Industrial Uses and Sustainable Supply of Quillaja saponaria (Rosaceae) Saponins Author(s): Ricardo San Martn and Reinaldo

Briones Reviewed work(s): Source: Economic Botany, Vol. 53, No. 3 (Jul. - Sep., 1999), pp. 302-311 Published by: Springer on behalf of New York Botanical Garden Press Stable URL: http://www.jstor.org/stable/4256204 . Accessed: 14/04/2012 16:00
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INDUSTRIAL USES AND SUSTAINABLE SUPPLY OF

(ROSACEAE) SAPONARIA QUILLAJA SAPONINS'

RICARDO SAN MARTfN AND REINALDO BRIONES

of San Martin, R., and R. Briones. (Department Chemicaland BioprocessEngineering,CathUSES AND SUSTAINolic University, Av. Vicufia Mackenna 4860, Santiago-Chile). INDUSTRIAL SAPONINS. Economic Botany 53(3):302-311, 1999. The bark of the tree Quillaja saponaria, indigenous to Chile, is one of the major sources of industrially used triterpenoid saponins. For decades quillaja extracts have been used as foaming agents in beverages, emulsifiers in foods, wetting agent in photography, etc. Overexploitation of the bark has caused important ecological damage and a shortage of this resource. However, this can still be remedied by using whole quillaja wood (and not just the bark), for the production of saponins. This raw material can be obtained in large quantities from pruning operations, reducing the need to fell trees. This review covers ecological aspects of quillaja exploitation, as well as a discussion of its novel industrial applications.
ABLE SUPPLY OF QUILLAJA SAPONARIA (ROSACEAE)

SAPONARIA. La Y SUSTENABLEDE SAPONINA DE QUILLAJA USOS INDUSTRIALES ABASTECIMIENTO

corteza del drbol Quillaja saponaria, originario de Chile, es una de las principales fuentes industriales de saponinas triterpenicas. Durante deadas los extractos de quillay han sido usados como espumante en bebidas, emulsificante en alimentos, agente humectante en fotografia, etc. La sobre explotacion de la corteza ha causado un importante danio ecol6gico y escasez de este recurso. Esto ain puede ser remediado usando en forma integral toda la biomasa del drbol y no s6lo la corteza. Esta materia prima es abundante, y se obtiene del raleo de los bosques existentes, sin necesidad de cortar drboles. Este trabajo cubre aspectos ecol6gicos de la explotaci6n del quillay, y novedosos usos industriales de sus saponinas. Key Words: Quillaja saponaria; saponins; sustainable production.

Saponins are high molecular weight glycosides, consisting of a sugar moiety linked to a triterpene or steroid aglycone (Hostettmann and Martson 1995). Interest in these compounds has increased significantly in recent years because of their properties as natural detergents and foaming agents, as well as their applications in cholesterol-reduction and flavor enhancement, their effect on cardiac activity, hemolytic activity, immunostimulating activity and other uses (Waller and Yamasaki 1996a,b). Among the most important botanical sources of industrial saponins is the bark of the tree Quillaja saponaria Molina, indigenous to Chile. The bark contains about 5% triterpenoid saponins (Kensil 1996), which for decades have been used as a surfactant in the production of photosensitized film, as a foaming agent in beverages and shampoos, a natural emulsifier in foods and similar uses. Its I Received 22 March1997, resubmitted; accepted18 April 1999.

use in foods has been facilitatedby the fact that quillaja extracts (QE) are approvedfor human consumptionby countriessuch as the U.S., EC, and Japan. Other common names for Q. saponaria and its bark are: quillaja tree, soap tree, soap bark, soap tree bark and quillay (Chilean common name). Also, because of the historical trading routes, the bark is known as Panama bark or Bois de Panama.Ourreview focuses on the industrialapplicationsof quillaja saponins, as well as new process approacheswhich allow a stable supply of saponinsand a sustainableexploitationof the resource. BACKGROUND Firstdescribedby Molina (1782), Quillajasaponaria trees grow naturallyin the central and southernregions of Chile (400 km northand 500 km south of Santiago). Figure 1 shows a photographof a quillajatree over 100 years old. In the past, extensive areas were covered by quillaja forests, but its continuous exploitation and

Economic Botany 53(3) pp. 302-311. 1999 ?D 1999 by The New York Botanical Garden Press, Bronx, NY 10458-5126 U.S.A.

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recognized by the indigenous people of Chile (Mapuches)who used aqueousbark extractsfor washing their hair and clothes. For this purpose the barkwas placed in boiling waterand allowed to settle all night before using the extract. In fact, the local word quillay is derived from the native Mapucheword "quillean"thatmeans "to wash." Another common local use is the prevention of moth damage by suspending bark slabs with clothes. Young pigs are fed with QE to treat diarrhea. The barkhistoricallyhas been exportedto the U.S., Europe and Japan, with no processing done in Chile. The present marketsize is about 180-200 tons of QE derived from 1000 tons of bark exported by Chile each year. The price of the extracts range from U.S. $12-18 per kg of non-purifiedliquid concentrate(about 50% solids), to over U.S. $100 per kg for more purified products.A QE marketvalue of about U.S. $7 million per year is a conservative estimate. The principalproducersof QE from bark are Berghausen and Bell Flavors in the U.S., Schmithman in Germanyand MaruzenPharmaceuticals in Japan.
Fig. 1. Adult quillaja tree (approximately 100 years old). the increase of agricultural areas have reduced significantly its natural population. Virgin quillaja forests are now only found in more inaccessible areas, particularly in the Andes region, up to 1500 m a.s.l. The tree grows well in areas with little rainfall and can withstand long periods without water. Average densities are about 50 trees per hectare. Natural growth rates are slow, with an average diameter increase of 0.60.8 cm/year in the central part of Chile (Vita 1974). On good quality soils the tree may grow much faster, however further research is needed to determine optimal growing conditions. Reproduction is by seeds, but the trees also regenerate vigorously from stumps that are left in the field after the trees are felled for the extraction of bark or when the above ground trunks are killed by fire. At the present time major part of the accessible quillaja forests consist of regenerated trees which grow as shrubs with five or more large branches per stump. A shrub-type tree grows to about 10 m, while old trees grown from seeds may be as tall as 30 m. The foaming properties of the bark were first PRODUCTION OF QUILLAJA SAPONINS FROM THE BARK

Although the wood contains significantquantities, Quillaja saponins are found primarilyin the bark. Using hot water as a solvent, the bark yields 20% extractives (on a w/w dry basis), with a saponincontent in the extractedsolids of about20% (Kensil 1996). To obtainbarkin economical quantities,trees of about 30 to 50 years old with a diameterof 20-50 cm are felled. To satisfy presentworld demand,over 50 000 trees are felled each year.This activity is regulatedby the Chilean National ForestryCorporation (CONAF). The law dating from 1944, allows exploitationbetween March 31 and December 31, provided a forestry managementplan has been approvedby CONAE A maximum of 35% of the basal tree area can be extractedevery 5-10 years from the same site. In practice, exploitation is carried out between Septemberand December because the bark only peels off easily during springgrowth. Priorto debarkingthe external part of the bark is removed with knives. The bark is air-driedin the shade and then it is tied up in bundles ready for export. Economical quantities of bark are obtained only from the main trunkand bigger branches,leaving signif-

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acid glucuronic quillakacld;

lucose >

xylose

OH
H 3,5-dlhydroxy-6-methyloctanolc acid

HylosemH

~
OH ~

galaclose H

~ ~ apOse ~ yls~ ~

~ ~ ~

~
~~~~O

arabinose
Fig. 2. Structure quillajasaponinQS-21 (Recchiaet al. 1995). of

icant quantities of biomass to rot in the field (95% of the weight of the tree, 20 000 tons per year). Despite increased governmental control and more strict environmentalregulations, the population of old quillaja trees has decreased dramaticallyas a result of continuousexploitation. Because of this, the price of the bark has increased more than four times in the last five years.
QUILLAJA SAPONINS DERIVED FROM WHOLE WOOD

that can withstandan increase in the world demandwithoutcausing ecological damage.Based on this novel process, a new company is now operatingin Chile (NaturalResponseS.A., Quilpue), as a joint venture between the Catholic Universityof Chile and Desert King International, Chula Vista, CA.
CHEMICAL COMPOSITION OF QUILLAJA SAPONINS

The ecological damage caused by the exploitation of the barkhas stimulatedresearchon the use of the whole quillajawood (wood with bark, small branches),as a more stable supply of saponins. In our laboratorywe have shown that whole wood contains about 8% water soluble compounds,with a saponincontentin the solids of 20% (determinedby reverse-phaseHPLC). The quality of the productsderived from whole wood compares very well with commercial productsderivedfrom bark.Using this new process, fewer than 10 000 trees per year (or 4000 tons of whole wood) can satisfy the present world demand for quillaja saponins. Moreover, this wood can be obtained entirely from the pruning of existing bush-type trees that regenerate afterthe exploitationof bark.This raw material can be estimatedat a minimumof 300 000 tons just in the central part of Chile (Duchens 1998). This new method therefore provides a sustainable approach to quillaja exploitation,

Quillaja saponins are bisdesmosides, that is, they contain two sugar moieties linked to the triterpenein positions 3 and 28. The triterpene has been identifiedas quillaic acid (Higuchi,Tokimutsu, and Komori 1988). Monomeric saponins have a molecularweight determined size by exclusion HPLC in the range of 1800-2000 (Kensil et al. 1991). Above their criticalmicelle concentration (300-800 mg/l), they aggregatein micelles containing about 50 saponins per micelle (Mitraand Dungan 1997). At least 20 different saponins have been identified from the bark (van Setten and van de Werken1996). Importantstructural featuresthat distinguishQ. saponaria saponinsfrom those of other plant species are a fatty acid domain and a triterpenealdehyde group at position 4. Figure 2 shows the structureof saponin QS-21 used as an adjuvant in human vaccines (Recchia et al. 1995). Though differenttechniquescan be used for the analysis of saponins, most companies use reverse phase HPLC (Kensil et al. 1991). Using this technique it can be shown that both bark

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and wood commercialextracts contain 15-20% saponins, though the distributionof individual saponins is somewhatdifferent.
PRODUCTION METHODS AND COMMERCIAL PRODUCTS

REGULATORY ASPECTS OF QUILLAJA SAPONINS

Emulsifier in Food and Beverages Extensive work performed in Japan has shown that purifiedQE (e.g., productQuillayanin C-100, Maruzen Pharmaceuticals,Japan), are effective emulsifiersin food and beverages. Oil-in-wateremulsions are similar to those ob1991). tained with sugarfatty acid esters, with an HLB The quality of the final extracts is evaluated value above 12 (Chino and Wako 1992; Murain terms of clarity and color in solution, as well kami 1988, 1996). They can be used also in the as foaming properties. Traditionally, quality productionof microemulsions,an emulsification standardshave been developed by major con- technique that minimizes power requirements sumers according to their requirements.How- (Kudo and Nishi 1992). Some industrialappliever, for novel applicationsthere is a need to cations include the production of mayonnaise standardize precise analyticalprocedures, partic- (Maedaet al. 1989), enhancementof oil-soluble ularly regarding the determinationof saponin flavorsfor candies (Toyaet al. 1994), dissolving content. of propolis (Kawai, Hirashita,and Kanae 1994)

QE are primarily commercializedwith very little purification.Standardliquid products are prepared using water extraction after the raw material has been adequately milled. Aqueous methanol is used by Japanesecompanies to attain higher extraction yields, although it is claimed that aqueous extracts are cleaner (Hostettmannand Martson 1995). Following extraction, the liquid is concentrated evaporation to by attain the desired concentration of solids. In some cases it is also necessary to purify the extract(e.g., contactwith activatedcharcoal,filtration) to remove compoundsthat tend to precipitate during storage. The final productscontain saponins, protein, tannins, calcium oxalate and sugars. Non-refinedliquid productscontainabout550 g solidsfA (50?Brix)and when dilutedwith water they yield a reddish-orangecolor. Typical preservatives are sodium benzoate (0.5-1 g/l) and ethanol.Spray-dried productsare prepared using 100% crude QE or by mixing the extract with carrierssuch as maltodextrins lactose. More and refinedproductsinvolve the removal of non-saponin compoundssuch as calcium oxalate, sugars, and tannins, which may interferein terms of color, chemical interactions,taste, and odor. For this purpose, purification with polymeric resins such as Diaion HP-20 and organic solvents have been used (Ogawa and Yokota 1985; Ogawa and Murakami1987). An alternativeapproach employs the removal of low molecular weight compoundsusing diafiltration with ultrafiltrationmembraneswith molecular cutoffs of 10-30 kDa that retain saponin micelles (Kensil

The toxicology of QE have been studied extensively in rats (Gaunt, Grasso, and Gangolli 1974; Phillips et al. 1979) and no toxic effects have been observed even at intake rates as high as 1500 mg/kg/day (Drake et al. 1982). Based on these studies, QE are approvedas additives in foods in the U.S. by the FDA under 21 CFR 172.510, FEMA GRAS number2973. Its current CAS number is 977002-27-9. In the European Union they are approvedin water-based non-alcoholic drinksundercode E 999. In Japanthey are allowed for human consumption and cosmetics. The World Health Organizationrecommends a maximumdaily intake of 5 mg of QE/ day-kg humanweight.
INDUSTRIAL APPLICATIONS

The scientific and patent literature shows about 200 references detailing differentuses of QE. What follows is a review of the most relevant scientific articles and patents,with emphasis in novel industrialapplications.
FOOD AND BEVERAGES

Foaming Agent in Beverages The most importantuse of QE is as a natural foaming agent in beverages (70% of world consumption), such as root beer and soft drinks (Mukai, Matsuda,and Kanazawa 1993) at concentrationsof 40-100 ppm. QE are used also in slush type drinks to improve the ice crystal structure/morphology the refreshment and value of the product(Nayyaret al. 1998).

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and red coloring material (Oono and Higashimura 1995), for soy sauce (Murakamiand Watanabe 1988a) and whipping cream (Murakami and Watanabe1988b). Otherfunctionaluses are as antioxidants (Hisayuki and Takashi 1987; Kooryama and Chiba 1996), leavening agents et (Watanabe al. 1989) and in health foods (Tashiro 1990).

of shellfish, the oral administration small doses of quillajasaponinsimprovesresistancetowards pathogens (Kikuchi et al. 1996; Mabe, Okubo, and Takahashi1996; Ninomiya et al. 1995a,b; Ninomiya et al. 1996). Quillaja saponins have also been used as delivery systems to enhance enteric uptakeof humangamma globulin in the tilapian Oreochromis mossambicus (Jenkins, Harris, and Pulsford 1991) and as a means for Production of Low Cholesterol Foods the potentiating immuneresponseelicited by imQuillajasaponinscan be used for the produc- mersion vaccination with commercial enteric tion of low-cholesterol dairy food products redmouthvaccine (Graysonet al. 1987). It must and (Richardson Jimenez-Flores1991; Sundfeld, be noted that at high doses, toxic effects have Krochta, and Richardson 1994), based on the been observed in salmon (Bureau, Harris, and ability of saponinmicelles to form insoluble ag- Young Cho 1998) and shrimp(Chen, Chen, and gregates with cholesterol, which can be easily Chen 1996). removed by filtration. A recent report details Agricultural Applications physicochemical properties of QE that can be to optimizethis process (Mitraand Dungan used QE have many potentialapplicationsin agri1997). Other patents are related to feeding culturesuch as wetting agents, biopesticidesand chickens with QE, for the production of low- plant growth stimulants.As wetting agents,their cholesteroleggs (Yamamotoand Kameda1993). capacity to reduce surface tension of water is comparableto that of chemical products(35-40 NON-FOOD APPLICATIONS dyn/cm). This is particularlyimportantfor orAdditives for Animal Feed where saponinsare among the ganic agriculture, Saponin-richextracts, particularlythose de- few productsallowed as wettingagents(Organic rived from Yucca spp, are used extensively as Crop ImprovementAssociation 1994). QE can feed additives to reduce atmosphericammonia also be used to increase percolation of hydrolevels in confinementlivestock facilities such as phobic soils (e.g., productOasys, Soil Technolpigs, broilers(Tymczyma1996) and cows (Wal- ogies Corp., Iowa). As biopesticides, saponinlace, Arthaud,and Newbold 1994), and to ame- rich extracts can be used to control nematodes liorate canine and feline fecal aroma(Lowe and (Emerson and Crandall1997), and phytopathoKershaw 1997). Recent reportsindicatethat QE genic fungi such as powdery mildew (Emerson have similarproperties(Ikedaand Suzuki 1995), and Crandall1997). In combinationwith capsiand because of their lack of toxicity, their en- cum oleoresin, they have been formulatedas a hancementof the synthesis of microbialprotein safe bio-repellentto control a variety of pests, and their lack of effect on digestibility,they can such as birds and insects, and fire ants (Wiersma be considered as potential feed additives (Mak- and Wiersma 1997). kar and Becker 1996). QE also have beneficial effects on seed gerPerhaps the most exciting potential for quil- minationand plant growth. Researchperformed laja in feeds is as a natural supplementto in- 55 years ago in France(Balansard, Pellisier,and crease immunoprotection animalswith the re- Conil 1945), showed that soaking corn seeds in of sulting reductionin the use of antibiotics.These QE at a concentration 20 ppm, increasedseed of immunologicalpropertiesare unique to quillaja germinationand stimulatedplant growth. Bensaponins. Oral administration QE to mice in- eficial effects have also been reportedfor radish of creases the resistance to rabies infection (Cha- roots (Fragsteinand Buchloh 1981). vali, Barton, and Campbell 1988; Chavali and Cosmetics Campbell 1987a,b; Maharaj,Froh, and Campbell 1986). In combination with bile powder, There has long been interestin the use of QE garlic powder, and bacterial cells containing in the formulation naturalshampoossince this of peptidoglycan, quillaja saponins increase pseu- was its original use by indigenous Chileanpeodorabies resistance in livestock, poultry and ple. For this purpose, light-colored,low tannin nursery fish (Yabiki et al. 1993). In fish and preparationsare preferredto reduce any aller-

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genic reactions (Poisson 1972, 1974), though some commercial formulationsuse non-refined (more natural)extracts,e.g., Phytologie, France. Also, in some formulationsit is used in combination with other natural compounds such as Aloe vera, e.g., Pharmos Aloe Vera, Germany. In Chile it is extensively used in many shampoos as a secondary surfactant.A recent work shows the compatibilityof purifiedQE with chemicals commonly used in shampoo formulationssuch as sodium lauryl sulfate, cocoamidopropylbetaine, methylparaben, and propylparaben glucamate (Ceppi 1998). Other applicationsinclude the solubilizationof vitamin E (Shirikawaet al. 1994) and essential oils (Murakami1986; Muramatsuand Suzuki 1993), hair tonic to reduce hair loss (D'Aquino Silva 1994) and the production of hand creams (Kinekawaet al. 1992). Photography QE have been used for decades in the production of films as wetting agents to obtain a uniform distributionof silver halide microcrystals dispersedin gelatin (Ito et al. 1993; Kato et al. 1994). For this applicationmajorphotographic companies (e.g., Konica, Agfa) use purified QE, with special emphasis in low-tannin, low color properties. Wastewater Treatment QE are used in waste treatmentin Japan.It is claimed that the additionof QE in the treatment of waste waterenhancesoxygen transferand the degradationof fats and decreasesthe amountof sludge and the load of sludge dewatering(Tashiro 1991, 1992, 1995, 1996). Specific applications include waste water treatmentof marine products and edible meat industries (Nagasaka 1995a,b;Nagasaka and Tashiro 1995). Miscellaneous Non-Food Applications Some special non-food applications of quillaja saponins are in the preparationof lightweight composites for building materials(Tonyan and Gibson 1993), high-solids aqueousdispersions of hydrophobizing agents (Craig 1995), reduction of sulfuric acid mist in zinc electrowinning (Mackinnon 1990, 1994), and aerobic ex situ bioremediationof a chronicallypolychlorobiphenyl(PCB)-contaminated (Fava and soil Di Gioia 1998).

Adjuvants for Animal and Human Vaccines The use of saponins as adjuvantsin animal vaccines was first tested againstfoot and mouth disease (Espinetet al. 1951). It was then shown that only quillaja saponins are effective adjuvants, and a fraction that minimized unwanted side effects was purified(Dalsgaard1974). This product,known as Quil-A, is producedby the Danish firm Superfos and is used commercially in many animal vaccines. Later it was shown that Quil-A is a complex mixtureof four major saponins with varying degrees of toxicity, that can be separatedusing RP-HPLC(Kensil et al. 1991). Some of the individualsaponins,notably saponin QS-21, showed such low toxicity that potentially it could be used as adjuvantin the preparationof human vaccines (Kensil et al. 1991; Kensil 1996; Kensil, Wu, and Soltysik 1995). Experimental trials include the testing of an HIV-1 vaccine in non-human primates(Newman et al. 1992), melanoma(Helling et al. 1995) and Plasmodiumfalciparum malaria (Stoute et al. 1997). QS-21 also augments both antibody and cell-mediatedimmuneresponses,suggesting thatthis adjuvant could be a valuablecomponent in subunit vaccines (Wu et al. 1992). Another important applicationis in the preparation imof munostimulatingcomplexes, ISCOMS (Morein et al. 1990). ISCOMS are used to present viral membraneproteinsin a multimericform and are produced by complexing cholesterol, saponin and anotherlipid (Morein et al. 1984). The potential of ISCOMShas been exploredin numerous articles and patents and some commercial vaccines are alreadyproducedby this method. Miscellaneous Pharmaceutical Applications Purifiedquillaja saponinsare used to lyse selectively red cells from whole blood preparations, allowing for leukocyte differentialanalysis (Ledis et al. 1985), and the preparationof nucleic acid from white blood cells (Ryder and Kacian 1993). Modified quillaja saponins such as saponin DS-1 derived from saponin QS-21 have been used to enhancenasal and oculardelivery of insulin (Kensil, Soltysik, and Marciani 1993; Pillion, Amsden, and Kensil 1996) and as a permeationenhancerfor mucosal delivery of the aminoglycosides, an importantclass of an-

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ally against rabies. Clinical ExperimentalImmutibacterialagents used for the treatmentof serinology 74:339-43. pneumonia infections such as ous gram-negative and peritonitis (Recchia et al. 1995). Also an Chen, J. C., K. W. Chen, and J. M. Chen. 1996. Effect of saponinon survival,growth,moltingand enteral formulationcontaining purified quillaja feeding of Penaeus japonicus juveniles. Aquaculsaponins and oils rich in omega 3 polyunsatuture 144:165-175. rated fatty acids, has been used for treatmentof Chino, Y., and M. Wako. 1992. Manufacture transof infection and inflammation(Forse and Chavali parent emulsions for foods and beverages. JP 04 1995). 51,853.

CONCLUSIONS it. and a methodfor preparing BrazilianpatentBR 9400875. Quillajasaponinshave a wide range of industrial applicationsthatrequirean adequatesupply Dalsgaard, K. 1974. Saponinadjuvants.III. Isolation of a substance from Quillaja saponaria Molina of raw materials. The use of bark as the sole vaccines. with adjuvantactivity in foot-and-mouth source of quillaja saponins is no longer viable, Archiv fur die gesamte Virusforschung44:243because over-exploitationof naturalforests has 254. ecological damage.The devel- Drake, J. J., K. R. Butterworth, I. F. Gaunt, J. Hoocaused important opment of a new process based on whole quilson, J. G. Evans, and S. D. Gangolli. 1982. Longlaja wood, as well as plantations,can solve this term toxicity study of QE in rats. Food Chemistry problem, allowing the use of quillaja saponins Toxicology 20:15-23. in novel and interestingindustrialapplications. Duchens, L. 1998. CONAF,Santiago,Chile. Personal ACKNOWLEDGMENTS
This work was supported by the Chilean Research and Scientific Council (FONDEF, Project #1 2010). DISCLOSURE: Dr. Ricardo San Martin is Professor at the Faculty of Engineering of the Catholic University of Chile, and is President of the Natural Response S.A., a private company partly owned by the Catholic University.

D'Aquino Silva, E. 1994. A hair tonic formulation

LITERATURE CITED Balansard, J., F. Pellisier, and S. Conil. 1945. Action de saponitesde Quillayaet de Sapindussur le pouvoir absorbant,la germinationet la croissancede Zea mais L. Proceedings Societe de Biologie de Marseille,Meeting November28. 140-142. Bureau, D. P., A. Harris, and C. Young Cho. 1998. The effects of purifiedalcohol extractsfrom soya product on feed intake and growth of chinook salmon (Oncorhynchus tshawytscha)and rainbow trout (Oncorhyncusmykiss). Aquaculture161:2743. Ceppi, P. 1998. Uso de las saponinasen cosmeticos. B.Sc. thesis, Facultyof Engineering,CatholicUniversity of Chile, Santiago,Chile. Craig, D. 1995. High solids aqueous dispersionsof hydrophobizing agents. U.S. patent5,403,392. Chavali, S. R., and J. B. Campbell. 1987a. Immunomodulatoryeffects of orally-administered saponins and nonspecific resistance against rabies infection. International ArchivesAllergy Application Immunology84:129-34. . 1987b. Adjuvanteffects of oral, and ly administeredsaponins on humoraland cellular immune responses in mice. Immunobiology174: 347-59. , L. D. Barton, and J. B. Campbell. 1988. Immunopotentiation orally-administered by quillaja saponins:effects in mice vaccinatedintraperitone-

communication. Emerson, R. W., and B. G. Crandall. 1997. Use of saponins in methods and compositions for pathogen control.U.S. patent5,639,794. a Espinet, R. G. 1951. Noveau vaccin antiaphteaux complexe glucoviral. Gaceta Veterinaria,Buenos Aires, Argentina13:268-273. Fava, F., and D. Di Gioia. 1998. Effects of TritonX100 and quillaya saponin on the ex situ bioremediationof a chronicallypolychlorobiphenyl (PCB)soil. Applied MicrobiologyBiotechcontaminated nology 50:623-630. Forse, R., R. Armour, and S. Chavali. 1995. Enteral formulations treatment inflammation infor of and fection. U.S. patent5397778. Fragstein, P. and G. Buchloh. 1981. The influence of saponins on the yield and mineral content in radishes Raphanus sativus. Angewandte Botanik 55:49-56. Gaunt, I. J., P. Grasso, and S. D. Gangolli. 1974. Short term toxicity of QE in rats. Food Cosmetics Toxicology 12:641-650. Grayson, T. H., R. J. William, A. B. Wrathmell, C. B. Munn, and J. E. Harris. 1987. Effects of immunopotentiating agentsin the immuneresponseof rainbow trout, Salmo gairdneri Richardson, to ERM vaccine. Journal Fish Biology 31(A):195202. Helling, F., S. Zhang, A. Shang, S. Adluri, M. Calves, R. Koganty, B. M. Longenecker, T. J. Yao, H. F. Oettgen, and P. 0. Livingston. 1995. GM2-KLH Conjugate Vaccine: increased immunogenicity in melanomapatients after administration with immunologicaladjuvantQS-21. Cancer Research55:2783-2788. Higuchi, R., Y. Tokimitsu, and T. Komori. 1988. An

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feline faecal aroma.Researchand VeterinarySciacylated triterpenoidsaponin from Quillaja sapoence 63:61-66. naria. Phytochemistry 27:1165-1168. Hisayuki, K., and I. Takashi. 1987. Antioxidant.JP Mabe, K., T. Okubo, and Y. Takahashi. 1996. Feed composition for preventing infectious disease of 62243681 A. Hostettmann, K., and A. Marston. 1995. Saponins. crustacea.JP 8131089 A. CambridgeUniversityPress, UK. Mackinnon, D. 1990. The effects of saponin, antiIkeda, M., and K. Suzuki. 1995. Feed additive for mony and glue on zinc electrowinningfrom Kidd reducing ammonia in urine-contains extract of Creekelectrolyte.Journalof AppliedElectrochemQuillaja saponaria Molina. JP 07222555 A. istry 20:955-963. Ito, K., T. Sanpei, M. Kato, and J. Aritomi. 1993. . 1994. The effects of foamingagents and their Rapidprocessingsilverhalideblack andwhitephointeractionwith antimony,manganeseand magnetographic material using non-ionic surfactantto sium on zinc electrowinningfrom synthetic acid preventsilver stain. JP 05,273,712. 35:11-26. sulfate electrolyte.Hydrometallurgy Jenkins, P. G., J. E. Harris, and A. L. Pulsford. Maeda, K., T. Tanada, and S. Akita. 1989. Manu1991. Enhancedenteric uptake of human gamma factureof improvedmayonnaise.JP 01,108,956. mos- Maharaj, I., K. J. Froh, and J. B. Campbell. 1986. globulin by QUIL-A saponinin Oreochormis sabicus. Fish and Shell Immunology1:279-295. Immune responses of mice to inactivated rabies Kato, M., K. Ito, J. Aritomi, H. Ito, and T. Sanpei. vaccine administeredorally: potentiationby quil1994. Processing of black-and-whitesilver halide Journal Microbiology32: of laja saponin.Canadian materialin presenceof non-ionicsurphotographic 414-420. factantto preventsilver stain. JP 06 03,774. Makkar, H., and K. Becker. 1996. Effect of quillaja Kawai, M., N. Hirashita, and J. Kanae. 1994. Mansaponins on in vitro rumen fermentation.Pages ufactureof propoliscompositionsfor healthfoods. 387-394 in G. R. Waller and K. Yamasaki,eds., JP 94 197734. Saponins used in food and agriculture.Advances D. Marciani. 1993. EnKensil, C., S. Soltysik, and in experimentalbiology. Vol. 405. Proceedingsof hancingdrugdelivery with modifiedsaponins.U.S. the American Chemical Symposium on saponins patent5273965. Chemistryand Biological Activity, August 22-25, . 1996. Saponinsas vaccine adjuvants. Critical Chicago, IL. PlenumPress, New York. Reviews in Therapeutic Drug CarrierSystems 13: Mitra, S., and S. R. Dungan. 1997. Micellar prop1-55. erties of quillajasaponin.1. Effects of temperature, , J-Y. Wu, and S. Soltysik. 1995. Structural salt and pH on solution properties.JournalAgriand immunologicalcharacterization the vaccine of culturalFood Chemistry45:1587-1595. adjuvantQS-21. Chapter22 in M. F Powell and M. J. Newman, eds., Vaccine Design: the subunit Molina, J. I. 1782. Saggio sulla Storia Naturallede Chile. Vol. 2:175. adjuvantapproach.PlenumPress, New York. Morein, B., B. Sundquist, S. Hoglund, K. Dals, U. Patel, M. Lennick, and D. Marciani. gaard, and A. Osterhaus. 1984. Iscom, a novel 1991. Separationand characterization saponins of structurefor antigenic presentationof membrane with adjuvant activity from Quillaja saponaria proteins from enveloped viruses membranes.NaMolina cortex. Journalof Immunology 146:431ture 38:457-460. 437. , K. Loevgren, K. Dalsgaard, J. Thurin, and Kikuchi, M., K. Imagawa, T. Takizawa, Y. Aihara, B. Sundquist. 1990. Sterol-containing iscom maN. Mukai, H. Wakebe, S. Sakamato, and Y. Natrix with immunostimulating activity. PCT Intergata. 1996. Crudedrug compositionagainstHelinationalApplicationWO 90 03,184. cobacter pylori. JP 8119872 A. Kinekawa, Y., Y. Namikoshi, S. Okuda, and R. Tsu- Mukai, S., T. Matusuda, and Y. Kanazawa. 1993. Manufacture foaming beverageswith saponins, of kamoto. 1992. Handcreamsuitablefor workersof saccharidesand carbondioxide. JP 05 38,275. food processing.JP 04 36,210. perfumescontainKooryama, T., and I. Chiba. 1996. Oxidation-stable Murakami, F. 1986. Water-soluble ing essential oils solubilized by saponins. JP emulsions of oil and fats with transparent appear61,266,496. ance and food containingthem. JP 9651928 A2. . 1988. Emulsifying propertiesof quillaja saKudo, S., and E. Nishi. 1992. Surfactant method and ponins. GekkanFudo Kemikaru 4:47-53. for producingthe same. U.S. patent5,152,928. . 1996. Properties and applications of food Ledis, S., R. Harold, and T. Senal. 1985. Method emulsifiers.Saponins.Bessatsu Fudo Kemikaru8: and reagentsystem for four-population differential determination leucocytes. PCT International of 52-56. ApplicationWO 85 05,684. , and T. Watanabe. 1988a. Production of Lowe, J. A., and S. J. Keshaw. 1997. The amelioratemulsified fat and oil-containingsoy sauce. JP 63 ing effect of Yuccashidigeraextracton canineand 233761.

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BOOK REVIEW
Wild Plants and Native Peoples of the Four Corners. William W. Dunmire and Gail Tierney. 1997. Museum of New Mexico Press, P.O. Box 2087, Santa Fe, New Mexico 87504. 313 pp. (paperback). $22.50. ISBN 0-89013-319-0. It is rare to encounter an ethnobotanical book of any technical nature successfully written for a general audience without formal training in anthropology and/or botany. Rarer yet is to find a book written with those intentions that is also credible and useful to practicing anthropologists and botanists, especially those interested in the other's discipline. Dunmire and Tierney have compiled such a book about plants in the Four Corners Region of the American Southwest by drawing on an impressive review of primary and technical literature, interviews, personal observations, and an excellent collection of illustrations and color photographs. Many books on economic plants are structured as inventories of plants and their uses that are either independent of cultural affiliation or independent of ecological assemblages. The first chapter introduces the subject by discussing the concept of place and uses this as the organizing principle in the book. The physiography and the kind of vegetative communities that can currently be supported on the land in this region are described. The following chapters introduce the cultures inhabiting this area through time (Ancestral Puebloans, Hopi, Navajo, Utes, and Jicarilla Apache), and how they used and managed plants. A brief history of the people is given, their culture is described, and the kinds of settlements they occupied are discussed in the context of plant procurement for human use. Pictures of artifacts utilizing plant materials are inter-

spersedthroughout chaptersto help illustratehow the plantsare used. For each time period,the authorsprovide an idea of how environmental change in the region may have influencedthe availableplant resources, and how this may differ from the present "place" describedin the first chapterof the book. Thoughhundredsof plants are discussedin general terms throughoutthe text, a select group of approximately50 plantspecies commonto this place aregiven two to four page descriptionsin the final chapterof the book. After a brief introduction ecozones-reto inforcing the role environmentplays in plant distribution-the habitat is mentioned where the selected plants are most common, the cultureshistoricallyutilizing the plant are describedas are the useful components of the plant and the modes of preparation of those components.The plantsin this chapterare beautifully illustratedand well photographed, I found but the identification descriptors sparseandpotentiallydifficult to use. One needs to alreadyknow the name of the plant or flip throughnearly 150 pages to find it, which may not be appropriate a generalaudience. for Perhapsthis section of the book would be easierto use if there were a very simplistickey based on leaf type or flower shape, for example. One of the highlightsof this book is a chartof over 300 plant species known to have been used by the people occupyingthe region. The uses, culturalgroups known to use them and referencesare all in one place. This book will be a useful tool for ethnobotanists and those with a general interestof the economic uses of plants alike.
ROBIN C. D. CURREY SCHOOLOF NATURAL RESOURCESAND ENVIRONMENT UNIVERSITYOF MICHIGAN