Transcript 7NCC`Veso`Green`methods`11

Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Development of methods for
trace element determination
in accordance with
GREEN chemistry principles
V. Kmetov, V. Stefanova, K. Simitchiev, D. Georgieva
Department of Analytical Chemistry and Computer Chemistry,
University of Plovdiv, Bulgaria
N.Kovachev, A. Canals
Department of Analytical Chemistry and Food Science,
University of Alicante, Spain
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
MW
SPE
CPE
ASDI
MNPs
Prevention
GAMA
Atom Economy
Green Analytical Methods Academic Centre
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Green
A nalytical
M ethods
A cademic Centre
http://gama.argon.uni-plovdiv.bg/
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
DO 02-70
UA
National Science Found of Bulgaria
INTIGRATED RESEARCH CENTRES AT THE
UNIVERSITIES
UNIVERSITY CENTRE FOR DEVELOPMENT OF
GREEN CHEMISTRY METHODS FOR TRACE
ANALYSIS OF ENVIRONMENTAL OBJECTS
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
MW
SPE
CPE
ASDI
MNPs
Microwave-assisted solid phase extraction
of Pd and Pt for their ICP-MS determination
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
• sample in 1 M HCl
flow rate 3 ml min-1
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
adsorption stage
ICP-MS
• thioureido propyl
functionalized silica gel
0.12 g packed
microcolumn
• 1 ml eluent 0.5%
thiourea flow rate
0.5 mL min-1
Reduce
Derivatives
MW 800W
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
desorption (elution) stage
Sample preparation system: DMO – domestic microwave oven, WCC – water cooling circuit, MC –
microcolumn, PP – peristaltic pump, S/W – sample or water,
E/W – eluent or water, SMR – separated matrix recipient, ELR – eluate recipient
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
MW
SPE
CPE
ASDI
MNPs
Microwave-assisted solid phase extraction
of Pd and Pt for their ICP-MS determination
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
MW
SPE
CPE
ASDI
MNPs
Microwave-assisted solid phase extraction
of Pd and Pt for their ICP-MS determination
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
MW
SPE
CPE
ASDI
Microwave-assisted solid phase extraction
of Pd and Pt for their ICP-MS determination
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
MNPs
• For the first time MW is applied for elution process of Pd and Pt in
environmental and biological samples
• Low eluent volumes and concentrations are used
• The developed method is robust, cheap and environmentally friendly
Seventh National Conference
on Chemistry
International Conference on
MW
Green Technologies and
Environmental Protection
Prevention
SPE
CPE
ASDI
MNPs
Microwave- assisted Cloud Point Extraction
Atom Economy
Heating
above CP
Less Hazardous
Chemical
sedimentation
Water phase
separation
Dissolution of the
surfactant-rich
phase
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
Sample solution
metal ion ( )
complexes Inclusion (
into the micelles
)
Surfactant-rich
phase
SRP – diluted to 2.5 g
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
MW
SPE
CPE
ASDI
MNPs
Microwave- assisted Cloud Point Extraction
Atom Economy
Less Hazardous
Chemical
Model
solutions
Urban dust
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
Pt, Pd, Rh
2-mercaptobenzo
thiazole,
N,N’diphenylthiourea
ammonium O,O’diethyldithio
phosphate
ICP-MS
ICP-OES
Laprilen,
Tritace,
Vivace
Enalapril
Pt, Pd, Rh
Pt, Pd, Rh
2-mercapto
benzo
thiazole,
ICP-MS
ICP-OES
2-mercapto
benzo
thiazole,
ICP-MS
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
MW
SPE
CPE
ASDI
MNPs
Microwave- assisted Cloud Point Extraction
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
• For the first time CPE is performed with a MW
• It incorporates non-hazardous surfactant
• It uses a high efficiency MW energy source that reduces 8 times the incubation
time
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
MW
SPE
CPE
ASDI
MNPs
Microwave- assisted Cloud Point Extraction
and Air Segmented Discreet Introduction FAAS
Prevention
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Figure 1. Effect of water phase pH on the analyte recovery. Conditions: 2% TX-100; 500:1 molar APDC
excess; hot plate incubation for 45 min at 80 0C.
Vitamins
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
Zn, Cu, Pb
and Cd
APDC
ASDI FAAS
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Atom Economy
Less Hazardous
Chemical
Vitamins
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
SPE
CPE
ASDI
MNPs
Microwave- assisted Cloud Point Extraction
and Air Segmented Discreet Introduction FAAS
Prevention
Designing Safer
Chemicals
MW
Zn, Cu, Pb
and Cd
APDC
ASDI FAAS
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
MW
SPE
CPE
ASDI
MNPs
Microwave- assisted Cloud Point Extraction
and Air Segmented Discreet Introduction FAAS
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
MW
SPE
CPE
ASDI
MNPs
Air Segmented Discreet Introduction FAAS
determination of Zn in blood serum
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
• Sample volumes
from 0.15 – 1 ml
(frozen serum )
Energy
Efficiency
• Dilution factors from
2 - 11
Renewable
Feedstocks
• Sample injections
from 2- 6 s
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
MW
SPE
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Real-time
analysis
Accident
Prevention
ASDI
MNPs
Air Segmented Discreet Introduction FAAS
determination of Zn in blood serum
Atom Economy
Design for
Degradation
CPE
• Low sample consumption
• Low dilution factors and methodological LOQ
• Higher sample throughput and measurement automation
Seventh National Conference
on Chemistry
International Conference on
MW
Green Technologies and
Environmental Protection
Prevention
SPE
CPE
ASDI
MNPs
Solid Phase Extraction by Magnetic Nanoparticles
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Magnet
2% APDC
Safer Solvents
Model
solution
Energy
Efficiency
continuously
mixing
5 min
contact
Phase
separation
Dissolution of MNPs
HNO3 0.5 ml
5 mol l-1 on water bath
15 min.
MNPs
Renewable
Feedstocks
Reduce
Derivatives
(Fe3O4 and
MnFe2O4),
0.01 g
E%
ICP-MS Agilent 7700
Catalysis
R%
Design for
Degradation
Real-time
analysis
Accident
Prevention
5min for
MnFe2O4
and 10 min
for Fe3O4
ICP-OES Optima 4200 Perkin Elmer
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
MW
SPE
CPE
ASDI
MNPs
Solid Phase Extraction by Magnetic Nanoparticles
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
Prevention
MW
SPE
CPE
ASDI
Solid Phase Extraction by Magnetic Nanoparticles
Atom Economy
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
MNPs
• Method effective for a group separation/preconcentration
• Simple synthesis of MNPs
• Small amount of sorbent phase and good compatibility with ICP-MS
Seventh National Conference
on Chemistry
International Conference on
Green Technologies and
Environmental Protection
MW
SPE
CPE
ASDI
MNPs
Prevention
Atom Economy
Acknowledgement to
GAMA project DO 02-70, financed by NSF of Bulgaria
Less Hazardous
Chemical
Designing Safer
Chemicals
Safer Solvents
Energy
Efficiency
Renewable
Feedstocks
Reduce
Derivatives
Catalysis
Design for
Degradation
Real-time
analysis
Accident
Prevention
Thanks
for your
attention !