4° Workshop “AgriNanoTechniques”

Nanomaterials for products and

application in agriculture

Nanofertilizers for sustainable crop management

Luca Marchiol
Agriculture environmental pressure (percentage of impact)

0 50 100 150 200

2010
GHG emissions
2050
Staple crops
2010
Legumes
Bluewater use
2050 Nuts and seeds

Fruits and Vegetables

2010
Vegetable oil
N fertilizers
2050 Sugar

Other crops
2010
P fertilizers Animal products
2050

modified from: Springmann et al. 2018. Nature 562, 519–525

 Conventional N-, P- Fertilizers
CO2 CO2 N2 Corn kernel
CH4
N content = 46%
P content = 52%
Energy CH4
Haber-Bosch Urea
Nutrient Use Efficiency
N2O, NH3
N content = 46% Agriculture
AESynthesis= 35% P content = 52% product

CO2 CO2

Energy P rocks
MAP
Atom Conversion Efficiency
Nutrient
loss
AESynthesis= 35% Eutrophication
Urea = 0.35 x 0.50 x 0.46 = 0.08 → 8%
Emissions
to land Atom Economy MAP = 0.35 x 0.25 x 0.52 = 0.05 → 5%
modified from Urso and Gilberston. 2018. ACS Sustainable Chem. Eng. 6, 4, 4453–4463
NANOTECHNOLOGY
 Conventional Agriculture Nano-enabled Agriculture
New varieties
Enhance √
Agrochemicals
Sense
Irrigation
Mechanization Deliver √
N2 fixation

Efficient
Sustainable
Environmental
impact
Yield

1920 2000 2080

modified from: Lowry et al., 2019. Nature Nanotechnol 14, 6, 541–553
 Nanofertilizers_Expectations

Nutrient loading capacity →

Nutrient release rate →
Nutrient use efficiency →
Crop quality and productivity →
Economic feasibility →
Environmental compatibility →
 Nanofertilizers_Soil application
Engineered Nanomaterials (ENMs) properties

Shape

Composition

Surface runoff Size

Plant uptake
Attachement
Degradation
ENMs
Aggregation
Aggregation
Dissolution
Chemical Straining
transformations
Mn+
Charge

Movement to subsurface or groundwater

Corona

Usman et al. 2020. Sci Tot Environ 721, 137778

Nanofertilizers_Foliar application
Xylem
Bundle sheath

Leaf hair

Chloroplasts

Cuticle

Upper epidermis

Palisade mesophyll

Vascular
Spongy mesophyll bundle

Lower epidermis

Cuticle
Air space
Stomata
Phloem
Guard cells
Types of Nanofertilizers

Composition Macronutrient Micronutrient Nanomaterial Plant growth

Structure nanofertilizer nanofertilizer enhanced fertilizer stimulator
Cu, Fe, Mn
Metallic
Mo, Zn
Nutrient loaded zeolites
Ceramic Ca, Mg, Ca-P nCeO2, nTiO2
Mesoporous nSiO2
SWCNTs, MWCNTs,
Polymeric N, K Nano-chitosan fertilizer Graphene, Fullerenes,
C containing NPK
O O
C C
N NH2
H

modified from: Marchiol et al. 2020. Advances in Agronomy 161, 27-116

 Macronutrient Nanofertilizer
Urea-Hydroxyapatite Nanohybrids for Slow Release of Nitrogen

8
Urea
0.8 7.5

Cumulative N (g)

Yield (t ha-1)
0.6 6.5
Urea-HA nanohybrid
6
0.4
5.5

0.2 5

4.5
0
0 1000 2000 3000 4000 No U U-HA
Ca10(PO4)6(OH)2 Time (seconds) Fertilization (100 kg N ha-1) (50 kg N ha-1)

O
N release behavior in water Field trial - Oryza sativa
C
2HN NH2

Kottegoda et al. 2017. ACS Nano, 11, 1214−1221.

Micronutrient Nanofertilizer
50 7
Control Control
Foliar Foliar

Effects of nZnO 40
Soil 6 Soil

Biomass (g plant-1)
Flowers (n plant-1)
5
on tomato growth 30
4

20 3

2
10
1

0 0
0 10 100 250 500 750 1000 0 10 100 250 500 750 1000
nZnO (mg kg-1) nZnO (mg kg-1)
250 200
Control Control
Foliar Foliar
Soil Soil
Soil Foliar
Phloem

200

Lycopene (g plant-1)
Fruit yield (g plant-1)
Xylem

150
application application
150
100

100

50
50

0 0
0 100 500 1000 0 100 500 1000

Raliya et al. 2015. Metallomics 7, 1584-1594 nZnO (mg kg-1) nZnO (mg kg-1)
Nanomaterial enhanced fertilizers
Mesoporous silica nanoparticles - MSNs
enhance seedling growth and photosynthesis
in wheat and lupin
● MSNs uptake/accumulation in different plant fractions
● MSNs stimulated photosynthesis and plant growth
(mg L-1)
0 200 500 1000 2000 0 200 500 1000 2000

plant uptake

50 nm 10 nm

Sun et al. 2018. Chemosphere 152, 81-91

Plant Growth Stimulator a
4 7 ns

Graphene Oxide (GO) 3

6

Dry mass (g pot-1)

new carrier for slow release of

Dry mass (g pot-1)

b
4
plant micronutrients 2
c 3

2
Cu-GO
1 or Zn-GO
1

0 0
45 35 ns
a
40
Release in soil 30
35

Zn uptake (µg pot-1)

Cu uptake (µg pot-1)

Zn or Cu 30
25

25 20

20 b 15
15
10
10 c

5 5

0 0
Ctrl Zn-GO ZnSO4 Ctrl Cu-GO CuSO4

Kabiri et al. 2017. ACS Appl. Mater. Interfaces 9, 49, 43325-43335 Pot trial - Triticum durum
Nanofertilizers_Research needs Other key drivers

Social acceptance?

Environmental
footprint?

Scalability?

Economic viability?

Kah et al. 2018. Nat Nanotechnol. 13, 8, 677–684

Take-home messages

● Nanofertilizers have a very interesting potentially but very limited published performance
data at the field scale, so far. More field studies needed.

● Most of current studies report on the properties of laboratory nanoformulations and not
necessarily commercial products;

● Needed implementation of Safe-by-Design for nanomaterial development and safe

innovation. Environmental implications!

● EFSA Journal 2018, 16, 5327: Guidance on risk assessment of the application of
nanoscience and nanotechnologies in the food and feed chain: Part 1, human and animal
health. Expected part 2, Agriculture?
Readings

1. Ramírez-Rodríguez et al. 2020. Reducing nitrogen dosage in Triticum durum plants with
Urea-doped nanofertilizers. Nanomaterials 10, 1043. doi.org/10.3390/nano10061043

2. Gilbertson et al. 2020. Guiding the design space for nanotechnology to advance
sustainable crop production. Nat. Nanotechnol. doi.org/10.1038/s41565-020-0706-5

3. Gomez et al. 2021. Effects of nano-enabled agricultural strategies on food quality:

Current knowledge and future research needs. J. Hazardous Materials. 401,123385.
doi.org/10.1016/j.jhazmat.2020.123385
 4° Workshop AgriNanoTechniques
Nanomaterials for products and
application in agriculture

Nanofertilizers for sustainable crop management

[email protected]