Seventh National Conference on Chemistry International Conference on Green Technologies and Environmental Protection Development of methods for trace element

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


Green Technologies and Environmental Protection

Atom Economy

Less Hazardous Chemical

Designing Safer Chemicals

Energy Efficiency

Renewable Feedstocks

Prevention

Reduce Derivatives

Catalysis

Design for Degradation

Real-time analysis

Safer Solvents

Accident Prevention



G A M A DO 02-70

Green Analytical Methods Academic Centre

GGGreen AAAnalytical MMMethods AAAcademic Centre

http://gama.argon.uni-plovdiv.bg/

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

PUAU

SUUFT

UA

MW SPE CPE ASDI MNPs

Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention



Microwave-assisted solid phase extraction of Pd and Pt for their ICP-MS determination


Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention

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

adsorption stage

desorption (elution) stage

• sample in 1 M HClflow rate 3 ml min-1

• thioureido propyl functionalized silica gel 0.12 g packed microcolumn

• 1 ml eluent 0.5% thiourea flow rate 0.5 mL min-1

MW 800W

ICP-MS





Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention





Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention





•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

Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention



Microwave- assisted Cloud Point Extraction


Dissolution of the surfactant-rich

phaseHeating

above CPWater phase separation

sedimentation

Surfactant-rich phase

complexes Inclusion ( ) into the micelles

Sample solution metal ion ( )

Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention

SRP – diluted to 2.5 g





Model solutions

Pt, Pd, Rh

2‑mercaptobenzothiazole,

N,N’-diphenylthiourea

ammonium O,O’-

diethyldithiophosphate

ICP-MS

ICP-OES

Laprilen, Tritace, Vivace Enalapril

Pt, Pd, Rh

2‑mercaptobenzo

thiazole,

ICP-MS

Urban dust

Pt, Pd, Rh

2‑mercaptobenzo

thiazole,

ICP-MS

ICP-OES

Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

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

Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention



Microwave- assisted Cloud Point Extraction and Air Segmented Discreet Introduction FAAS


Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention

Vitamins

Zn, Cu, Pb and Cd

APDC

ASDI FAAS

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.





Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention

Vitamins

Zn, Cu, Pb and Cd

APDC

ASDI FAAS





Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention



Air Segmented Discreet Introduction FAAS determination of Zn in blood serum


Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention

• Sample volumes from 0.15 – 1 ml (frozen serum )

• Dilution factors from 2 - 11

• Sample injections from 2- 6 s



Air Segmented Discreet Introduction FAAS determination of Zn in blood serum


Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention

•Low sample consumption

•Low dilution factors and methodological LOQ

•Higher sample throughput and measurement automation




Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention

Magnet

Model solution

5 min contact

Phase separation

Dissolution of MNPs HNO3 0.5 ml 5 mol l-1 on water bath 15 min.

MNPs

(Fe3O4 and MnFe2O4),

0.01 g

2% APDC

E%

R%

continuously mixing

ICP-MS Agilent 7700

ICP-OES Optima 4200 Perkin Elmer

Solid Phase Extraction by Magnetic Nanoparticles

5min for MnFe2O4

and 10 min for Fe3O4





Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention





•Method effective for a group separation/preconcentration

•Simple synthesis of MNPs

•Small amount of sorbent phase and good compatibility with ICP-MS

Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention




Atom Economy



Energy Efficiency


Prevention

Reduce Derivatives

Catalysis


Real-time analysis

Safer Solvents

Accident Prevention

Acknowledgement to GAMA project DO 02-70, financed by NSF of Bulgaria

Thanks for your

attention !

Documents

Seventh National Conference on Chemistry International Conference on Green Technologies and Environmental Protection Development of methods for trace element