Copper nanoparticles and compounds impact
agronomic and physiological parameters in
cilantro (Coriandrum sativum)
Nubia Zuverza, PhD Student
The University of Texas at El Paso
Dr. Gardea-Torresdey’s Research Group
March, 2015
•19th largest city in the US
•Ranked as the safest large
city in the US during the
last three years
(Annual City Crime Rankings by CQ press)
2
Copper nanoparticles and compounds impact agronomic and
physiological parameters in cilantro (Coriandrum sativum)
Outline
• Introduction
• Materials
– Cilantro
– Copper products
• Procedure
– Soil treatment
– Plant growth and harvest
– Sample preparation and analysis
• Results
–
–
Agronomic parameters
Nutritional value (physiological parameters)
• Summary
http://www.renaissanceherbs.com.au/system/0000
/0167/08_31_52_944_coriander_Medium_.jpg
3
Introduction
Fate of nanoparticles in the environment
Holden, P.A; Nisbet, R.M.; Lenihan, H.S.; Miller, R.J.; Cherr, G.N.; Schimel, J.P.; Gardea-Torresdey, J.L.
Accounts Chem. Res. 2013, 46, 813-822.
4
Introduction
Use of nanomaterials in agricultural activities
Nanotechnology
Extraction/Production
Nanosensors
Wastes
NPs
Nanoremediation
Nano-pestcides
Nano-herbicides
Contamination
Soil
N K
P
Groundwater
Hong, J., Peralta-Videa, J.R., Gardea-Torresdey, J.L. 2013. Nanomaterials in agricultural production: benefits and
possible threats? In: Sustainable Nanotechnology and the Environment: Advances and Achievements. Edited by
Sharma, V. and Shamin, A.N., ACS Symposium Series Vol. 1124, 73-90 (DOI:10.1021/bk-2013-1124).
Introduction
ENMs and Plants
A
B
Fe3O4 NP(44,45)
ZnO NP(42,43)
CeO2NP(42,50,51)
?
Root hair
Zn2+
Cu2+
Cortex
?
?
?
?CeO2 NP
MWCNT(29,30,35,36)
?
?
Metaxylem
Phloem
Cambium
Protoxylem
? C70 fullerenes
?Fe3O4 NP
Al NP(55)
Al3+
?
AgNP(52,53)
Ag 2+
?
?
?C70 fullerenes
?
SWCNT(27,28,34)
Pericycle
Fe3O4 NP
Al3+
?Al NP
Ag 2+
?Ag NP
?
Endodermis
? Ni(OH)2 NP
C70 fullerenes(21,40)
?
Epidermis
? ZnO NP
? CeO2 NP
? Cu NP
Zn2+
?
Cu2+
CuNP(17)
TiO2 NP(24,41)
?
Ni(OH)2 NP(22) C60(OH)20 fullerols(21)
?
? Fe3O4 NP(44,45)
?
CeO2NP(42,50,51)
Al NP(55) ?
?
? TiO 2 NP(24,41)
Cu NP(17)
?
? ZnO NP(42,43)
NP(52,53)
?
? SWCNT(27,28,34)
Ni(OH)2NP(22)
C70 fullerenes(21,40) ? ?
Ag
?
?
Studies with varied conclusions (indicative of species dependency)
Uptaken and translocated
?
? Uptake/translocation not confirmed (varied conclusions)
?
?
MWCNT(29,30,36) ?
?
?
?
Uptake by roots; but translocation not studied/ not confirmed due to
very few studies on the NP
Rico, C. M.; Majumdar, S.; Duarte-Gardea, M.; Peralta-Videa, J. R.; Gardea-Torresdey, J. L. Interaction of nanoparticles
with edible plants and their possible implications in the food chain. J. Agric. Food Chem. 2011, 59, 3485-3498.
6
Introduction
7
Introduction
Nanotechnology
in agriculture
Nanopesticide
“GRAND
ENTRY TO
THE
FOODCHAIN”
Nanofertilizers
Nano Bio Marketing 2011. http://nanobiomarketing.com/en/ contents/view/knowledge/101
8
Introduction
Gardea-Torresdey, J. L.; Rico, C. M.; White, J.C. Trophic Transfer, Transformation, and Impact of Engineered Nanomaterials in
Terrestrial. Environ. Sci. Technol.2014, 48, 2526-2540.
9
Materials- copper
Copper NPs and compounds
• Cu(OH)2 CuPRO 2005
– 53.8% copper hydroxide
• Cu(OH)2 Kocide 3000
– 46.1% copper hydroxide
•
•
•
•
Cu NPs, 40nm
Cu bulk, <60 μm
CuO NPs, <50nm
CuO bulk, <5μm
• CuCl2
10
Materials - cilantro
http://www.grubstreet
.com/2012/01/foreign
_cinemas_gayle_pirie_
lo.html
Cilantro
http://clatl.com/omnivore/arc
hives/2010/04/16/cilantro-itsnot-just-for-food-snobs
http://pixgood.com/rabbiteating-lettuce.html
• Coriandrum sativum
http://www.roadfood.com/Forums/What-ISa-taco-m145993.aspx
http://cocinaycomparte.com/recetas/sopade-albondigas-con-arroz-y-cilantro
– (cilantro)
•
•
•
•
Cu into food chain – spices
Herb, culinary spice
Eaten fresh
Antioxidant properties
http://jessfuel.com/wpcontent/uploads/2013/04/RoastedTomatilloSal
saVerde13.jpg
https://kathleeniscookinginmexico.files.word
press.com/2010/03/chipotle-fish-soup-3.jpg
http://ajillofalltrades.blogsp
ot.com/2011/09/best-salsarecipe.html
11
Procedure - soil treatments
Cilantro exposed to copper soil
Suspension
preparation
Cu Concentration in soil:
0 ppm (control)
20 ppm
80 ppm
Suspension
sonication
Soil + Cu
12
Procedure – plant growth & tissue harvest
30 days growth
Harvest
Tissue
washing
Measurement
13
Procedure – sample prep. and analysis
Sample analysis
Microwave oven
Sample weight = 100 mg
Sample digestion
Samples dried at 70 °C
ICP-OES analysis
14
Agronomic results
Cu Effects on Coriander Roots Elongation
16
14
Elongation (cm)
12
10
8
20 ppm
6
80 ppm
4
2
0
CNTRL Cupro Kocide
nCu
µCu
Cu treatment
nCuO
µCuO
CuCl2
Paper in preparation
15
Agronomic results
Cu Effects on Cilantro Shoot Elongation
9
8
Elongation (cm)
7
6
5
4
20 ppm
80 ppm
3
2
1
0
CNTRL
Cupro
Kocide
nCu
µCu
nCuO
µCuO
CuCl2
Cu treatment
Paper in preparation
16
Results
Cu Effects on Cilantro Chlorophyll
45
40
35
SPAD
30
25
20 ppm Cu
20
80 ppm Cu
15
10
5
0
CNTRL
CuPRO
Kocide
nCu
µCu
nCuO
µCuO
CuCl2
Cu Treatment
Paper in preparation
17
Physiological results
Copper concentration in cilantro shoots
Paper in preparation
18
Physiological results
20ppm Cu effects in cilantro shoots
nutritional value
B Zn Mn Ca P
CuPRO
+ + Kocide
- nCu
+ + µCu
nCuO
+
µCuO
- CuCl2
+ + -
S Mg
+
+
-
Paper in preparation
19
Physiological results
80ppm Cu effects in cilantro shoots
nutritional value
B Zn Mn Ca P
CuPRO
+ + Kocide
- nCu
+
µCu
+ - nCuO
+
µCuO
+
- CuCl2
+
-
S Mg
-
-
-
-
Paper in preparation
20
Summary
CuPRO
20
80
Nutrients
Shoot
length
Chlorophyll
content
Mg

P

S
Ca

B
Mn
Zn
Kocide
20
80
nCu
20












80
80
nCuO
20
80
µCuO
20
80



















µCu
20


CuCl2
20
80














• Agronomic parameters in cilantro were mostly affected by 80 ppm nCu and
both 20 and 80 ppm bulk CuO
• Chlorophyll content was increased by 80ppm CuPRO and nCu; decreased by
both concentrations of bulk CuO
• Nutritional value was affected by all copper compounds
Paper in preparation
21
Acknowledgements
 CEIN NSF-EPA # EF0830117.
 USDA-UPRM grant # 2008-38422-19138.
 National Science Foundation (NSF) CHE-0840525.
 Dudley Family for Endowed Chair.
 LERR and STAR Grants of the University of Texas System.
 NIH BBRC 2G12MD007592
 Science and Technology Mexican National Council (CONACyT)
22
Gardea-Torresdey”s Research Group (Fall 2014)
http://www.ssslogic.com/gardea
23
In Memory
Prof. William “Bill” Glaze
ES&T Editor-in-Chief
1988-2002
“A Mentor, and a Friend”
Passed away December 17, 2014
“A 21st century pioneer in environmental
science and technology.”
24
Questions?
SNO 2014 student awardees
25
Physiological results
Cu Effects on Cilantro Roots Elongation
16
14
12
Elongation (cm)
10
8
20 ppm
80 ppm
6
4
2
0
CNTRL
Cupro
Kocide
nCu
µCu
nCuO
µCuO
CuCl2
Cu treatment
Paper in preparation
27
Agronomical results
Copper uptake by cilantro roots
Paper in preparation
28
Agronomical results
Copper concentration in soil
Paper in preparation
29
Agronomical results
Nutrients concentration in cilantro roots exposed to 20ppm copper compounds
*
**
*
*
***
Paper in preparation
30
Agronomical results
Nutrient concentrations in cilantro roots exposed to 20ppm copper compounds
* *
*
*
* *
* *
** *
** *
*** *
Paper in preparation
31
Agronomical results
Nutrients concentration in cilantro roots exposed to 80ppm copper compounds
**
***
*
***
Paper in preparation
32
Agronomical results
Nutrient concentrations in cilantro roots exposed to 80ppm copper compounds
Paper in preparation
33
Physiological results
20ppm Cu effects in cilantro shoots nutrients
400
60
50
40
B
30
Mn
20
Zn
10
*
0
*
Cntrl CuPRO Kocide nCu
*
*
*
Concentration (mg/kg)
Concentration (mg/kg)
70
350
300
250
Fe
200
Ni
150
Al
100
Si
50
0
Cntrl CuPRO Kocide nCu
µCu nCuO µCuO CuCl2
Concentration (mg/kg)
Mg
P
S
Ca
Cntrl CuPROKocide nCu
µCu nCuO µCuO CuCl2
Cu treatment
nCuO µCuO CuCl2
Cu treatment
Cu treatment
18000
16000
14000
12000
10000
8000
6000
4000
2000
0
µCu
CuPRO
Kocide
nCu
µCu
nCuO
µCuO
CuCl2
Increases Decreases
Mn, Ca
P
S
Ca, Mg, P
Mn, Ca
S, P
Zn, Mg, P
B
S, Mg, P
S
Ca, Mg, P
Mn, Ca
P
Paper in preparation
35
Physiological results
300
30
250
Concentration (mg/kg)
35
25
20
B
15
Ni
10
Zn
5
Al
0
200
150
Mn
100
Fe
Si
50
0
Cntrl CuPRO Kocide nCu
µCu nCuO µCuO CuCl2
Cntrl CuPROKocide nCu
Cu treatment
Concentration (mg/kg)
Concentration (mg/kg)
80ppm Cu effects in cilantro shoots nutrients
Cu treatment
18000
16000
14000
12000
10000
8000
6000
4000
2000
0
Mg
P
S
Ca
Cntrl CuPRO Kocide nCu
µCu nCuO µCuO CuCl2
µCu nCuO µCuO CuCl2
Cu treatment
CuPRO
Kocide
nCu
µCu
nCuO
µCuO
CuCl2
Increases
Mn, Ca
B
B
B
Mn
Decreases
P
Mg, Ca, P
Zn, Ca, P
Mg, S, P
Zn, Mg, Ca, P
Mg, S, P
Paper in preparation
36