurization, there is no need of carrying
solvent methods are versatile, operational at mild out an extra separation step, as the product is
conditions and they avoid the use of great amounts of recovered without solvent. Several reviews (Jung
organic solvents. In fact, they are so versatile that they and Perrut 2001; Meure et al. 2008; Cocero et al.
can be used in the encapsulation and/or micronization 2009; Martı́n et al. 2010) enumerate and describe
of compounds, topic that will be handled in the next supercritical micronization and encapsulation tech-
section. Moreover, antisolvent methods constitute an niques. Some of them, like Supercritical Antisolvent
alternative when the interesting compounds in a (SAS), Supercritical Solvent Impregnation (SSI),
matrix are too polar to be extracted by means of Particles from Gas Saturated Solutions (PGSS) and
SFE. Antisolvent processes have been thoroughly used Supercritical Assisted Atomization (SAA) have been
in the nutraceutical, medical and pharmaceutical used in the field of biopesticides and will be reviewed
industries, due to the high added value of the final briefly, while other techniques such as Supercritical
compounds and due to the intrinsic requirements that Fluid Emulsion Extraction (SFEE)(Della Porta et al.
have to be fulfilled in these industries (particle size 2010), Supercritical Assisted Injection in a Liquid
distribution, safety, good manufacturing practices, Antisolvent (SAILA) (Campardelli et al. 2012), or
controlled delivery of the active principle). In spite of Concentrated Powder Form (CPF)(Grüner et al. 2003)
these known advantages, these processes still have to have not appeared up to date in literature handling
be implemented in the field of biopesticides. with biopesticides development.
Supercritical antisolvent (SAS)

Supercritical micronization and encapsulation
methods This technique is based on the use of scCO2 as
antisolvent and has been mainly used to micronize
Beyond extraction (SFE) and fractionation (SAE/ pharmaceuticals and biomedical antibiotics (Martı́n
SAF) of natural compounds with pesticidal properties, and Cocero 2008; Martı́n et al. 2010). Some examples
supercritical fluids can also contribute advantageously can be found in bibliography such as the encapsulation
to the formulation of biopesticides. Some of the of green tea (Sosa et al. 2011) or rosmarine antiox-
limitations of biopesticides are their low solubility in idants (Visentin et al. 2012), or the micronization of
water, their high volatility and their high reactivity antibiotics or pharmaceuticals such as rifampicin
with the ambient. In order to overcome these draw- (Reverchon et al. 2007), minocycline hydrochloride
backs, natural products can be formulated as compos- (Cardoso et al. 2008), ampicilin (Montes et al. 2011)
ites or capsules which are nowadays produced by or ibuprofen (Martı́n et al. 2009) from organic
several traditional techniques, classified in physical solutions.
processes (spray-drying, spray-chilling, extrusion, air Although both techniques SAF/SAE and SAS use
suspension coating…) or in chemical processes scCO2 as antisolvent, the objective, operating condi-
(coacervation, liposomal entrapment, molecular inclu- tions and the characteristic of the product are different.
sion….) (Desai and Jin Park 2005). SAF/SAE aim to separate an extract into fractions with
Supercritical fluids have been developed as an different composition that can be liquid, solid or a
alternative to these traditional encapsulation processes paste. In SAS, the objective is to produce a free
taking advantage of their previously commented flowing powder of particles in the micron and
properties (tunable density, easy separation solute– submicron scale. In this case, if a polymer is added
solvent, mild operating conditions …). When working to the solution or extract, the encapsulation or co-
with scCO2, those moderate conditions are used due to precipitation of the compounds can be achieved.
its low critical temperature and pressure. This allows The coprecipitation of a synthetic herbicide (diu-
the processing of thermolabile compounds and as it is ron) loaded in amorphous microparticles of a biode-
an inert medium it also allows the processing of easily gradable polymer (l-polylactic acid) is an example of
oxidable compounds. Furthermore, the use of super- the use of this technique (Taki et al. 2001). Long
critical fluids reduces or eliminates the use of toxic or needle-like crystals with a mean length of 500 lm
contaminant organic solvents and by means of a were obtained.
123
424 Phytochem Rev (2012) 11:413–431
Supercritical solvent impregnation (SSI) Varona et al. (2010) used this technique to encap-
sulate lavandin essential oil in polyethylene glycol
This technique allows the impregnation of carriers (PEG). The encapsulation efficiencies of this oil with
(protecting compounds) with active substances by biocidal activity reached values of up to 66 %. They
dissolving the substance in a supercritical fluid and also developed a modification of the process, PGSS-
then contacting the resulting fluid mixture with the drying, in which the coating material was fed to the
carriers to be impregnated (Kikic and Vecchione static mixer in an aqueous solution. However, the
2003). If the operational parameters are correctly encapsulation efficiencies reached a range of 6–55 %.
chosen, the loading and the depth penetration can be Varona et al. (2013) used both techniques (PGSS
varied. This method has been thoroughly used to and PGSS-drying) also to encapsulate the oil of
obtain diverse materials such as mesoporous silica lavandin, but using other carriers such as soybean
(MCM-41) impregnated with a-tocopheryl acetate lecithin, n-octenyl succinic anhydride modified starch
(Belhadj-Ahmed et al. 2009) or chitosan impregnated or poly-caprolactone. The antibacterial activity
with lactulose (Dı́ez-Municio et al. 2011). against Escherichia coli, Staphylococcus aureus and
In the field of biopesticides, the supercritical Bacillus cereus of the lavandin oil was enhanced by
impregnation with lavandin (Lavandula hybrida) the encapsulation, due to the protection and control
essential oil of modified starch has been accomplished release of the oil. Among the tested carriers, soybean
(Varona et al. 2011). This method achieved similar lecithin was the most efficient as it was able to form
loadings to those obtained by using methods such as liposomes which can interact with cells. PGSS-drying
PGSS or PGSS-drying, however, their impregnation particles showed a higher antibacterial activity than
efficiency was lower for the same load. The distribu- those formed by spray-drying with a similar essential
tion coefficient of essential oil between the starch and oil load.
the supercritical phase and the essential oil load Pemsel et al. (2010) used this technique to encap-
depended on the density of the CO2. sulate the Cydia pomonella granulovirus in a formu-
The impregnation of l-lactide random copolymers lation containing 77 % fat (commercially obtainable
with repellents and antibacterial agents (Japanese palm oil-based fat), 12 % virus, 9 % surfactant
cypress oil, D-limonene, hinokitiol, trans 2-hexenal) (lecithin-based surfactant) and 2 % UV protectant
using SSI has also been attempted (Tsutsumi et al. (modified titanium oxide or a benzophenone deriva-
2009, 2011, 2012). The mild working conditions tive). Encapsulation is needed as the granulovirus is
during the impregnation due to the supercritical fluid very sensitive to UV and it has a very low uptake by
allowed the incorporation of these thermolabile com- the Cydia pomonella. The obtained particles showed a
pounds, resulting in new controlled release materials. spherical morphology (maximum diameter 23 lm),
A similar technique has been used to mix a synthetic the bioassays proved that the granulovirus was
fungicide (Imazalil) and a carrier (b-cyclodextrin) in encapsulated and there was no loss of virulence
presence of scCO2 in an autoclave to make an inclusion compared to commercial formulation.
complex taking advantage of the gaseous nature of CO2
when depressurizing it (Lai et al. 2003). Although this Supercritical assisted atomization (SAA)
fungicide is not a biopesticide, its mixing technique
can result interesting for biopesticides. It is a similar technique to the PGSS, but in this case, the
scCO2 acts as co-solute and as pneumatic agent respon-
Particle from gas saturated solutions (PGSS) sible for the atomization (Reverchon 2002). The encap-
sulation procedure is based on the double atomization of
It is a two step process in which the first one comprises a quaternary mixture (scCO2, organic solvent, biopoly-
the saturation of the solute with carbon dioxide in a mer and active principle) inside a precipitator chamber,
static mixer operating at high pressures. The second after being put in contact in a packing filled mixer. This
step consists in the expansion of the saturated solution technique has been successfully used in the atomization
of gas through a nozzle. The Joule–Thomson effect of pharmaceuticals and other substances. The micron-
causes the particle formation due to a fast and ization of ampiciline microspheres covered by hydro-
pronounced reduction in temperature (Weidner 2009). xypropylmethylcellulose (HPMC) has been studied by
123
Phytochem Rev (2012) 11:413–431 425
Reverchon and Antonacci (Reverchon and Antonacci SFE is by far the most used supercritical method-
2007). The granulometry depended on the concentration ology to obtain and optimize biopesticides. It is
of HPMC in the initial solution. The SAA technique has employed as an alternative to traditional methods such
also been used for the production of microparticles from as hydrodistillation or organic extraction, because it
thermolabile compounds like bovine serum albumin overcomes the drawbacks of them (avoids the thermal
(Adami et al. 2011) or lysozyme (Adami et al. 2009). degradation, hydrolysis or hydrosolubilization of the
In the field of pesticides, an attempt has arisen to compounds in the former, or the inherent inconve-
encapsulate rotenone due to its instable nature and its niences of using organic solvents of the latter). SFE
formerly condition of biopesticide. The used carriers were has been successfully used to extract bioactive com-
PEG, polyvinylpyrrolidone and sodium alginate. The pounds from natural matrices, obtaining extracts
morphology of the obtained microspheres and the similar to the hydrodistilled or organically extracted.
encapsulation yield depended on the carrier and on the In fact, the supercritical extracts are not only compa-
working conditions. The effective loading of the micro- rable to the classical ones, but they can achieve a better
spheres and coacervates was analysed by means of HPLC, quality, as the desired compounds can be preferen-
obtaining values near to 100 % (Martı́n et al. 2011d). tially extracted. The desired compounds can be
In general, the encapsulation processes using CO2 partially fractionated by means of consecutive sepa-
have very promising applications due to the simplicity, rators, extraction steps or use of entrainers. In most of
cleanliness and encapsulation efficiencies. The particle the studies, the SFE extracts are chemically compared
size (down to the submicron scale), a system easily to the ones obtained by traditional methods, but their
compliant with the Good Manufacturing Practices and activity (in this case, the biopesticidal activity) has not
the favourable technical and economic conditions for been measured, so an effort should be made in order to
large scale production are additional advantages in systematically perform routine pesticidal tests. As a
their application. However, as in the case of supercrit- general rule, if the hydrodistilled or organic fractions
ical antisolvent methods, this encapsulating methods from a plant show pesticidal activity, the supercritical
have been mainly developed in the pharmaceutical, extract will show also pesticidal activity if the
nutraceutical and medical industries and there is still a supercritical extraction conditions are properly
great field of interest in the biopesticide encapsulation. selected. However, this rule has to be taken cautiously,
as the activity can be even higher (or smaller) if there
are synergistic effects with compounds present in only
General overview one type of the extracts. That is the fundamental
reason why the activity of the supercritical extracts
Supercritical fluids are being studied in a wide range of should be inspected to further increase the knowledge
applications as they possess several interesting prop- about the SFE of biopesticides and convert this
erties which make them ideal solvents. Their tunable knowledge into industrial exploitation. Nonetheless,
density, the high diffusivity and penetrability mixed various patents handle with the production of biopes-
with their solvent power, the easy separation solute ticides by means of SFE and several studies point out
solvent and their versatility, makes them attractive to the adequacy of developing SFE as a routine method in
not only the academy, but also to the industry. the obtention of biopesticides.
Furthermore, there are additional advantages when SAE/SAF methods have been to date less applied to
using CO2 as supercritical solvent, such as its low cost, the obtention of biopesticides. The interesting com-
its mild operational conditions, its Generally Recog- pound has to be previously extracted by other solvent
nized as Safe nature (GRAS) and its inert character. (preferentially an organic one), so one of the advan-
In the production of biopesticides, a potentially tages of the use of supercritical fluids, the absence of
interesting field for the development of methods with organic solvent, cannot be applied. However, super-
supercritical fluids, three sections have been distinguished critical antisolvent methods have shown several
in this review: Supercritical Fluid Extraction (SFE), advantages over traditional antisolvent techniques,
Supercritical Antisolvent Extraction or Fractionation including mild operation conditions, a non oxidant
(SAE/SAF) and Supercritical Micronization and Encap- medium (if the supercritical fluid is CO2), fast oper-
sulation (consisting of various techniques). ational times and a controlled particle size distribution
123
426 Phytochem Rev (2012) 11:413–431
if the technique is used as a encapsulating tool. The Anastas APT, Warner JC (2000) Green chemistry: theory and
antisolvent techniques have been widely used in practice. Oxford University Press, USA
Aresta M, Dibenedetto A, Dileo C et al (2003) The first synthesis
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research to conduct. In spite of this, some attempts have Aro H, Järvenpää E, Könkö K et al (2009) Isolation and puri-
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and pilot-scale supercritical fluid techniques. Eur Food Res
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Barton P, Hughes RE Jr, Hussein MM (1992) Supercritical
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Acknowledgments Authors are grateful for financial support J Supercrit Fluids 59:36–42
from MICINN-FEDER (CTQ2009-14629-C02-01 and CTQ2009- Braga MEM, Ehlert PAD, Ming LC, Meireles MAA (2005)
14629-C02-02), from Gobierno de Aragón-Fondo Social Europeo Supercritical fluid extraction from Lippia alba: global
(group E52) and from Gobierno de Aragón-La Caixa-Sumalsa yields, kinetic data, and extract chemical composition.
(GA-LC-042/2010). L. M has been supported by Gobierno de J Supercrit Fluids 34:149–156
Aragón and Universidad de Zaragoza (GA-LC-042/2010). Brunner G (2005) Supercritical fluids: technology and applica-
tion to food processing. J Food Eng 67:21–33
Burt S (2004) Essential oils: their antibacterial properties and
potential applications in foods—a review. Int J Food
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Phytochem Rev (2012) 11:413–431

Supercritical methodologies applied to the production

Rotenone Azadirachtin Pyrethrin I (R=CH3)

Darabi et al. (2011)

Liang et al. (2012)

patents handling with the SFE of biopesticides, such as

place at 9.8 MPa and 40 C for 60 min, obtaining an

extract containing 13.60 % of cis-abienol (compared to

the hexane extract, containing just 1.31 %). Another

formed by its essential oil or its supercritical extract

otypes of Artemisia absinthium by organic or super-

critical CO2 extractions (Gonzalez Coloma et al. 2012).

Apart from EPA approved biopesticides, there is also

a category of minimum risk pesticides included in the

biopesticides category that are exempt from registration

under section 25(b) of the Federal Insecticide, Fungi-

tion Agency 1947) which include oils (hydrodistilled

and/or pressed oils) of several species. As the extracts

of SFE, extracts with similar properties and composi-

cottonseed…) counts already with an SFE official

method (Firestone 1998). Other volatile oils (compris-

obtained by SFE: cinnamon (Zhao and Liang 2006;

Marongiu et al. 2007; Miao and Deng 2011), clove

Eugenol, eugenyl acetate

Rozzi et al. 2002), mint (Barton et al. 1992; Dı́az-

Maroto et al. 2002; Almeida et al. 2012), peppermint

(Goto et al. 1993; Castillo et al. 2003; Sovová et al.

Grosso et al. 2010a, b; Garcı́a-Risco et al. 2011b). In

these minimum risk pesticide category there are also

single compounds that have been extracted from natural

Supercritical antisolvent (SAS)

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