Download - Atomic Spectroscopy Basics (2012)
![Page 2: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/2.jpg)
INTRODUCTION
ספקטרוסקופיה בליעה
Absorption Spectroscopy:
AAS
ספקטרוסקופיה פליטה
Emission Spectroscopy:
FES, ICP-AES(OES)
ספקטרוסקופיה מסה
Mass Spectrometry
![Page 3: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/3.jpg)
E – energy difference between two levels;
h – Plank’s constant, 6.626068 × 10-34 m2kg/s;
c – speed of light, 299 792 458 m/s;
λ – wavelenght, nm
Ion Emission
Atom Emission
INTRODUCTION
![Page 4: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/4.jpg)
Nebulizer converts the
solution into a spray
Flame (or Plasma) causes the solvent to evaporate,
leaving dry aerosol particles, then volatilizes the particles,
producing atomic, molecular and ionic species
INTRODUCTION
![Page 5: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/5.jpg)
SAMPLE PREPARATION
Drying
Grinding
Dry or Wet Acid
Digestion
Process Goal Problems
Sample stabilization,
homogenization and
accurate weighing
facilitation
Sample homogenization,
organic matter reduction
facilitation
Organic matter destruction,
solid material dissolution
Thermal
decomposition and
reduction in dry
weight
Pollution by metals
from the mill parts
Analyte loss,
contamination, not
complete solid
dissolution
![Page 6: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/6.jpg)
SAMPLE PREPARATION EQUIPMENT
Most samples have to be prepared for analysis on ICP, FF and AA. Solid samples are
solubilized. Organic matter is "mineralized" i.e. converted to inorganic compounds.
Hot Plate
Microwave-assisted Digestion
Digestion Block
![Page 7: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/7.jpg)
SAMPLE PREPARATION EQUIPMENT
Microwave Laboratory Oven “Ethos One”
and Teflon vessels
![Page 8: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/8.jpg)
SAMPLE PREPARATION EQUIPMENT
“Ethos One”: Temperature and Pressure control
![Page 9: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/9.jpg)
SAMPLE PREPARATION EQUIPMENT
“Ethos One”: “Vent-and-Reseal” technology
![Page 10: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/10.jpg)
SAMPLE PREPARATION EQUIPMENT
“Ethos One”: Digestion profile
6 samples
0
50
100
150
200
250
0.00 0.05 0.10 0.15 0.20 0.25
Time (minutes)
Te
mp
era
ture
(°C
)
0
200
400
600
800
1000
1200
Po
we
r (w
att)
![Page 11: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/11.jpg)
Cd, 1 mg/L, in weak acid
Cd, 1 mg/L, in base
11
MATRIX
Analyte concentrations are equal, but intensities are different
![Page 12: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/12.jpg)
MATRIX
The elements that are stable/soluble in HNO3
![Page 13: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/13.jpg)
MATRIX
The elements that are stable/soluble in HCl
![Page 14: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/14.jpg)
MATRIX
The elements that are stable/soluble in H2SO4
![Page 15: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/15.jpg)
MATRIX
HNO3
HCl
H2SO4
![Page 16: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/16.jpg)
QC PROCEDURES
Replicates – method precision * evaluation.
Spike – addition of the known concentration of
analyte to the sample at the preparation step. The
evaluation of the preparation quality and matrix effect.
Matrix matching – preparation of the calibration
standards in the same matrix as the samples.
Standard Reference Material preparation and
analysis for method accuracy ** evaluation.
*Precision is how close the measured values are to each other.
**Accuracy is how close a measured value is to the actual (true) value.
Internal standard – addition of the element that
sample does not contain (Y, Sc) in known
concentration. The evaluation of the matrix effect.
![Page 17: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/17.jpg)
QC PROCEDURES
SRM 1570a Spinach Leaves Elemental Analysis
Method precision Method accuracy
![Page 18: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/18.jpg)
FLAME EMISSION SPECTROSCOPY (FES)
Propane-butane flame ( 2000 – 3000 º C);
Optical filter is used to monitor for the selected emission wavelength
produced by the analyte;
Suitable for elements with low excitation energy (Na, K, Li, Rb, Cs and Ca).
![Page 19: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/19.jpg)
FLAME EMISSION SPECTROSCOPY (FES)
Flame
Optic Filter
Nebulizer
Data Display
Flame Photometer M-410
(Sherwood Scientific, UK)
![Page 20: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/20.jpg)
FLAME EMISSION SPECTROSCOPY (FES)
![Page 21: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/21.jpg)
FLAME EMISSION SPECTROSCOPY (FES)
![Page 22: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/22.jpg)
ATOMIC ABSORPTION SPECTROSCOPY (AAS)
Gases mixture flame (1800 – 4500 º C): air-propane, air-acetylene etc. ;
Atomic absorption spectrometry quantifies the absorption of ground state atoms in the
gaseous state ;
The atoms absorb ultraviolet or visible light and make transitions to higher electronic
energy levels . The analyte concentration is determined from the amount of absorption.
![Page 23: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/23.jpg)
ATOMIC ABSORPTION SPECTROSCOPY (AAS)
Operation principle of AAS
Light source – hollow cathode lamp. Each element has its own unique lamp.
Atomic cell – flame (gas mixture) or graphite furnace (accepts solutions, slurries, or even
solids).
Detector – photomultiplier.
![Page 24: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/24.jpg)
ATOMIC ABSORPTION SPECTROSCOPY (AAS)
![Page 25: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/25.jpg)
ICP-AES
Inductively Coupled Plasma -
Atomic Emission Spectrometry
ATOMIC EMISSION SPECTROSCOPY
![Page 26: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/26.jpg)
ICP-AES
Basics
Atomic emission spectroscopy measures the intensity of
light emitted by atoms or ions of the elements of interest at
specific wavelengths;
Inductively Coupled Plasma spectrometers use emission
spectroscopy to detect and quantify elements in a sample;
ICP-AES uses the argon plasma (6000-10000º C) for
atomization and excitation of the sample atoms;
ICP-AES determines approximately all of the elements
except gases and some non-metals (C, N, F, O, H).
![Page 27: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/27.jpg)
ICP-AES SPECTROMETER ARCOS
![Page 28: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/28.jpg)
Schematic diagram of the processes in the ICP
![Page 29: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/29.jpg)
ICP SPECTROMETER
Main Systems
![Page 30: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/30.jpg)
ICP-AES: SAMPLE INTRODUCTION SYSTEM
Nebulizer (cross-flow)
Spray Chamber
Argon Supply
To Waste
Torch with Plasma
Sample
Solution
Entrance
![Page 31: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/31.jpg)
ICP-AES: NEBULIZER
Cross-flow nebulizer Modified-Lichte nebulizer
Burgener nebulizer
![Page 32: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/32.jpg)
ICP-AES: NEBULIZER
aerosol
![Page 33: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/33.jpg)
ICP-AES: NEBULIZER
Modified Lichte Nebulizer
aerosol
![Page 34: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/34.jpg)
ICP-AES: NEBULIZER
aerosol
![Page 35: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/35.jpg)
ICP-AES: TORCH
Auxiliary
Argon Flow
Coolant
Argon Flow
Nebulizer
Argon Flow
![Page 36: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/36.jpg)
ICP-AES: TORCH
![Page 37: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/37.jpg)
Inductively Coupled Plasma Source
A plasma is a hot, partially ionized
gas. It contains relatively high
concentrations of ions and electrons.
Argon ions, once formed in a plasma, are
capable of absorbing sufficient power from
an external source to maintain the
temperature at a level at which further
ionization sustains the plasma indefinitely.
The plasma temperature is about 10 000 K.
ICP-AES: PLASMA
![Page 38: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/38.jpg)
Inductively Coupled Plasma Source
ICP-AES: PLASMA
![Page 39: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/39.jpg)
ICP-AES: RADIAL (SOP) AND AXIAL (EOP)
![Page 40: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/40.jpg)
ICP-AES: RADIAL (SOP) AND AXIAL (EOP)
SOP: Side-on-Plasma EOP: End-on-Plasma
more suitable for hard matrices (concentrated samples);
alkali metals (Na, K, Li) calibration is more linear;
less spectral interferences;
lower sensitivity (Limit-of-Detection is higher);
more suitable for light matrices;
alkali metals (Na, K, Li) calibration is less linear;
more spectral interferences;
higher sensitivity (Limit-of-Detection is lower);
![Page 41: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/41.jpg)
ICP-AES: OPTICS
![Page 42: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/42.jpg)
ICP-AES: OPTICS
![Page 43: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/43.jpg)
ICP-AES: BACKGROUND CORRECTION
Background Correction
Position 1
Background Correction
Position 2
Linear Function Approximation
![Page 44: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/44.jpg)
ICP-AES: BACKGROUND CORRECTION
Linear Function
Approximation
Polynomial Function
Approximation
![Page 45: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/45.jpg)
ICP-AES: SPECTRAL INTERFERENCES
Sulfur in plant sample Boron in plant sample
Sulfur in standard
(10 mg/L)
Boron in plant sample
Boron in standard
(1 mg/L)
Sulfur spectral interference on Boron line 182.6 nm
![Page 46: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/46.jpg)
ICP-AES: SPECTRAL INTERFERENCES
Iron spectral
interference on
Boron lines 249.7
and 208.8 nm
Fe 25 ppm
B 0.1 ppm
Fe 25 ppm
![Page 47: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/47.jpg)
ICP-AES: SPECTRAL INTERFERENCES
Mn 10 ppm
Au 1 ppm
Manganese spectral interference on Gold lines 242.7 mn
Numerical Data
![Page 48: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/48.jpg)
ICP-AES: CALIBRATION CURVE
![Page 49: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/49.jpg)
ICP-MS: BASICS
Cones sample the center
portion of the ion beam
(+)
(+) (+) (+)
Electrostatic lens
focuses the beam
into the slit
Shadow stop blocks
the photons
![Page 50: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/50.jpg)
ICP-MS: BASICS
Quadropole mass filter can
separate up to 2400 amu (atomic
mass units) per second by switching
alternating voltages applied to
opposite pairs of the rod
![Page 51: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/51.jpg)
ICP-MS: BASICS
![Page 52: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/52.jpg)
ICP-MS: BASICS
![Page 53: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/53.jpg)
ICP-MS: BASICS
![Page 54: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/54.jpg)
ICP-AES (MS), FES AND AAS: APPLICATION
Clinical Analysis: metals in biological fluids (blood, urine);
Environmental Analysis: trace metals and other elements in waters, soils, plants,
composts and sludges;
Pharmaceuticals: traces of catalysts used; traces of poison metals (Cd, Pb etc);
Industry: trace metal analysis in raw materials; noble metals determination.
Forensic science: gunshot powder residue analysis, toxicological examination
( e.g., thallium (Tl) determination)
![Page 55: Atomic Spectroscopy Basics (2012)](https://reader033.vdocuments.site/reader033/viewer/2022042700/558635d8d8b42a962c8b45ad/html5/thumbnails/55.jpg)
ZBM LABORATORY WEBSITE
http://departments.agri.huji.ac.il/zabam/