At its forth meeting the Conferences of Parties to the Stockholm Convention decided to list perfluorooctane sulfonic acid (PFOS), its salts and perfluorooctane sulfonyl fluoride (PFOSF) in Annex B (Restriction) of the Convention with the following acceptable purposes and specific exemptions for production and use, as listed in Part III of Annex B (Annex 3). Alternatives to PFOS are addressed in this publication to provide information that may permit Parties to substitute PFOS with safer alternatives.
The reasons for addressing selected exempt uses of PFOS in this publication are:
• Those which today are thought to be the major uses
• Those where countries have applied for exemptions and industries in certain countries are considering to need exemptions (Annex 3)
• Those were POPRC information is thought to be missing and were POPRC requested Parties and observers to provide information on use of PFOS or its alternatives and on quantities of PFOS:
* Aviation hydraulic fluid;
* Chemically driven oil production;
* Electric and electronic parts for some colour printers and colour copy machines
* Insect baits for the control of leaf-cutting ants from the Atta and Acromyrmex species. Peer reviewed studies and pilot projects would be useful to evaluate the feasibility of alternatives to PFOS within an integrated pest management approach.
Where countries have asked for exemptions Parties might need particular support on information on alternatives. According to the Convention, Parties using PFOS and related substances need to first register for the necessary acceptable purposes and/or specific exemptions. They will afterwards need to take action to phase out uses when suitable alternatives substances or methods are available.
The specific exemptions and/or acceptable purposes which have been registered by some Parties are compiled on the BRS Website.
A UNIDO report on PFOS concluded that while developing countries might use PFOS in many sectors, industrial countries are likely restricted only to a smaller number of specific industrial uses. According to the report, China was by far the largest producer and user between 2003 and 2008. Industrial countries such as Japan and Germany were also producers and users of PFOS among developed countries in the period of 2003-2008.
China is considered the largest producer of PFOS with a production capacity of 100 t/y, . The perfluorootane sulfonates (PFOS) are mainly used for metal plating, aqueous fire-fighting foams (AFFFs) and sulfluramid in China, and the use amount is about 30-40 t/y, 25-35 t/y and 4-8 t/y respectively.
 Zhang Lai et. al. (2012), The inventory of sources, environmental releases and risk assessment for perfluorooctane sulfonate in China, Environmental Pollution 165 (2012) 193 – 198.
 Lim, Wang B, Huang J, Deng S, Yu G (2011) Emission Inventory for PFOS in China: Review of Past Methodologies and Suggestions, The Scientific World JOURNAL 11, 1963–1980.
After the listing of PFOS, its salts and PFOSF in the Convention, the POPs Review Committee came to support the Parties in their actions on switching to alternatives. The working group on guidance on alternatives to perfluorooctane sulfonic acid, its salts, perfluorooctane sulfonyl fluoride and their related chemicals constituted under POPs Review Committee prepared for its 9th meeting the “Revised draft guidance on alternatives to perfluorooctane sulfonic acid, its salts, perfluorooctane sulfonyl fluoride and their related chemicals”
The guidance summarizes the most recent information about alternatives to PFOS, its salts, PFOSF and their related chemicals in order to enhance the capacity of developing countries and countries with economies in transition to phase out PFOS, its salts and PFOSF taking into account the need for longer phase-in schedules for alternatives for some uses and the fact that for certain uses alternatives may not be currently readily available in all countries.
The document concludes that fluorinated or non-fluorinated alternatives exist for nearly all current uses of PFOS and that, importantly, they will normally be less hazardous.
It should be noted that perfluorohexane sulfonate (PFHxS), a homologue of PFOS, has been determined by POPRC to have the same POP characteristics (persistence, bioaccumulation, toxicity, long-range transport) as PFOS (UNEP, 2008) and therefore the POPRC concluded that PFHxS and its related substance are not acceptable alternatives to PFOS.
The most common PFOS alternatives in use are fluorotelomers, which are precursors for PFCA. Formerly, C8-fluorotelomers were a frequent choice; they have been shown, however, to degrade into PFOA, which also has hazardous properties. For that reason some producers of fluorochemicals in the EU, Japan, and US have agreed to commit to working toward the elimination of PFOA, chemicals that breakdown to PFOA, and related higher homologues by 2015. As a result, there has been a shift by producers to C6-, C4- and C3-perfluoroalkylated chemicals, and subsequent concerns about some of the properties of these substitutes have been raised. Some alternatives may eliminate PFOS or other fluorinated or chemical alternatives completely. Sometimes, but not always, there is enough information to determine whether they are suitable from both, a functionality and environmental health and safety perspective.
Table 12: Availability of information used for the assessment of alternatives to the use of PFOS in open applications
PFOS and related substances have been used as surface coatings to increase the oil and water repellency of textiles. A number of alternatives to PFOS and related substance are now available for these uses.
A distinction needs to be made between the uses for hydrophobingand for increasing oil repellency for specific application. There are a wider range of approaches for hydrophobing as this can be achieved by less chemically aggressive approaches compared to oil repellency.
Per and Poly-fluoroalkyl alternatives
Side-chain fluorinated polymers are used extensively by the textile industry and by consumers for the treatment of all-weather clothing, umbrellas, bags, sails, tents, parasols, sunshades, upholstery, leather, footwear, rugs, mats, carpets etc, to repel water, oil and dirt (stains).
PFOS derivatives have been banned in many countries and replaced with either shorter-chain analogues, fluorotelomers or with non-fluorinated chemicals.
The POPRC guidance includes the following alternatives for the impregnation of textile fabrics, leather, carpets, rugs and upholstery and similar articles:
(a) Other polyfluorinated compounds with shorter alkyl chain length such as:
(i) Substances based on perfluorobutane sulfonate (PFBS);
(ii) fluorotelomer-based substances, including polymers;
(b) Flurorotelomer triethoxy silane such as polyfluorooctyl triethoxy silane (1H,1H,2H,2H-perfluorooctyl triethoxy silane, a NanoCover® product) used in a bathroom floor spray product. This and similar substances were banned in Denmark in April 2010 because of toxic effects on mouse lungs
For example 3M launched a product called Scotchgard® Protector containing 1–5% of a perfluorobutane sulfonyl urethane (the identity of the chemical has not been provided by the company), which has also been suggested as an alternative for stain-repellent impregnation of textiles, leather and carpets. DuPont has introduced a new brand name, Capstone®, for a series of alternative products for various applications based on short-chain fluorotelomers, mainly involving C6 chemistry. Other companies such as Daikin, Asahi and Clariant (and maybe others) have introduced short-chain fluorotelomers as well. Bluestar Silicones markets some silicone-based PFOS alternatives for textile applications under the trade name Advantex®. The technology offers long-lasting water repellence, quick drying, waterproofness and breathability. The environmental persistence of these replacements is uncertain and is the subject of ongoing research.
Fluorocarbon-free silicon-based alternatives
Fluorocarbon free alternatives based on:
(a) Silicone-based products;
(b) Mixtures of silicones and stearamidomethyl pyridine chloride, sometimes together with carbamide (urea) and melamine resins;
are available on the market.
Fluorocarbon-free hydrocarbon-based alternatives
A) Fluorocarbon-free, water-repellent finishing agent
There is a fluorocarbon-free, water-repellent finishing agent for textiles produced available which is marketed by a German company. Several known brands are utilizing this advanced technology for their hydrophobic outdoor wear. It is the ecological alternative to conventional durable hydrophobic finishes based on perfluorinated polymers.
In another product, also no perfluorinated compounds are used in the manufacturing processwhich is the corresponding finishing product used in the textile mills for producing the aforementioned product.The latter product is composed of special waxes and star-shaped, hyper-branched polymers also called dendrimers. It can be applied to all types of substrates but is mainly used for outdoor textiles.
This PFOS/PFAS-free waterproofing agent has according to the producer a range of advantages:
According to the OECD test methods, the product is not easily biodegradable but eliminable.
The second product can be easily eliminated from the effluent (> 80%) and is considered harmless regarding water toxicity (EC-50 (bacteria) > 100 mg/l, LC-50 (fish) > 100 mg/l) as well as oral toxicity (LD-50 (rat) > 5000 mg/kg).
B) Functional finishing agent
New textile finishing products from another producer are the result of an interdisciplinary development project. Experience with the textile industry, polymer processing and surface technology was combined to develop a new solution for the functional finishing of textiles. The new products include:
1. A water-repellent: Water-based, aliphatic polyurethane emulsion, reactive, one- or two-component, hydrophobic.
2. A water attracting agent4: Water-based, aliphatic polyurethane emulsion, latent reactive, one-component, hydrophilic.
3. An abrasion protection agent4: Water-based, aliphatic polyurethane emulsion, reactive, one- or two-component.
According to the producer, the fluorocarbon-free waterproofing agent has a range of properties to improve the performance of textiles:
Efficiency: It offers textile finishers advantages. In addition to the desirable performance properties it also reduces manufacturing, chemical stocking and disposal costs. It does not require retooling for application purposes. It can be applied using all known textile wet finishing processes. With a solid content up to 70 percent, it makes it possible to achieve high add-ons in a single pass. Less water needs to be evaporated, and fewer stabilising agents are required. This is primarily an economic advantage for textile manufacturers resulting in better machine utilisation and reduced logistical and energy costs. In addition, because the emulsifiers are easily degradable, wastewater requires no treatment, further reducing costs. With this new product, multiple functions can be achieved through a single treatment, meaning that textile finishers can dispense with many of the chemicals they would otherwise need.
Versatility: The different handling and surface properties the product provides to textiles makes it suitable for a wide range of applications, e.g. outdoor and sportswear, workwear, protective clothing, interior of vehicles, fabrics for furniture and the home.
Compliance: The product conforms to all international laws and standards and meets or exceeds all applicable legal and regulatory standards, as well as the RSL (Restricted Substances List) guidelines of leading brands and retailers. It complies with legal requirements for the sale within the EU (REACH), as well as individual country requirements, such as the Consumer Product Safety Improvement Act (CPSIA) in the U.S. The fact that the product is 100% solvent-free and safe to use is critical in meeting these regulations. It contains nothing but polyurethane (PUR) and does not contain substances that have been classified as toxic, harmful or non-biodegradable. The emulsifiers used for the product are readily biodegradable.
The properties of this finishing agent are neither new nor unique in themselves. It achieves a durable water repellent effect in a cost-effective product without needing to use persistent chemicals and does not contain substances that are considered in any way dangerous, either to humans or to the environment.
C) Water and dirt repellence
There is another new finishing agent that ensures a high level of water and dirt repellence (mud) on textile produced by a Swiss company. The technology is environmentally sound, free from fluorocarbons and biodegradable.
This finishing agent consists of paraffin chains that wrap themselves around the individual fibres of a fabric. This reduces the surface tension of the textile so that water and mud with a considerably higher surface tension run off simply.
According to the producer:
 Increasing water repellency.
 High molecular weight siloxanes are normally used.
 See, for example: Liu, Jinxia and Sandra Mejia Avendaño. 2013. Microbial degradation of polyfluoroalkyl chemicals in the environment: A review. Environ Int 61 (0): 98-114.
 High molecular weight siloxanes are normally used.
 The commercial name of the product concerned is BIONIC-FINISH®ECO marketed by Rudolf Chemie Ltd., Geretsried/Germany.
 The commercial name of this product is RUCO-DRY® ECO which is also marketed by Rudolf Chemie Ltd., Geretsried/Germany.
 The commercial name is Purtex® and the producer is the Freudenberg Group, Weinheim/Germany.
 Purtex® WR, Purtex® WA, Purtex® AP marketed by the Freudenberg Group, Weinheim/Germany.
 The commercial name of the product is ecorepel® marketed by Schoeller Techologies AG, Sevelen/Switzerland.
 in accordance with OECD 302 B (80 – 100%).
In chromium plating PFOS can be substituted by per and poly-fluoroalkyl alternatives as well as fluorocarbon-free alternatives.
The German national metal plating association (ZVO) describes the availability of PFOS-free alternative products from 10 German suppliers. . While information is lacking about the exact identity of several of these chemical compounds, three were fluorinated chemicals and seven were fluorine-free. The non-fluorinated alternatives were not stable enough in the hard chrome plating bath. It is stated that all 10 products could be used for decorative chrome plating, for which alternative Cr-III processes seem to exist already in many cases.
Per and Poly-fluoroalkyl alternatives
Reported PFOS alternatives used in chromium plating are for example perfluorobutane sulfonate (PFBS) (CAS RN 29420-49-3; CAS RN 45187-15-3) based chemicalsand H4PFOS (1H,1H,2H,2H-Perfluorooctanesulfonic acid; CAS-Nr.: 276-19-97-2). PFBS are rapidly eliminated from the body with a relatively low bioaccumulation potential. The toxicity and ecotoxicity of H4PFOS is less clear. The use and release of H4PFOS is higher compared to PFOS. The German Federal Environmental Agency consider H4PFOS not a good alternative substance for PFOS since it is still highly fluorinated and persistent and since it is more difficult to remove from the waste water resulting in higher quantities emitted to waste water treatment plants and ultimately into surface waters compared to PFOS).
In China additionally available PFOS alternatives used for chrome plating are F-53 (1,1,2,2-tetrafluoro-2-(perfluorohexyloxy)ethane sulfonate, CAS RN 756426-58-1) and F-53B (potassium 2-(6-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyloxy)-1,1,2,2-tetrafluoroethane sulfonate, CAS RN 73606-19-6). The persistence, the potential to bio-accumulate and the fish toxicity has been assessed and found similar to that of PFOS and therefore a recommendation or the use of this alternative cannot be given (see Case study: Scientific assessment of a PFOS alternatives in chromium plating).
Fluorocarbon-free based alternatives
Non-fluorinated alternatives for hard chrome plating are available on the European market. However these are rather new and some are still being tested. These alternatives appear functional with some slight process changes including stirring the chromium bath.
The experiences with alkylsulfonates in recent years show that alternative substances for PFOS in bright chrome plating are available. This substitution is also possible for hard chrome plating, according to the statements of the specialist companies. However, here the practical experience and transferability of existing alternatives to other hard chrome platers are lacking. According to the published patent application, the mixture contains unbranched and branched long chained alkylmonosulfonic acids and alkyldisulfonic acids. According to the product safety datasheet the product is biodegradable.
Another possible non-fluorinated surfactant alternative for decorative plating may be Enthone® (ethoxylated oleyl amine, CAS no. 26635-93-8). Alternatives to the PFOS derivatives are less stable and durable in the chrome bath than PFOS since they degrade through oxidation.
The Norwegian association of electroplaters (Norsk Galvanoteknisk Landsforening, or NGLF) has reported that the industry has already started to phase out the use of PFOS-containing wetting/anti-mist agent by using the Cr-III process instead of the Cr-VI process where possible.
The use of control devices, such as Composite Mesh Pads (CMP) or Packed Bed Scrubbers (PBS), to catch aerosols from chromium plating baths offers an alternative to the use of PFOS. CMP are currently considered to be maximum achievable control technology of chrome VI aerosols, but these installations cost more than current operations. Closed tanks with increased ventilation have been suggested as alternative solutions to CMP and PBS for applications where use of chromium-III is not yet possible. However, such systems need further improvement to be as effective as control devices in getting rid of chromium emissions. There is some concern that increased ventilation will also result in increased energy consumption and loss of some chromium from baths. Other methods such as using physical covers (netting, balls) for baths to diminish hydrogen burst and reduce misting currently do not work but should be further investigated.
 Personal communication from Christoph Matheis, Zentralverbandes Oberflächentechnik e. V. (ZVO), 6 March 2009.
 Environmental Canada (2014) Format for the collection of information on alternatives to the use of perfluorooctane sulfonic acid, its salts, perfluorooctane sulfonyl fluoride and their related chemicals. 31.01.2014.
 German Federal Environmental Ministry (2014) Format for the collection of information on alternatives to the use of perfluorooctane sulfonic acid, its salts, perfluorooctane sulfonyl fluoride and their related chemicals.14.02.2014.
 Presentation by Jun Huang, Tsinghua University, at the national workshop on nine new persistent organic pollutants and the implementation of the Stockholm Convention in China, Beijing, 1–2 July 2010.
 Wang et al (2013) First Report of a Chinese PFOS Alternative Overlooked for 30 Years: Its Toxicity, Persistence, and Presence in the Environment. Environ. Sci. Technol., 47, 10163–10170.
 German Federal Environmental Agency (2013) Progress report ‘‘Replacement of PFOS with halogen-free substitute materials in galvanisation’ December 2013. Submission to POPRC 9.
 Bundesrepublik Deutschland Deutsches Patent-und Markenamt (2008) Offenlegungsschrift DE102006042076A12008.03.20.
 TIB Chemicals (2011) TIB SUACT CR-H, Sicherheitsdatenblatt gemäß 1907/2006/EG, Artikel 31. 25.07.2011.
Information from Norwegian Pollution Control Authority (former Statens Forurensningstilsyn), 2009.
 Poulsen et al. Substitution of PFOS for use in nondecorative hard chrome plating, 2011, Environmental Project No. 1371 2011, Danish Ministry of Environment.
PFOS derivatives have been used in food contact applications including plates, food containers, popcorn bags, pizza boxes and wraps as well as in non-food contact applications such as folding cartons, containers, carbonless forms and masking papers. Before 2000 about 32% of the total use of PFOS in the European Union was for paper coating but the use of PFOS for this purpose is no longer allowed.
Historic PFOS use in the production of waterproof and greaseproof papers has been replaced mainly by other fluorinated chemicals. The alternative chemical surfactants for paper and cardboard use in packaging are short-chain telomer-based substances and perfluoropolyethers, and poly (dimethyl siloxane).
Grease-proof paper existed before PFOS technology was introduced to the market, and so it is clear that other technologies are available as substitutes.
A 2006 survey by the Norwegian Food Safety Authority concluded that no fluorinated substances were used in fast-food packaging in Norway. Nordic Paper, a Norwegian paper manufacturer, uses mechanical processes to produce extra-dense paper that inhibits leakage of grease through the paper without the use of any additional chemical.
A number of different types of fire-fighting foams which included PFOS have been produced:
(a) Fluoro-protein foams used for hydrocarbon storage tank protection and marine applications;
(b) Aqueous film-forming foams (AFFF) developed in the 1960s and used for aviation, marine and shallow spill fires;
(c) Film-forming fluoroprotein foams (FFFP) used for aviation and shallow spill fires;
(d) Alcohol-resistant aqueous film-forming foams (AR-AFFF), which are multi-purpose foams;
(e) Alcohol-resistant film-forming fluoroprotein foams (AR-FFFP), which also are multipurpose foams, developed in the 1970s;
Fire-fighting foams containing PFOS have been very effective for extinguishing highly flammable liquid fuel fires (e.g. at airports, oil refineries or storage facilities). However, they represent a direct release of PFOS to the environment. Fire-fighting foam production is still a major use of PFOS in China.
Fluorine-containing fire-fighting foam alternatives
Today most AFFF fire-fighting foams are manufactured with fluorochemicals/telomers based on a perfluorohexane (C6) chain.
Manufacturers, distributors and users of AFFF fire-fighting agents and their chemical components have formed a trade association, the Fire Fighting Foam Coalition (FFFC), whose stated aim is to ensure that accurate industry information about PFOS alternatives, including telomer-based products, is disseminated to appropriate audiences.
The alternatives to the use of PFOS fluorosurfactants in fire-fighting foams are:
(a) Non-PFOS-based fluorosurfactants with shorter chain length such as:
(i) C6-fluorotelomers such as perfluorohexane ethyl sulfonyl betaine, often used in combination with hydrocarbons such as ®Capstone® products (DuPont);
(ii) Dodecafluoro-2-methylpentan-3-one (3M).
Non-fluorine containing fire-fighting foam
There are fluorine-free alternatives on the market,
(i) Silicone-based surfactants;
(ii) Hydrocarbon-based surfactants,
(iii) Synthetic detergent foams, often used for forestry and high-expansion applications and for training (“Trainol”); new products with glycols (Hi Combat ATM from AngusFire);
(iv) Protein-based foams (e.g. Sthamex F-15), which are less effective for flammable liquid fuel fires and are mainly used for training but also have some marine uses.
In some applications these foams are less effective than fluorine-containing AFFF foams (POPRC Draft guidance PFOS Alternatives).
The Norwegian producer Solberg Scandinavian AS states that the performance of the fluorine-free Arctic Re-Healing Foam™ RF is close to that of AFFF and that it is a good alternative for a range of uses. It has been approved for the control and extinguishing of class B flammable liquid hydrocarbon and polar fuel fires. Arctic Re-healing Foam RF meets the requirements of parts 3 and 4 of the European Committee for Standardization (CEN) EN 1568 specifications.
Solberg foams can also be used for Foam/Water Sprinkler System. The company has an upgrade program utilising RE-HEALING™ Foam (RF), the first UL-listed and FM-approved fluorine-free foam concentrate. This contains no fluorine or other organ halogens - whether surfactant or polymer based.
Customers with foam/water sprinkler systems containing fluorine based foam concentrates, and particularly those with older technology foams including PFOS and PFOA, can substitute to the non-fluorine containing alternative. The Program facilitates upgrades by users of fluorine containing Aqueous Film Forming Foam (AFFF) to the fluorine-free RE-HEALING Foam while maintaining the existing system compliance certification by NFPA 11.
Fluorine-free alternatives to fire-fighting foams in the United Kingdom were approximately 5–10% more expensive than fluorosurfactant-based foams (Risk and Policy Analysts and Building Research Environment. 2004). The price should fall as the market size increases and a major shift towards fluorine-free fire-fighting foam alternatives would probably eliminate the difference in cost.
 Due to the lower effectiveness compared to AFFF this foam is e.g. not used as alternative at offshore installations or for the petroleum industry.
 Information from Norwegian Pollution Control Authority (former Statens Forurensningstilsyn), 2009.
According to the POPRC PFOS alternative report, there is uncertainty about alternative substances in this area. Aviation hydraulic fluids can be based on, for example, phosphate esters and fluorinated chemicals other than PFOS.
POPRC is currently gathering information from Parties on alternatives for this application and this will be included in an update of this publication.
N-Ethyl perfluorooctane sulfonamide (EtFOSA; sulfluramid; CAS no. 4151-50-2) is both a surfactant and a pesticide used in tropical areas against termites, cockroaches and other insects and in Brazil for control of leaf-cutting ants from the Atta spp. and Acromyrmex spp. The 2006 OECD survey indicates that sulfluramid was used in insecticides at a concentration of 0.01-0.1% with an annual volume of up to 17 tonnes. Fluorosurfactants may also be used as “inert” surfactants in pesticide products. These substances are released directly to the environment.
PFOS is no longer used to manufacture ant bait or insecticides against beetles and ants in the European Union, and the United States Environmental Protection Agency cancelled the registration of sulfluramid in May 2008 and PFOS is no longer used to manufacture ant baits or insecticides against beetles and ants in the European Union.
Information submitted to the secretariat of the Stockholm Convention indicates that sulfluramid had been used to control cockroaches, white ants and fire ants) in China and is used in Brazil in more than 95% of baits for the control of leaf cutting ants. The quantity of PFOS used was not reported. Since sulfluramid is degraded to PFOS this use represents a direct release of PFOS to the environment.
The active ingredients currently registered in Brazil for producing bait to control leaf-cutting ants are sulfluramid, fipronil and chlorpyrifos. The latter two, however, are considered more acutely toxic to humans and the environment than sulfluramid . Furthermore, the effectiveness of these substances has been questioned and alternatives are now being reviewed in Brazil. According to the Brazilian Annex F information, sulfluramid cannot currently be efficiently replaced in Brazil by any other registered products commercialized for the same purpose. However, ant baits containing S-methoprene and pyriproxifen are registered in New Zealand for the control of exotic ants by aerial and ground applications. In the EU, PFOS-related substances are not used in the manufacture of pesticides.
There are many differences between leaf-cutting ants and exotic ants (urban ants), including in alimentary behaviour and these differences explain why some active ingredients are effective for controlling urban ants but not for controlling leaf-cutting ants. Since 1958, over 7,500 chemical compounds for ant control have been studied in many countries. According to the industry association, the Leaf-Cutting Ant Baits Industries Association, less than 1% of those 7,500 compounds have shown promise.
Studying the adaptation mechanisms of leaf-cutter ants is recommended to improve effectiveness of strategies for their ecological management. Several mechanical, cultural, biological and chemical methods have been studied since the 1950’s for controlling leaf-cutting ants. The management of the ants using resistant plants toxic plants, and by manipulating predators, parasitoids and micro-organisms, has had inconsistent results. However, diversification of crop systems, including the conservation of undergrowth and strips of native vegetation offers some potential for management. Biological control can be effective. In laboratory studies, the entomopathogenic Metarrhizium anisopliae can cause the decline and ultimate death of small colonies and research indicates that the entomopathogenic fungi Beauveria bassiana and Aspergillus ochraceus both show a high degree of control with 50% mortality within 4-5 days. Effective natural products include limonoids extracted from the roots of the endemic South Brazilian plant Raulinoa echinata.. Biological, mechanical and cultural control methods, besides plant resistance, can reduce the quantity of chemicals applied in the plantations. Mixing compostable materials with ant nests (Atta cephalotes) in a Columbian study caused a rapid decrease of ant nests (73%) within three months. The results of this study indicate that composting treatment might be used as an alternative method to control leaf-cutting ants (A. cephalotes).
 Enhancers used in pesticide formulation but not consisting active ingredients.
 UNEP (2007) Addendum Risk management evaluation on perfluorooctane sulfonate UNEP/POPS/POPRC.3/20/Add.5
 Environmental Risk Management Authority of New Zealand (ERMA NZ) (2007), Decision, 2007-11-11.
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 Della Lucia TMC, Gandra LC, Guedes RNC. (2014) Managing leaf-cutting ants: peculiarities, trends and challenges. Pest Manag Sci 70(1):14-23.
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 Maique W. Biavatti*, I; Rosângela WesterlonI; Paulo C. Vieira; M. Fátima G. F. da Silva; João B. Fernandes; M. Fernanda G. V. Peñaflor; Odair C. Bueno; Javier Ellena, Leaf-cutting ants toxicity of limonexic acid and degraded limonoids from Raulinoa echinata. X-ray structure of epoxy-fraxinellone, Journal of the Brazilian Chemical Society Print version ISSN 0103-5053. Chem. Soc. vol.16 no.6b São Paulo Nov./Dec. 2005.
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