N anotechnologies for nutrient _ biocide delivery in agricultural

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					nutrient & biocide delivery
      Nanotechnologies for

 in agricultural production
                                Special Interest Report
                              for the ObservatoryNANO



                                                          2010
                                                                 This special interest report is designed to be a quick reference text on the major elements of
                                                                 nanotechnology developments for biodegradable and edible food packaging. Identified as a
                                                                 an area of special interest in the 1st year of the ObservatoryNANO project

                                                                 The target audience for this report includes policy makers, funding agencies and other
                                                                 interested parties.

                                                                 For more detailed information on the technologies or products referred to in this report,
                                                                 please consult the online resources which provide in-depth analysis of Science and
                                                                 Technology developments and Economic developments, or get in touch with the specific
                                                                 points of contact:
                                 Please cite this report as:
 ObservatoryNANO (2010) Nanotechnologies for nutrient            Science & Technology Trends:
 and biocide delivery in agricultural production. Working        Douglas K. R. Robinson – douglas.robinson@nano.org.uk
                                Paper Version, April 2010.
                                                                 Economic Aspects and Market Analysis:
                                        www.observatorynano.eu   Gabriela Salejova-Zadrazilova – zadrazilova@tc.cz
                                                    Table of contents

Executive summary ............................................................................................................. 3
Introduction ........................................................................................................................ 5
   Definition................................................................................................................................. 5
   Methodology ........................................................................................................................... 5
Science and Technology aspects ......................................................................................... 6
   Why is there an interest in nano-augmented delivery? ............................................................ 6
   State of R&D ............................................................................................................................ 6
      Nanoemulsions .................................................................................................................... 7
      Nanoparticles ....................................................................................................................... 7
      Nanodispersions................................................................................................................... 8
      Nanoclays ............................................................................................................................ 8
      Technology Readiness Level as an indicator of technology developmental stage .................. 9
   Current situation within the EU.............................................................................................. 10
Economic aspects .............................................................................................................. 11
   General market description ................................................................................................... 11
   Economic drivers ................................................................................................................... 13
      Regulation and Standardisation.......................................................................................... 14
      Rise in Energy Costs............................................................................................................ 14
      Climate Change .................................................................................................................. 14
      Clean water supplies amidst an increasing global population ............................................. 14
   Economic barriers .................................................................................................................. 15
      Perception of the sector ..................................................................................................... 15
      Additional cost ................................................................................................................... 15
   Selected company profiles active in the agrochemical industry .............................................. 15
   Selected Products .................................................................................................................. 17
Acknowledgements ........................................................................................................... 20
References ........................................................................................................................ 21
                                         Executive summary
      The changing demands on agricultural production and management

Maximising output, minimising waste, and reducing the impact on the environment are key
drivers for the agricultural industry. The agriculture sector as a whole employs over 11 million
people within the EU (approximately 2.3% of the population). As such it represents a major
opportunity for innovation to ensure that the EU progresses towards the Lisbon goals.
In the area of agricultural production and management, there are a number of issues facing the
sector:
    •    Inflation of food price. The FAO Food Price Index (FFPI) has begun to rise steadily,
         fuelled by volatile and inflated prices of a key range of commodities such as cereals, fats,
         oils and dairy products.1 A number of factors have led to this; low global food stocks
         (reduced buffer), weather events and disease outbreaks, the activities of speculators in
         commodities such as agricultural goods, and food policy artificially preventing domestic
         food price increase, has lead to a situation increasingly referred to as the food crisis.2
         This leads to high demand pressures on agricultural production and management.
    •    Increasing population and Nutrition transition towards a higher protein diet. As can be
         seen in rapidly developing countries there is a transition from a cereals and tuber
         dominated diet to more meat. For example rearing poultry for protein, rather than
         derive it directly from crops, requires approximately four times the land area to deliver
         the equivalent feed volumes. This can be seen in China and India3
    •    Climate change and its effects on weather systems. In Europe, one major effect could
         be on harvesting routines, where delayed harvesting often leads to rotting crops. A
         further secondary effect of climate change4 is the variability in the occurrence of crop
         pathogen and disease spread. A recent example being the UK potato harvest of 2008
         where the damp summer resulted in the highest occurrence of potato blight since the
         Irish Potato Famine of the 1840's.
    •    Adaptive supply chains from farm to fork: There is a shift from stable supply chain1
         relations to more flexible and agile relationships with shifts and reorientations based on
         the needs of the value chain. This means suppliers need to remain aware of the
         dynamics of the value chain and adapt meaning a constantly co-evolving situation
         between supply and value chains.




1
  Supply chain is taken as the provision of an element to a food product (such as wheat, barley, bioplastics for
packaging etc.) and value chain is the chain of developments from raw materials to end product in the grocers, on the
shelves of supermarkets or for sale directly from source. Thus the value chain is a complex interlinking of many
supply chains, requiring a great deal of management and coordination. ICT is playing a large role in this adaptive
supply chain management but is beyond the scope of this report ( for more information on advanced supply chain
management see Ivanov Sokolov and Kaeschel (2009). A multi-structural framework for adaptive supply chain
planning and operations control with structure dynamics considerations. Journal of Production, Manufacturing and
Logistics)


                                                         3
   •   Environmental sustainability and Agricultural management: As with all industries,
       there is pressure to be environmentally and economically sustainable in the long term.
       This encompasses new legislation affecting the number of pesticides which can be used;
       and decreasing agricultural waste (or finding novel uses for it), for example Europe's
       fruit and vegetable industries generate about 30 million tonnes of waste a year5.


Technical Innovation as part of the solution?
New technologies promise to deliver options for these challenges outlined. One area receiving a
lot of attention in recent years is nanotechnology applied to advanced delivery systems and
nanoformulations for pesticides and nutrients. However, nanotechnology developments have
their own challenges, from upscaling and manufacturing, to regulatory uncertainty and lack of
standards, as well as uncertainty in risk assessment and management.
This report focuses on nanotechnology innovations for three functional improvements;
   (1) increased efficacy;
   (2) controlled release; and
   (3) targeted delivery for nutrients such as:
           a. fertilisers and plant growth enhancers
           b. biocides such as fungicides, herbicides and pesticides.


To date, information covering the breadth of nanotechnology developments within these areas
has not been made readily available, with reports focussing on particular nanotechnologies. As
may be imagined, many developments for the three desired functions given above parallel those
in the pharmaceutical and nutrition sectors. This report focuses on those nanotechnologies
where there is active research and development for agricultural purposes.
This report includes, within its scope, the technological developments, market applications in
the sector, and also looks at broader drivers and barriers to the further development of nano-
augmented delivery systems for agriculture.




                                                  4
Introduction

Definition
Agricultural production for the purpose of this report is defined as the processes to produce
materials from plant cultivation and raising domesticated animals. This material includes
foodstuffs, fuel, and raw materials for other industries including the pharmaceutical, textile, and
construction industries.

Methodology
The data gathering approach for this report has been structured along three lines with three
methodologies.
The three lines of investigation are:
    (1) Scientific and Technological Developments;
    (2) Market and broader economic factors; and
    (3) Other framing conditions that will affect innovation such as regulation, standards and
        environmental, health and safety issues (EHS) and societal issues.
These together provide a multi-faceted but integrated investigation into the challenges and
opportunities in this area, providing relevant input in line with the elements set down in the EU
Action Plan for Nanosciences and Nanotechnology6 and the proposed European Code of
Conduct for responsible nanosciences and nanotechnologies research.7
The three methods used:
    (1) Literature and patent analysis;
    (2) Interviews; and
    (3) Focus workshops2.
This integrated analysis brings together technology and economic assessment along with
indications of the drivers and barriers, boundary conditions, market factors, regulatory issues
and societal aspects, along with profiles of selected companies and products.




2
 This report uses evidence and insights gained from an interactive workshop held in Glasgow on 11/11/2009 entitled:
Nanotechnologies for Agricultural Production and Management: Horizon and state-of-the-art scanning workshop as
part of the ObservatoryNANO project 2008-2012


                                                        5
Science and Technology aspects
Why is there an interest in nano-augmented delivery?
Pesticides are used to kill organisms that are detrimental to agricultural production, including
viruses, bacteria, fungi, parasites, weeds, and insects. They have been used for millennia
(sulphur being the first recorded); however, modern pesticides place their own burdens on
farming systems, for example accumulation in soils and ecosystems, which can have unexpected
and often deleterious effects, as was the case with DTT. This is not just historic; atrazine is
widely used to control weeds, but is persistent in soil (with a half-life of anything between 41
and 231 days, dependent on depth of soil and water content8). It has a permissible limit of 3
ppb, but this is often exceeded locally and it can also migrate far from source leading to
contamination of rivers and drinking water.
The situation causes further concern when one considers that, depending on the environmental
conditions and mode of application, as much as 90% of conventional pesticides are lost to the
air during application, as run-off, or decompose; this affects both the environment and cost to
the farmer9. There is therefore an urgent need to a) find alternatives to current pesticide
deployment and b) find ways of rapidly and locally detecting levels of the pesticide and either
removing or degrading it.

State of R&D
In the last few years there has been activity by companies in the re-formulation of pesticides,
which are coming off patent, to protect market position by superior products. This is largely in
the area of new adjuvants or delivery systems (as is the case with pharmaceuticals). For crop
pesticides it is also driven by the need to resolve issues with current formulations including: use
of organic solvents (most pesticides are poorly soluble, and many of the organic solvents used in
their formulations have irritant properties); sensitivity to UV light (many have half-lives
measured in hours or minutes, e.g. phoxim 40 minutes, avermectin 6 hours); bioavailability
(crossing leaf cuticles); deposition and drift (due to droplet size when spraying); foaming; rain-
fastedness (sticking to leaves); and combining multiple pesticides into a single product.
Another issue is that of legislation. In the EU there is a drive to limit the numbers of pesticides
available. Directive 91/414/EEC is the EU regulation covering the use of pesticides, and is
essentially risk-based. However, recent amendments could decrease the number of pesticides
available to farmers (15% of the 300 accepted chemicals have been estimated by the UK
government’s Pesticides Safety Directorate), which various agrifood industry associations are
concerned could affect yield and quality of produce10.
The innovation driver for the agrochemical industry is thus to move towards measured release
of small (but sufficient) amounts of pesticide over a period of time, in response to
environmental stimuli (such as UV, moisture, or temperature) or to target pests more
effectively.
In the technological assessment of nano-augmented delivery systems for agriculture our
research shows that there are four (sometimes overlapping) clusters of activities in this area.
Following this, the state of R&D has been divided into four sub-domains: nanodispersions,
nanoemulsions, nanoparticles and nanoclays.




                                                6
Nanoemulsions
Nano-emulsions are systems that are metastable. The challenge is to stabilize them against
crystallisation, agglomeration and sedimentation by means of sufficient amounts of suitable
surfactants and additionally protective colloids.3
They can consist of lipid or polymeric vesicles or particles, in the size range of 20-200 nm. They
can have multiple phases, the simplest being oil-in-water. They are essentially similar to
emulsions in that they require energy input to be made, and differ from thermodynamically
stable micro-emulsions (which are in fact nanoemulsions) which form spontaneously when
surfactants/cosurfactants and solvents are added to a liquid medium (and are therefore
technically not emulsions). Both nano- and micro-emulsions have particles within the same size
range. Nano-emulsions of solid particles can be dried, through evaporation of the outer phase,
to leave particulates, which can then be suspended in water for application.
Nano-emulsions can be produced by both high energy (mechanical process using rotators,
ultrasound, or pressure homogenisers)11 and low energy means (either spontaneous
emulsification, due to solvent diffusion as a result of mixing or dilution or by phase inversion
temperature, a process which is controlled by specific surfactants, such as polyethoxylated
surfactants, in response to temperature change)1213.
In terms of agricultural applications, nano-emulsions could be used for hydrophilic and
hydrophobic pesticides. Examples are pyrethroids such as γ-cyhalothrin and β-cypermethrin14
and others like Artemisia arborescens L essential oil15.
Potential advantages described by the research community are the solubilisation of
hydrophobic pesticides (hence no need for toxic organic solvents). However, it should be noted
that manufacturing opportunities are not developed, as the precise mechanisms by which nano-
emulsions form and how their properties controlled are still the subject of intense basic
research. The benefit of nano-emulsions over coarser systems is not so clear. Information from
our interviews with industrial representatives suggests that the use of tailor made adjuvants
together with micron particles is likely to override the nano-emulsions which are much more
complicated with regard to preparation as well as stabilisation. Moreover the nanoparticluate
active ingredient itself is not sufficient for perfect performance; it still needs special adjuvants as
door openers for entering the leaf, in case of systemic actives.

Nanoparticles
Silica has been developed and commercialised for a number of years for medical applications16,
as it is known to be biocompatible. It can also be engineered as hollow nanoparticles with
different pore diameters and shells of different thickness. This has led a number of research
groups to investigate its potential as a drug delivery vehicle for medical and veterinary
treatments, and more recently for pesticides, such as avermectin and validamycin, where it has
been shown to afford protection against UV degradation and controlled release dependent on
pore diameter and shell thickness17,18. In research experiments nano silica has been reported to
provide insecticide activity on its own, through desiccation of insects’ cuticles. It has also been
successfully applied as a thin film to boost cereal germination and decrease fungal growth19.
However, nano silica is not a preferred auxiliary in crop protection products due to the adverse
effect upon inhalation.

3
  One industrial expert emphasised that it is hard to come down to the nanoscale here and even harder to come to
stable dispersions


                                                       7
There have been a number of studies exploring the use of nanoparticles in the controlled
release of bioactive substances in wood202122 and the use of micro and nanoparticles as a tool for
plant science23. Recently the use of silica nanoparticles has been effective in the controlled
release of substances into protoplasts within plant cells.24 Work in Spain has focused on
developing tools for controlled and targeted release of substances in plant organs which are
susceptible to pathogens.25 Further work from this group reported more recently has shown a
deepening in the understanding of the mechanisms of interaction between plant cells and
nanoparticles.26

Nanodispersions
To overcome the poor activity of micron size suspensions, nanodispersions of insoluble
compounds can be created which have properties similar to that of solutions. Challenges
remain in processing of these nanodispersions and in maintaining stability over longer durations.
Recently a method has been reported combining a processing technique of modified emulsion
templating and freeze drying; the resulting powder composites are stable, highly porous and
form nanodispersions when added to water. The technique has been demonstrated with the
antimicrobial agent Triclosan.27

Nanoclays
Nano clays and layered double hydroxides are also being developed in this regard28. Both
materials show good biocompatibility, low toxicity, and the potential for controlled release.
Chemicals can be loaded between layers of both materials (an arrangement that can be
influenced by buffer conditions, in particular pH). In the case of hydrophobic chemicals, this
arrangement prevents re-crystallisation, increases solubility, and therefore bioavailability. A
number of research activities have been completed with regards to layered double hydroxides
as pesticides, growth regulators, plant nutrients, and slow-release fertilizer.2930 α- naphthalene
acetate, a plant growth regulator, has also been intercalated with nanoclays to explore storage
and controlled release of the plant growth regulator.31
The promise of layered double hydroxides lies in their acid neutralizing potential and high anion
absorption capacity. This may lead to increase in R&D in this area, due the recent push to limit
soil and water contamination by removing anionic compounds and pesticides (c.f. Directive
91/414/EEC).
For nano clays controlled release can be engineered through coating with different polymers,
which manipulates electrostatic interactions between the chemical load and the clay particles32.
In addition, nano clays can protect against UV-degradation of pesticides33.
Layered double hydroxides have high affinity for anionic species and are dissolved in acidic
conditions. A number of experimental studies have demonstrated their potential use in the
deployment of agrochemicals such as fertilisers34, plant growth promoters35, and pesticides36.




                                                8
Technology Readiness Level as an indicator of technology developmental stage
To give a quick reference indication of the status of the nanotechnology research and
development, we apply a five step Technology Readiness Level (TRL) system, developed by the
ObservatoryNANO partner VDI.

                  1        Basic research                               1

                  2        Applied research                             2          5

                  3        Prototype                                    6          7

                  4        Market entry                                 8

                  5        Mature markets                               9
    Figure 1: ObservatoryNANO TRL scheme corresponding to the US Department of Defence nine point scheme.



Application                           Basic         Applied                        Market         Mature
                 Technology                                        Prototype
  Area                              Research        Research                       entry          Market
Biocides        Nanodispersions
& nutrients
Biocides        Nanoemulsions
Fungicide       Microemulsions
& insecticide   nearing the
                nanoscale
Pesticide       Silica
                nanoparticles
Fungicide       Nano silica film
Controlled      Nanoclay
nutrient and
biocide
release


   Table 1 –Technology Readiness Level (TRL) assessment of Research and Development status for the
                                   technologies described above.




                                                     9
Current situation within the EU
Through our discussions with industrial experts, the general feeling is that industry is not
focussing on nano products because the enhanced properties that could be enabled by
nanotechnologies are much more easily achieved through the addition of tailor made adjuvants.
Currently most biocides are comprised of an “active” dissolved in a solvent. This approach
provides reasonable efficacy among most formulation types due to the molecular dispersed
active ingredient. The situation could turn in favour of nanotechnology enabled solutions if
regulation would prohibit the use of the current biocides used. In our interview,
nanosuspensions (including nanodispersions) may then emerge as a good candidate. Since
there is a relatively high cost in delivering these nanosuspensions, such developments are less
likely unless regulatory pressure (or other pressures) come into play.
The following FP7 projects funded by the European Commission are relevant to the broad theme
of nanotechnology for improved delivery of biocides and nutrients:
   •   InForm is a new €1.7 million FP7 project involving a diverse range of 17 research
       institutions which seeks to create platforms for exchange in the development of
       nanoformulations across six themes: (1) Formulation of nano-bio materials (2) Handling
       and processing of nanopowders (3) Process intensification and soft nanomaterials
       formulations (4) Physical chemistry at the nanoscale (5) The nanoscale and the
       formulation of smart and functional coatings, films and tapes (6) Toxicology and health
       effects of nanomaterials.     The partners have an interest in nanoformulation for
       agricultural applications and participated in the ObsservatoryNANO workshop on this
       topic.
       Partners: The University of Manchester (UK) (coordinator), Automaxion SARL (France),
       Bayer CropScience AG (Germany) Consejo Superior de Investigaciones Científicas
       (Spain), First Press Release: 30th July 2009 Page 1 of 2 Daren Laboratories (Israel),
       Dechema (Germany), Higgins Consultancy Ltd. (UK), Indian Institute of Technology
       Madras (India) Institute of Chemical and Engineering Sciences, A*STAR (Singapore),
       Novartis (UK), Royal Society of Chemistry – Formulation Science and Technology Group
       (UK), Societé Chimique de France (France), Southwest Forestry University (China),
       Strider Research Corporation (USA), University of Malaya (Malaysia), University of
       Sydney (Australia), YKI, Institute for Surface Chemistry (Sweden)


   •   PROFICIENCY is FP7 project carried by the Polish Institute of Soil Science and Plant
       Cultivation. The project aims to strengthen adopting a totally integrated interdisciplinary
       approach around four interdisciplinary priority research areas (Soil Quality; Land Use;
       Production Systems and Techniques; and Plant Products Quality and Safety) to converge
       towards excellence on a crucial topic: Managing the Production of Food and feedstuff,
       their safety and quality under global Climatic Change. This €3.14 million project started
       in December 2009 and will continue for 42 months.




                                               10
Economic aspects
General market description
The global agrochemical market size reached $119 billion in 2009 and was expected to continue
to grow in the next few years to reach nearly $200 billion in 2010.4 With respect to the main
segments of the agrochemical market, there is a higher share of fertilizers (approx. 57 %), which
are also expected to grow faster than pesticides. The expectations come from increasing use of
fertilizers in the past in order to improve soil fertility.

                                                                   Global agrochemical market

                                     200
                                              Pesticides
                                     180
                                              Fertilizers
                                     160
      Global market in billion USD




                                     140

                                     120

                                     100

                                      80

                                      60

                                      40

                                      20

                                       0
                                           2009             2010          2011          2012    2013   2014



    Figure 2: Global Agrochemical market. Source: Own calculations according to the estimations of BCC
                                            Research Report.
Asia is the largest market for agrochemicals (approx. 43 %) with leading position of India and
China. The consumption of agrochemicals in the U.S. is estimated at 18.5 % of the global
agrochemicals consumption. In Europe, the consumption of agrochemicals has been decreasing
over the last 10 years especially due to lower consumption in the EU-15 countries.5
From the production perspective, there are around 650 firms active in the production of
agrochemicals in Europe. A large part of them are based in France (approx. 18 %), Spain (14 %),
UK (10 %) and Germany (9 %).




4
 BCC Research Report 2009.
5
 For example by the largest users of fertilizers the consumption has decreased between 1997 and 2008 by 8 % in
Spain, 12 % in Germany, 23 % in France and 29 % in the UK.


                                                                                 11
                                                                                                    6
                  Figure 3: Number of enterprises in agrochemical industry in Europe in 2007
There are more than 500 nanotechnology patents in the area of agriculture. Not all are labelled
as such and few are below 100nm in scale. Notably almost 50% of the patents are held by
China, Korea, Russia and Japan.
In the area of sensor systems based on nanotechnology, solid state sensors and bioarray-based
are the most developed. These are, however, largely used in other application fields, such as
bioscience R&D, environmental monitoring, and internal combustion engine management
systems. There is substantial commercial activity in the search of better active ingredients,
especially with regard to human and environmental aspects.
Regarding activities on nano formulations it should be mentioned that BASF is the most prolific
(derived from patent analysis). For example BASF has been conducting basic research and has
applied for a patent on a pesticide formulation, “Nanoparticles Comprising a Crop Protection
Agent,” that involves an active ingredient whose ideal particle size is between 10 and 150 nm.
Bayer Crop Science has applied for a patent on agrochemicals in the form of an emulsion in
which the active ingredient is made up of nanoscale droplets in the range of 10-400 nm. Several
recent patents for nanotechnology enabled delivery systems that have application for pesticides
are held by Chinese institutions. The high patent activity in this field is to a certain extent


6
    Data for the Czech Republic, Ireland and Greece are from 2006. Source: Own graphics based on Eurostat data




                                                          12
connected with the aim of large companies to extend the lifespan of the previous patent on
original pesticides.
R&D in nano-based agrochemicals is concentrated within a small number of world’s leading
companies in agriscience sector. Since these companies already dominate the agrochemical and
seed market, further strengthening their market position and thus a consolidation of the
contemporary oligopoly market structure is expected (10 largest companies control around 80 %
of the market). The figure below shows the consolidation over the past 15 years of the major
players in the agriscience sector.




             Figure 4: Consolidation in the Agriscience Sector (source Phillips McDougall)


Slow release systems based on nano-clays are available from at least one company (based in the
EU), and have been trialled in desert regions37. A second company (based in the US)
manufactures drip flow herbicide systems, which potentially could be adapted for fertiliser
use38. The following section gives some product examples.

Economic drivers
Innovation in crop management is driven by the aim to boost the yield potential of seeds and
thus to increase the productivity per acre, to increase resistance of agricultural production
towards environmental stress and to better utilize the soil by crops with respect to its moisture
and nutrients. Nanotechnology applications in crop management have a potential to achieve all
these goals by increasing agrochemicals efficiency and their targeted impact without additional
environmental stress. Below are listed some of the particular driving forces for innovation in
agrochemical manufacture and application.




                                                  13
Regulation and Standardisation
As mentioned earlier in the report, in the EU there is a drive to limit the numbers of pesticides
available. Directive 91/414/EEC is the EU regulation covering the use of pesticides, and is
essentially risk-based. However, recent amendments could decrease the number of pesticides
available to farmers (15% of the 300 accepted chemicals have been estimated by the UK
government’s Pesticides Safety Directorate), which various agrifood industry associations are
concerned could affect yield and quality of produce39.This has major implications for the sector
and provides a driver for new solutions in the three desired functionalities mentioned in the
introduction: (1) increased efficacy; (2) controlled release; and (3) targeted delivery.

Rise in Energy Costs
Rise in energy prices in the future may be an economic driving factor for increased efficiency in
both the production and application of agrochemicals. Highly efficient nano-based
agrochemicals can significantly contribute to use of less fossil-fuel intensive agricultural inputs.

Climate Change
Globally, the climate change contributes to reducing quality of soil, growing variability of
weather (rainfall and temperature changes) and drying out of agricultural areas.7 These effects
of climate change stimulate innovation in crop management in order to use more effective and
targeted agrochemicals.
In Europe, one major effect could be on harvesting routines, where delayed harvesting often
leads to rotting crops. A further secondary effect of climate change40 is the variability in the
occurrence of crop pathogen and disease spread. A recent example being the UK potato harvest
of 2008 where the damp summer resulted in the highest occurrence of potato blight since the
Irish Potato Famine of the 1840's. This provides a driver for precision agriculture.

Clean water supplies amidst an increasing global population
Access to clean water is, and will continue to be, a global issue according to the WHO, which
estimates that 20% of the world’s population have inadequate access to clean drinking water
and that by 2025 the increased demand on water supplies will mean that each person will have
approximately 25% the volume that they would have had in 1960. Agriculture places
considerable demand on fresh water8 and in turn, contributes significantly to pollution of
groundwater through the use of pesticides and fertilisers. At present this is a political driver,
but as Food Futures 200941 this may become a real economic incentive and therefore a driver
for more effective, targeted and controlled use of agrochemicals.




7
    IAASTD: Agriculture at a Crossroads. Global Report, 2009.
8
    Globally, agriculture consumes up to 80 % of fresh water.


                                                           14
Economic barriers

Perception of the sector
The further development in this area is strongly dependent on the perception of
nanotechnologies in food and food contact materials by the public. Food companies are still
hesitant to incorporate nanomaterials for uncertainty of future regulations and standards and
for fear of negative consumer reactions.

Additional cost
Manufacturing nanoparticles for agrochemicals application can be time-consuming and
laborious. Producing stable low-viscosity dispersions the nanoparticle dispersions requires costly
raw materials which need to be reformulated, and due to the complicated molecules that need
to be developed, this requires additional R&D activities. 9



Selected company profiles active in the agrochemical industry


Name of the
                            Monsanto                Syngenta                 BASF            BayerCropScience
company
URL                      www.monsanto.com       www.syngenta.com         www.basf.com        www.bayercropscienc
                                                                                                   e.com

Revenue                    $11.365 billion        $11.620 billion       €62.300 billion         €5.600 billion
                               (2008)                 (2008)                (2008)                 (2009)

Number of                      21,700                 24,000                 97,000                 20,000
employees                      (2009)                 (2009)                 (2009)                 (2009)

Public funding                  N/A                     YES                   N/A                     N/A
received (Y/N)
If Y: Amount, Year              N/A              €3 million, 2009             N/A                     N/A

Description                 Agricultural           Agribusiness          Chemicals,             Innovative crop
                           biotechnology                                manufacturing,        science company,
                            corporation                                    energy            crop protection, non
                                                                                               agricultural pest-
                                                                                              control, seeds and
                                                                                             plant biotechnology



Monsanto is a global provider of agricultural products with major focus on enhancing farm
productivity and food quality. Monsanto actively collaborates with BASF in a long-term joint
R&D and commercialization programme in the development of high-yielding crops that are
more tolerant to adverse environmental conditions. The company holds a patent from 1994 that
grants a control over 100% of the world’s genetically engineered soybeans covering 36.5 million

9
  S. Schaer, G. Arnosti, S. Pilotek, F. Tabellion and H. Naef: Converting of Nanoparticles in Industrial Product
Formulations: Unfolding the Innovation Potential. Nanotech Vol. 2, 2005.


                                                      15
hectares in 2002 - that’s over half of the world’s total soybean area. According to Consulting
Resources Corporation (CRC), Monsanto has some involvement in nanotechnology in terms of
adequate activity but it is not likely to be an emerging leader in that area.
Syngenta, as the world's largest agrochemical corporation and third largest seed company,
contributes to the agribusiness sector by providing two main types of products; seeds and crop
protection. Syngenta Crop Protection, Inc. has patented plant-protecting active ingredient
mixtures improving the growth of plants and seeds. Syngenta sells pesticide products
formulated as emulsions containing nano-scale droplets but refers to these products as
microemulsion concentrates. In the United States, the Environmental Protection Agency (U.S.
EPA) does not consider Syngenta's nano-emulsions as nanomaterials or based onr
nanotechnology.
BASF is the world’s leading chemical company. Its portfolio covers chemicals, plastics and
performance products, agricultural products, fine chemicals and oil and gas. The BASF Crop
Protection division develops and produces active ingredients and formulations for the
improvement of crop quality and yields. In its programme “Smart Protection” is exploring and
developing environmentally friendly products and crop protection that meet the legally required
limits. BASF spends around 10 % (over €300 million) of its crop protection sales on research per
annum. In 2006-2008, the company also had a budget of €180 million for investment in
nanotechnology. BASF and Harvard University announced an agreement to establish the BASF
Advanced Research Initiative with a budget up to $20 million, focused on biofilm development
on various surfaces or interactions between bacteria and nanoscale materials and the
development of new nanoformulations having a function of controlled and targeted release of
active substance. BASF has applied for a patent on a pesticide formulation, “Nanoparticles
Comprising a Crop Protection Agent,” with active ingredient whose ideal particle size is 10-150
nm.

BayerCropScience is a subsidiary of Bayer AG and with annual sales of about $6.4 billion is one
of the world leading crop science companies covering the crop protection, non agricultural pest-
control, seeds and plant biotechnology sectors. The company plans to invest $750 million in the
development of new solutions in its seeds and traits10 business from 2008 to 2012. This new
intent is following on from existing collaboration between BayerCropScience and the Australian
Scientific and Industrial Research Organisation (CSIRO). The cooperation will broaden research
and development basis of BayerCropScience’s seeds and also promises novel trait solutions for
seed business. Patents on agrochemicals, in the form of emulsions in which the active ingredient
is made up of nanoscale droplets (size 10-400 nm), have been assigned to BayerCropScience.
The company refers to the invention as a ”microemulsion concentrate” with advantages such as
reduced application rate, a more rapid and reliable activity, and extended long-term activity.




10
  R&D in “traits” means the investigation (and understanding of) the biological mechanisms in
seeds and plants that lead to specific observable traits – for exploitation in optimizing plant
breeds.

                                              16
Selected Products
Nanotechnology is still in its early stage within agrochemical industry compared to for example
biotechnology. However, the lower cost of some production equipment, research and
development based on nanotechnology is sought to allow for more industrial diversity and
equality. In response to the developing trend of nanotechnology applications in agriculture
sector, potential nanomaterial risks associated with its use must be transparent among
governments, industry and science at global level (FAO and WHO, 2009).
Providing information on existing and emerging applications of nanotechnologies in
agrochemicals, as well as any associated potential risks on basis of statements developed from
secondary sources, is a non trivial task. There are some records of the first nano agrochemicals
in development, which are nano-reformulations of existing pesticides, fungicides, plant, soil and
seed treatments (FOE, 2008). Pakistan-US Science and Technology Cooperative Programme is
focused on development of combined fertiliser and pesticide in terms of nanoclay capsule
containing growth stimulants and biocontrol agents. The new type of product is designed for
slow release of active ingredients and therefore the crop treatment requires only one
application over its life cycle. Another nano agrochemical in development is herbicide
formulated by Tamil Nadu Agricultural University in India and Technologico de Monterry in
Mexico. This type of a new product will attack the seed coating of weeds, destroy soil seed
banks, and prevent weed germination. Australian Commonwealth Scientific and Industrial
Research Organization intends to bring in commercial use pesticides and herbicides with nano-
encapsulated active ingredients. Very small size of nanocapsules increases their potency and
may enable targeted release of active ingredients.
Agrochemical companies are reducing the existing chemical emulsions to the nanoscale and
substituting active ingredients with their encapsulated nanosized equivalents in attempt to bring
a number of benefits into potential applications of nanotechnology to pesticides, and other
agrochemicals such as fertilizers and plant growth regulators. Employing nanomaterials in this
industrial and research area could reduce use of certain agrochemicals such as pesticides, and
further provide a better ability to control the application and dosage of active substance to the
target. All aspects of possible toxicity of nanomaterials and their health and environmental
impact are currently not being entirely explored. The further development of this risk area will
be strongly dependent on changed behaviour of these materials parallel to their nano-size, safe
and responsible handling of these materials by consumers and the extent of consumer exposure
to nanomaterials.
With the reference to the U.S. EPA statement, several manufacturers have been interested in
releasing nanoscale pesticides (FOE, 2008). Nevertheless, almost no major agrochemical
companies, except Syngenta, have announced that they are manufacturing products, which
contain nanomaterials having a diameter less than 100nm. Syngenta has been selling its Primo
MAXX® for several years. Primo MAXX® is by far the most widely used plant growth regulator
(PGR) by golf course superintendents and other professional turf managers since its introduction
in 1993. It is marketed as a “micro-emulsion” concentrate. Turf quality and stress tolerance will
increase with multiple applications. KARATE®, insecticide is a water-based, quick release
microencapsulated formulation which targets damaging chewing and sucking insects on a wide
range of crops (it is registered on more than 100 crops including cotton, maize, cereals and
vegetables)42. The active ingredient is Lambda-cyhalothrin rapidly penetrates the insect
cuticle,disrupting nerve conduction within minutes. Additional brands include ICON®,
DEMAND®, COMMODORE®, WARRIOR®43, and KUNG FU®. Syngenta’s Banner MAXX ™ is a


                                               17
systemic fungicide that provides effective broad-spectrum disease control in turf and
ornamentals. It is marketed as a microemulsion concentrate formulation providing excellent
tank mix compatibility and stability. Banner MAXX enters through the surface stem or root
system and prevents fungal cell growth by inhibiting sterol biosynthesis. 44 Subdue MAXX™ is a
systemic fungicide, which offers control of Pythium and Phytophthera blight. It is marketed as
microemulsion concentrate formulation providing excellent tank mix compatibility, less
equipment wear, and stability. ApronMaxx® RFC (Rhizobia Friendly Concentrate) is a
combination of the active ingredients in Apron® XL and Maxim® 4FS seed treatment fungicides
and blue colorant. ApronMaxx® RFC offers the widest range of disease protection available for
soybeans in a concentrated rhizobia-friendly formulation that is safe to nitrogen-fixing bacteria
applied to the seed. ApronMaxx RFC offers a lower application volume than ApronMaxx RTA and
is designed for on-site treating with combinations of Cruiser® seed treatment insecticide and
liquid inoculants. ApronMaxx RFC helps protect crop investments by improving plant stands and
vigour, therefore enabling soybean growers to avoid replanting costs and maximize yield
potential. The first commercial insecticide/fungicide seed treatment combination on the market
for soybeans, CruiserMaxx® Beans protects seeds and seedlings against a wide range of yield-
threatening insects and diseases to help increase stand and vigour, promoting earlier canopy
closure and improving yields.45
Geohumus®, a product of Geohumus International is a soil enhancer with water storage capacity
based on nanotechnology, which can be also used as a mineral repository in agriculture. It has a
larger water storage capacity than previous wetting agents and a product lifetime of 3 – 5 years.
geohumus® is a high-efficiency polymer that consists of a water storing hybrid material, volcanic
rock flour and plant available colloidal silicate. It can store large amounts of rain and drinking
water at the root remaining available to the plants over a prolonged period without evaporating
or seeping away. Only 100g of geohumus® is necessary for a surface of 1m².46 The nutritional
elements can be set flexibly and can continually deliver a stable and long-term supply of
nutrients to the plant. The silicate contained in granulate additionally strengthens the plant and
thus geohumus® offers more yield certainty, crop quality, and more profitable plant production.




                       Figure 5: Geohumus® water saving and swelling capacity

Sequoia Pacific Research Company is a manufacturer of soil binder SoilSet, which uses organic
biodegradable ingredients to create a nano-structured matrix as a soil binder, similar to natural
plant and crop residues. SoilSET works through chemical reactions at the molecular level by
combining a nano-structured solution to elements that naturally exist in soil. Once the SoilSET
concentrate has been mixed with either fresh or brackish water, an electro-chemical reaction

                                                18
creates a new organic binder at the nano particle level, which agglomerates soil particles from
one-half to three-fourths inches into the surface. SoilSET-treated soil increases soil moisture
retention, reduces water and wind erosion, and aids rapid seed germination and growth. SoilSET
was first field tested in 2002 on a California burn area from the Trough Fire in Mendocino
National Forest. According to an official report from the U.S. Forest Service after application,
SoilSET can prevent erosion on moderate to steep slopes, withstand high summer temperatures
and solar radiation, and does not dissipate with the first fall rains. SoilSET is also designed to
prevent fibre clumping and increase application spread rate and pumping ability.47 Agro
Nanotechnology Corporation have developed a pre-planting treatment, Nano-Gro™, for seeds
and bulbs to the market; Nano-Gro™ is a plant growth regulator and immunity enhancer. The
active ingredients in Nano-Gro™ come packaged in coded sugar pellets less than ⅛" in diameter.
Just one pellet is capable of treating 42 kg of wheat seeds or 33 tomato plants. When Nano-
Gro™ is delivered to the plants or a seed dissolved in water, the plant perceives that as a stress
factor. Agro Nanotechnology Corporation claims that the heightened immunological response
allows the plant to fight disease and extreme moisture prevent infections or other
environmental calamities.
There are also some other promising technologies including Monsanto’s Roundup Ready®,
which are herbicide tolerant technologies in soybeans and corn. Roundup agricultural herbicides
have been on the market for 30 years and have been the most widely used herbicide in corn,
soybeans and cotton for over eight years. The Roundup herbicide, which is used extensively with
Roundup Ready genetically modified crops, is manufactured and already offered by Monsanto in
a number of microencapsulated pesticides. In 1998 Monsanto entered an agreement with
Flamel Nanotechnologies to develop “Agsome” nanocapsules of Roundup, which might have
been more chemically efficient than the conventional formula (DOTFarm, 2004). They employed
nanotechnology to modify the properties of the outer shell of a capsule in order to control the
rate of release and way of delivery to specific surface; however, Monsanto’s activities to bring
these nano-formulations in agribusiness to market, in cooperation with Flamel, has been
discontinued. Bioluminescence Spray introduced under the label of BioMark is a product of
AgroMicron, Ltd and enables to detect various pathogens such as common Salmonella and E-
Coli in food and water. Nanoengineered luminescent protein emits a visible glow when adhered
on the surface of microorganisms. This works in a similar fashion to an immune system antibody,
designed to lock on to a particular feature on the "coat" of the microbe. In this case the higher
the number of connections between bacteria and molecules, the more intense the glow
produced. BioMark is being sold throughout the food industry and can be widely used in ocean
freight containerized shipping of perishable goods. BASF CLEARFIELD® production system to
African maize growers is worth a mention. StrigAway® is a unique production system that
combines herbicide tolerant CLEARFIELD® maize seeds with an innovative herbicide seed
treatment. The maize seed is coated with a low dose of the herbicide StrigAway® to provide
effective protection against Striga. This seed-coating technology significantly improves maize
and increases per capita wealth by securing the yield and constant supply of locally grown food.
To ensure widespread use, BASF, together with its public research partners, plans to provide
local seed companies with the know-how to produce seeds protected by the StrigAway®
technology, preserving local production autonomy.




                                               19
Acknowledgements
We would like to thank the following experts for contributing to the project and this report:11
Dave Duncalf                     IOTA Nanosolutions
Malcolm A Faers                  Bayer CropScience
Kathy Groves                     Leatherhead Foods International
Steve Hankin                     Institute of Occupational Medicine
Paul Leonard                     BASF SE
Pat Mulqueen                     Syngenta
Roy Pemberton                    University of the West of England
Brajesh Singh                    Macaulay Land Use Research Institute
Alan Smith                       AZ Technology
Peter Spencer-Phillips           University of the West of England
Ibtisam E. Tothill               Cranfield University
Peter Whitehouse                 IOTA Nanosolutions
Wolfgang Wirth                   Bayer CropScience




11
  Contributions were made through input into our dedicated ObservatoryNANO workshop, our
nanotechnology conference session at the British Crop Production Congress 2009, through
telephone interviews and direct comments and input into earlier versions of this report.



                                                20
References
1
  FAO (2008), Crop Prospects and Food Situation, No. 2, April 2008, FAO Global Cereal Supply and Demand
Indicators, http://www.fao.org/docrep/010/ai465e/ai465305.htm.
2
 Von Braun, J. (2008), The World Food Situation: New Driving Forces and Required Actions, Food Policy
Report, International Food Policy Research Institute, p. 5.
3
 LEAD/FAO     (2006),    Livestock’s   Long    Shadow:    Environmental     Issues            and     Options,
http://www.virtualcentre.org/en/library/key_pub/longshad/ A0701E00.pdf, p. 16.
4
 Grieve B. (2009) Affordable Sensors: Changing the Rules of the Game for Future Farming. Syngenta
University Innovation Centres. February 2009. www.windmill.co.uk
5
 from GRUB S UP (Recycling and upgrading wastes from food production for use within the food chain).
FP6-funded                                   project                                http://www.ist-
world.org/ProjectDetails.aspx?ProjectId=6e1a2be91dcc4543bab4f0af1a13416f&SourceDatabaseId=7cff92
26e582440894200b751bab883f
6
  Communication from the Commission—Towards a European strategy for nanotechnology, 2004.
Luxembourg: Office for Official Publications of the
European Communities 2004, pp. 24 ISBN 92-894-7686-9
7
 Commission Recommendation of 07/02/2008 on a code of conduct for responsible nanosciences and
nanotechnologies       research,     European       Commission     (February      2008)      -
http://ec.europa.eu/nanotechnology/pdf/eu_nano_policy_2004-08.pdf
8
  KRUGER, E. L., SOMASUNDARAM, L., KANWAR, R. S. & COATS, J. R. (1993) PERSISTENCE AND
DEGRADATION OF [C-14] ATRAZINE AND [C-14] DEISOPROPYLATRAZINE AS AFFECTED BY SOIL DEPTH AND
MOISTURE CONDITIONS. Environmental Toxicology and Chemistry, 12, 1959-1967.
9
  MOGUL, M. G., AKIN, H., HASIRCI, N., TRANTOLO, D. J., GRESSER, J. D. & WISE, D. L. (1996) Controlled
release of biologically active agents for purposes of agricultural crop management. Resources
Conservation and Recycling, 16, 289-320.
10
     Pesticide regulations could threaten cereal yields (Food Navigator, 12.08.08)
11
  Meleson K, Graves S and Mason T G 2004 Formation of concentrated nanoemulsions by extreme shear
Soft Mater. 2 109
12
   ANTON, N., BENOIT, J. P. & SAULNIER, P. (2008) Design and production of nanoparticles formulated
from nano-emulsion templates - A review. Journal of Controlled Release, 128, 185-199.
13
   Wang L. Li Z. Zhang G, Dong J. and Eastoe J. (2007) Oil-in-water nanoemulsions for pesticide
formulations. Journal of Colloid and Interface Science 314 (2007) 230–235
14
   Wang L. Li Z. Zhang G, Dong J. and Eastoe J. (2007) Oil-in-water nanoemulsions for pesticide
formulations. Journal of Colloid and Interface Science 314 (2007) 230–235
15
   LAI, F., WISSING, S. A., MULLER, R. H. & FADDA, A. M. (2006a) Artemisia arborescens L essential oil-
loaded solid lipid nanoparticles for potential agricultural application: Preparation and characterization.
Aaps Pharmscitech, 7.
16
  pSivida manufactures BioSilicon for drug delivery purpose in a number of medical conditions:
www.psivida.com
17
  LIU, F., WEN, L. X., LI, Z. Z., YU, W., SUN, H. Y. & CHEN, J. F. (2006) Porous hollow silica nanoparticles as
controlled delivery system for water-soluble pesticide. Materials Research Bulletin, 41, 2268-2275.


                                                       21
18
  LI, Z. Z., XU, S. A., WEN, L. X., LIU, F., LIU, A. Q., WANG, Q., SUN, H. Y., YU, W. & CHEN, J. F. (2006b)
Controlled release of avermectin from porous hollow silica nanoparticles: Influence of shell thickness on
loading efficiency, UV-shielding property and release. Journal of Controlled Release, 111, 81-88.
19
     NanoPool http://www.nanopool.eu/english/news.htm
20
  Liu Y, Laks P, Heiden P: Controlled release of biocides in solid wood. I. Efficacy against brown rot wood
decay fungus (Gloeophyllum trabeum). J Appl Polym Sci 2002, 86:596-607.
21
   Liu Y, Laks P, Heiden P: Controlled release of biocides in solid wood. II. Efficacy against Trametes
versicolor and Gloeophyllum trabeum wood decay fungi. J Appl Polym Sci 2002, 86:608-614.
22
  Liu Y, Laks P, Heiden P: Controlled release of biocides in solid wood. III. Preparation and characterization
of surfactantfree nanoparticles. J Appl Polym Sci 2002, 86:615-621.
23
   Taylor NJ, Fauquet CM: Microparticle bombardment as a tool in plant science and agricultural
biotechnology. DNA Cell Biol 2002, 21:963-977.
24
  Torney F, Trewyn BG, Lin VS-Y, Wang K: Mesoporous silica nanoparticles deliver DNA and chemicals into
plants. Nature Nanotech 2007, 2:295-300.
25
   González-Melendi P, Fernández-Pacheco R, Coronado MJ, Corredor E, Testillano PS, Risueño MC,
Marquina C, Ibarra MR, Rubiales D, Pérez-de-Luque A: Nanoparticles as smart treatment delivery systems
in plants: assessment of different techniques of microscopy for their visualisation in plant tissues. Ann
Bot-London 2008, 101:187-195.
26
   Corredor E, Testillano PS, Coronado MJ, González-Melendi P, Fernández-Pacheco R, Marquina C,
Ibarra MR, de la Fuente JM, Rubiales D, Pérez-de-Luque A, Risueño MC (2009) Nanoparticle penetration
and transport in living pumpkin plants: in situ subcellular identification. BMC Plant Biology 2009, 9:45
27
  Zhang H, Wang D, Butler R, Campbell NL, Long J, Tan B, Duncalf DJ, Foster AJ, Hopkinson A, Taylor D,
Angus D, Cooper AI, Rannard SP (2008) Formation and enhanced biocidal activity of water-dispersable
organic nanoparticles. Nature Nanotechnology 3, 506–511 (1 August 2008)
28
  CHOY, J. H., CHOI, S. J., OH, J. M. & PARK, T. (2007) Clay minerals and layered double hydroxides for
novel biological applications. Applied Clay Science, 36, 122-132.
29
  Olanrewaju, J., Newalkar, B.L., Mancino, C., Komarneni, S., 2000. Simplified synthesis of nitrate form of
layered double hydroxide. Mater. Lett. 45, 307–310.
30
  Lakraimi, M., Legrouri, A., Barroug, A., De Roy, A., Besse, J.P., 2000. Preparation of a new stable hybrid
material by chloride-2,4- dichlorophenoxyacetate ion exchange into the zinc–aluminium– chloride layered
double hydroxide. J. Mater. Chem. 10, 1007–1011
31
    bin Hussein, M.Z., Zainal, Z., Yahaya, A.H., Foo, D.W.V., 2002. Controlled release of a plant growth
regulator, alpha-naphthaleneacetate from the lamella of Zn–Al-layered double hydroxide nanocomposite.
J. Control. Release 82, 417–427.
32
  LEE, W.F. & FU, Y.T. (2003) Effect of montmorillonite on the swelling behavior and drug-release
behavior of nanocomposite hydrogels. Journal of Applied Polymer Science, 89, 3652–3660.
33
   EL-NAHHAL, Y., NIR, S., MARGULIES, L. & RUBIN, B. (1999) Reduction of photodegradation and
volatilization of herbicides in organo-clay formulations. Applied Clay Science, 14, 105-119.
34
   OLANREWAJU, J., NEWALKAR, B. L., MANCINO, C. & KOMARNENI, S. (2000) Simplified synthesis of
nitrate form of layered double hydroxide. Materials Letters, 45, 307-310.
35
  BIN HUSSEIN, M.Z., ZAINAL, Z., YAHAYA, A.H. & FOO, D.W. (2002) Controlled release of a plant growth
regulator, alpha-naphthaleneacetate from the lamella of Zn–Al-layered double hydroxide nanocomposite.
Journal of Controlled Release, 82, 417-427.


                                                     22
36
   LAKRAIMI, M., LEGROURI, A., BARROUG A., DE ROY A. & BESSE, J.P. (2000) Preparation of a new stable
hybrid material by chloride-2,4-dichlorophenoxyacetate ion exchange into the zinc–aluminium–chloride
layered double hydroxide. Journal of Materials Chemistry, 10, 1007-1011.
37
   Geohumus is a patent-pending nanoparticulate that is super-adsorbent, and has undergone field-trials
in desert areas (http://www.geohumus.com/).
38
     Drip flow herbicides using nanoclay particles (http://www.geoflow.com/)
39
     Pesticide regulations could threaten cereal yields (Food Navigator, 12.08.08)
40
  Grieve B. (2009) Affordable Sensors: Changing the Rules of the Game for Future Farming. Syngenta
University Innovation Centres. February 2009. www.windmill.co.uk
41
  Ambler-Edwards S., Bailey K., Kiff A., Lang T., Lee R., Marsden T, Simons D., Tibbs H. (2009) Food
Futures-Rethinking UK Strategy. A Chatham House Report
42
     http://www.syngenta.com/en/products_brands/karate_page.html
43
 http://www.syngentacropprotection.com/prodrender/index.aspx?prodid=1052&ProdNM=Warrior%20II
%20with%20Zeon%20Technology
44
 http://www.syngentaprofessionalproducts.com/prodrender/index.aspx?ProdID=740&ProdNM=Banner
%20MAXX
45
     http://www.syngentacropprotection.com/Seed_Treatment/default.aspx
46
     http://www.geohumus.com/download/geohumus_flyer_eng.pdf
47
     http://www.sequoiaprc.com/faqs.asp




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