Atomic spectroscopy

How to choose the right

technique for your
application
AA, MP-AES, ICP-OES, ICP-MS…

Gregory LECORNET
Atomic spectroscopy
product specialist
Analysis

Measure the concentration of elements in samples

LSAG EMEAI FY15
Agilent Restricted
Page 2
 Atomic Spectroscopy Strategy - Markets

Chemical &
Food & Materials Science
Environmental Energy Pharmaceuticals
Agriculture

• Drinking and natural • Heavy metals

• Feed and fertilizer • Mining and Metals • Petroleum refining
water (USP<232>/<233>)

• Toys and Consumer • Alternative Energy • Incoming raw material

• Soil and sediment • Nutrient elements
Products (Biodiesel) testing

• Waste • Some trace toxic

• Some semicon etc • Fine and Bulk Chemicals • QA/QC of Final Product
(solids/liquids/gases) element apps

3
Goal of new instruments
Agilent’s philosophy has always been lowest running costs
with highest performance… and it still is!

Highest performance Lowest running costs

• Best detection limits • Fastest sample throughput

• Best Stability • Lowest gas consumption per sample
• High matrix tolerance • High matrix tolerance
• Best tools for interference correction • Best tools for interference correction

4
The Agilent Atomic Spectroscopy Portfolio
FAAS + GFAAS MP-AES ICP-AES ICP-MS ICP-QQQ

Agilent’s 55 and 200 Agilent’s 4200 Agilent’s 5100

Agilent’s 7800 Agilent’s 8800
Series

• Covering all classic techniques of atomic spectroscopy

• Unique technologies on the market : MP-AES and ICP-QQQ
2 essential questions to determine what elemental
instrumental technique is needed
How many samples
Detection limits?
or elements?
Many Samples or many Low Detection Limits
elements (sub ppb, ppt)
• ICP-OES, ICP-MS, MP-AES • ICP-MS, GFAAS

Few samples or few High DL’s (>1ppb)

elements • ICP-ES, MP-AES, FAAS
• FAAS, GFAAS
Additional Clarifying Questions
Sample Current
Budget?
Types? Usage?
MP-AES, FAAS*
Capital budget? up to 3% TDS Regulated
methods?
ICP-OES up to
Operating 25% TDS
budget? GFAAS greater
than 10% What techniques
Overall does the chemist
ICP-MS has HMI know?
Requirements? and can dilute
Performances

Flame AA Mono-element
technique

Furnace AA

MP-AES

ICP-AES

ICP-MS

ppb Working range %

Total cost
Purchasing cost + operating cost (10 years)

Acetylene + nitrous
Flame AA
oxide + lamps

Furnace AA Argon + lamps

MP-AES

ICP-AES Argon

ICP-MS Argon

Total cost
Atomic absorption

Flame

• 4/8 lamp capacity with automatic lamp selection

• Built-in D2 background corrector

• Dedicated model with Fast Sequential operation

• Option to add the GTA120 graphite furnace

Fast Sequential + SIPS
• Measures ALL elements in rapid sequence

• Samples aspirated once

•Saves labor and reduces running costs

SIPS

• Eliminates tedious standard preparation

• Calibrate the AA using just 1 standard

• Provides fast, on-line dilution of over range

samples
•Eliminates manual dilution & re-analysis of samples
 Fast Sequential Operation

Conventional AA

Fast Sequential AA

Fast Sequential AA reduces the analysis time by over 55 %, so you can save
money, and run more samples. Precision remains exceptional at < 0.4 % RSD.
Introducing the NEW Agilent 4200 MP-AES
The 4200 is second generation technology with proven
performance.
The 4200 has an expanded application range with still the
lowest running costs for entry level spectroscopy.

Confidentiality Label
13 October 15, 2015
 Microwave Plasma Emission Overview

Ground State Excited State Emission

Monochromator Quantitation
& Detector

Nitrogen Microwave excited

Plasma Plasma

Sample

Page 14
Optical Diagram
• Monochromator Czerny-Turner
Detector
• Holographic grating: 2400 t/mm
• Focal length: 60 cm
• Resolution <0.05 nm Pre-optics

Monochromator

CCD Detector
Cassette style Torch
• Peltier cooled CCD
• 532 x 128 pixels (pixels are 24 x 24 µm)
• Background correction simultaneously with peak measurement
• Greater than 90% Quantum Efficiency
• Wide dynamic range
 Instrumentation

Typical configuration

Nitrogen Generator Agilent 4200 MP-AES SPS3

Detection limits
Ease of Use

Simple software
• Applet quick start methods
• Auto optimisation tools
• FLIC and IEC tools
The Agilent 4200 MP-AES is the ideal FAAS replacement.

Improved Reduced Increased Ease of Use

Performance Running safety • MP Expert
• Increased working Costs • No acetylene • Simple sample
range • Runs on Air • No nitrous prep
• Lower detection with Nitrogen oxide • No burner
limits Generator change over
• Reduced • Reduced
interferences reagent costs
Waste waters
Waste waters
Determination of major and minor elements in
geological samples

The range of concentrations in geochemical analysis varies

from major elements that are present at percent levels, to trace
elements that are present at sub ppm levels.
Flame Atomic Absorption Spectrometry (FAAS) has long been
the instrument of choice for geochemical analysis but with
current trends in the market for lower detection limits, lower
cost of analysis, improved ease of use and improved safety, the
Agilent 4200 MP-AES is the ideal replacement for FAAS.
Sample preparation

Two CRMs prepared

• GBM398-4 Low grade Cu/Pb/Zn with Laterite
• GBM908-14 Cu-Zn-Pb Sulphide Ore
Acid digestion
• HNO3-HCl-HClO4-HF four-acid digestion
Sample dilution
• 0.4 g nominal sample weight brought to 100 mL final volume with 30% HCl
Calibration standards
• All calibration standards in 6% HNO3 and 19% HCl
- No modifiers or ionization buffers required
- No further sample dilutions required
Results and discussion
Table 4. MP-AES and certified CRM results
Reference MDL GBM398-4 GBM908-14

MP-AES Certified Recovery (%) MP-AES Certified Recovery (%)

Ag (mg/kg) 1 45.8 48.7 94 289.7 304.7 98
Cu (wt %) 0.002 0.37 0.39 95 2.30 2.37 97
Ni (wt %) 0.002 0.39 0.41 97 - Not reported -
Pb (wt %) 0.002 1.08 1.17 92 3.24 3.30 98
Zn (wt %) 0.002 0.50 0.51 98 4.24 4.27 99

All results are shown as results in the original sample.

Results demonstrate the ability of the 4200 MP-AES to:
• Measure Ag at low concentrations, with interferences corrected by IECs
• Achieve excellent recoveries across a wide concentration range (0.39% to
2.37% for Cu, and 0.51% to 4.27% for Zn)
• Determine all elements in a single sample preparation
 4200 MP AES Application Examples
Major elements in foods, beverages and agricultural samples |
Nutrients in soils
Metals & Cations in agricultural soil samples
Analysis of fertilizers.

Geochem samples in aqua regia digests Food &

Trace elements in geological samples Agriculture

Trace level gold in cyanide leach

Analysis of high purity gold
Platinum group elements in ore grade material
Various elements in plating solutions. Environmental
4200 MP AES Application Examples

Hg, Pb, Cd and Cr in electronics and plastics (for

WEEE/RoHs compliance
Analysis of waste waters, sediments and soils Materials
Science
Analysis of plant waste products.

Additives in lubricating oils

Wear metal contaminants in used oils
Analysis of petroleum, diesel and biodiesel fuel
Major elements in polymers Chemical &
Energy
Analysis of raw chemicals for contaminant levels.
Introducing the Agilent 5100 ICP-OES SVDV

• Highest throughput with highest performance

• Dichroic Spectral Combiner (DSC) technology enables

axial and radial measurements at the same time.
 • Lowest Cost of Ownership
24 Years of Agilent ICP-OES Innovation • Enhanced Performance
• Simple Operation
Agilent 5100 ICP-OES

Introducing increased
throughput via SVS2
Worlds fastest 710/720/730
simultaneous ICP-
OES. Patented CCD
Vista PRO & MPX
Axial and Radial models
available. Vacuum and
gas purge optics.

Liberty Series II
#1 selling ICP-OES.
High resolution radial
sequential ICP-AES
Vista Chip CCD detector 2014
Liberty
2006
1998-2000
1995
High QE PMT detector.

1991
First innovation
Horizontal torch and axial/radial
Vertical torch and radial view view

+ - + -
No EIE effect
Bad DL Best DL with axial Radial window gets
High robustness view dirty

We have made the combination

of all advantages

Vertical torch and

axial/radial view
Best DL with axial view
No EIE effect with radial view
High robustness
Longer lifetime of torches
Key benefit : Enhanced performance

Result of 30% NaCl (Brine)

30 % NaCl No salt deposition even after 3 h
ppb
Al 2
Ba 15
Ca 79
Cd <1
Co <1
Cr 2
Cu 2
Fe 17
Mg 5
Ni 11
Pb 11
Si 31
Sr 14
Zn 16 • Complex Matrix
• Longer Torch Life
Second innovation
• Patented DSC technology for ICP-OES provides DV without
compromise.

• Single reading of the plasma for both radial and axial.

Mirror

Hole
DSC

5100 SVDV Mode Selector

What is the DSC and how it works?
DSC : Dichroic Spectral Combiner
- Glass with metallic coating
- This coating offers optic properties

Mirror
165 nm 785 nm

Reflexion < λ c at 420 nm < Transmission

Hole
DSC
SVDV

Light from axial

view

Reflexion
λ < 420 nm Light from Transmission
Radial view λ > 420 nm
To optics To optics

Transmission λ > 420 nm Reflexion λ < 420 nm

Light from axial view

Light from radial

view Reflexion λ < 420 nm

To optics

Transmission λ > 420 nm 34

5100 : the fastest ICP

Optics with 1 slit

DSC (167 – 785 nm)

Fastest Vertical
CCD torch
5100

FASTEST ICP of the market

Cost of ownership - example

Cost of ICP 1 Cost of 10 years of argon consumption

Cost of of 10 years of argon

Cost of ICP 2
consumption

Cost of of 10 years of argon

Cost of 5100
consumption

Total cost

At the end, the 5100 is the most economic option!

Agilent’s Fitted Background Correction
Easily handles complex background structure
Pb 220 with FITTED background Pb 220 with FITTED background
correction – 1000 ppm Mo correction – 2000 ppm Al
Agilent Patented FACT Correction

Fast Automated Curve-fitting Technique (FACT) for accurate removal of

spectral interferences
• Peak modeling approach - Uses spectral data from analyte and interference
standards to de-convolve the analyte peak from nearby interference peaks

Advantages

• Resolves extremely complex

spectral interferences

• Gives access to extra wavelengths

for improved validation

• Allows resolution of interferences

as close as 3 pm
Introduction
Monitoring of biodiesel samples for metal contaminants
often involves analyzing many samples per day via ICP-
OES.

Laboratories are constantly trying to improve productivity

and reduce operating costs while achieving the required
detection limits and measurement accuracy.

Metal ASTM D6751 EN 14214 – 2012

mg/kg mg/kg
Group I metals: Na & K 5 (combined) 5 (combined)
Group II metals: Ca & 5 (combined) 5 (combined)
Mg
Phosphorus 10 4
Sulfur 15 10

Table 1. Regulated levels of metals in biodiesel

Results and discussion

Spike recoveries Elements λ (nm) B100 Sample Spiked Solution Spike

(ppm) (ppm) (% recovery)
• Spike concentration Ca 422.673 0.005 0.52 105
approx 0.5 ppm for each K 766.491 <MDL 0.49 97
of 6 elements Mg 279.553 <MDL 0.5 100
Na 588.995 0.005 0.49 97
• Spike recoveries were all P 213.618 0.39 0.9 102
within ±5% of the S 181.972 0.26 0.79 103
expected values
Table 4. Measured values and spike recoveries (0.5 ppm) for 6 elements
in B100 biodiesel sample, all results measured are in solutions.

45
The Agilent ICP-MS Portfolio
Agilent is the worldwide market leader in ICP-MS with
almost 50% market share in units

Agilent 7800 ICP-MS

10x better: matrix tolerance, signal to noise
performance, and wider dynamic range.
And software so simple yet powerful it
writes methods for you.
The most robust, sensitive, and easy to Routine ICP-MS applications
use ICP-MS ever. • Throughput and reliability
• Ease of use

8800 Triple Quad ICP-MS

Ground breaking technology that
redefines application and performance
possibilities.
World’s first and only ICP-MS to
deliver the unique power of MS/MS.
High-end ICP-MS applications
• Difficult interference problems
• Maximum sensitivity and flexibility
Why ICP-MS?
In many samples, we have to measure :
- Trace elements at ppb levels : As, Cd, Pb, Se, Cr,…
- Major elements at ppm levels : Ca, Mg, Na ,K, Fe, Cu,…

Flame AA Furnace AA

- Mono-elemental technique - Long time of analysis

- Consumables : acetylene, lamps - High matrix effects
- Consumables : graphite tubes + argon

47
Why ICP-MS?
Flame AA Furnace AA

ICP-MS
- multi-elemental analysis
- Traces + major elements
Examples of Samples analyzed by ICP-MS
Environmental Semiconductor
Drinking Water, Ambient Water, Sea Water, Process Chemicals, Photo resists & strippers,
Soils, Sludges, Solid Waste, Contaminants in Si Wafers
Plant material, Agriculture,
Speciation of Hg, As, Pb, Sn,… Nuclear
Cooling Water, Impurities in U Fuel,
Food Analysis U Isotope Ratio Measurement,
Nutrition, Supplements
Toxic element and species monitoring, Geological
QA/QC, Proof of origin Soil, Rocks, Sediments,
Isotope Ratio Studies, Laser Sampling
Clinical
Blood, Urine, Serum, Hair, Tissues, Forensics
Gun Shot Residue,
Pharmaceutical Materials Characterization, Place of Origin,
Routine heavy metal contamination, Poisoning
Drug discovery, Clinical trials
Consumer Goods
PetroChem/General Chemical Textiles, Toys
Oils, Gasoline, Bioethanol, R&D, QA/QC
Archaeological
Metals Industry Artifact analysis, Proof of origin,
Product QC - high purity metals Tooth, bone, shell, coral analysis
R&D - steels
ICP-MS Schematic Diagram

Ion lens
Quadrupole Electron
Multiplier
Cell Gas Inlet
Spray chamber

Collision/Reaction cell
Skimmer cone
Torch
Octopole Reaction System (ORS)

Sampling
Nebulizer
cone
HMI – High matrix Introduction
HMI is an aerosol dilution device
It dilutes the sample using a make-up flow of
argon gas, added after the spray chamber
Increases matrix tolerance 10x
CeO/Ce oxid rate > 0.2%
Capacity to measure undiluted samples
(seawaters, urines, 20 - 30 g/L of TDS…)
Polyatomic Interferences in Complex Matrices
Isotope Principal Interfering Species (mixed matrix)
45 13
Sc C16O2, 12C16O2H, 44CaH, 32S 12CH, 32S 13C, 33S 12C
47 31
Ti P 16O, 46CaH, 35Cl12C, 32S 14NH, 33S14N
49 31 18
Ti P O, 48CaH, 35Cl14N, 37Cl12C, 32S 16OH, 33S 16O
50 34 16
Ti S O, 32S 18O, 35Cl14NH, 37Cl12CH
51 35
V Cl16O, 37Cl14N, 34S 16OH
52 36
Cr Ar16O, 40Ar12C, 35Cl16OH, 37Cl14NH, 34S 18O
53 36
Cr Ar16OH, 40Ar13C, 37Cl16O, 35Cl18O, 40Ar12CH
54 40
Fe Ar14N, 40Ca14N, 23Na31P
55 37
Mn Cl18O, 23Na32S, 23Na31PH
56 40
Fe Ar16O, 40Ca16O
57 40
Fe Ar16OH, 40Ca16OH
58 40
Ni Ar18O, 40Ca18O, 23Na35Cl
59 40
Co Ar18OH, 43Ca16O, 23Na35ClH
60 44
Ni Ca16O, 23Na37Cl
61 44
Ni Ca16OH, 38Ar23Na, 23Na37ClH
63 40
Cu Ar23Na, 12C16O35Cl, 12C14N37Cl, 31P 32S, 31P 16O2
64 32
Zn S 16O2, 32
S 2, 36Ar12C16O, 38Ar12C14N, 48
Ca16O
65 32
Cu S 16O2H, 32
S 2H, 14
N16O35Cl, 48
Ca16OH
66 34 16 32 34 33 48 18
Zn S O2, S S, S 2, Ca O
67 32 34 33 48 18 14
Zn S SH, S 2H, Ca OH, N16O37Cl, 16O235Cl
68 32
Zn S 18O2, 34
S2
69 32 18 34 16
Ga S O2H, S 2H, O237Cl
70 34
Zn S 18O2, 35
Cl2
71 34 18 35 40
Ga S O2H, Cl2H, Ar31P
72 40 32 35 37 40
Ge Ar S, Cl Cl, Ar16O2
73 40
Ge Ar32SH, 40Ar33S, 35
Cl37ClH, 40
Ar16O2H
74 40
Ge Ar34S, 37
Cl2
75 40 34 40
As Ar SH, Ar 35Cl, 40
Ca 35Cl, 37
Cl2H
77 40 37 40 37
Se Ar Cl, Ca Cl
78 40
Se Ar 38Ar
80 40
Se Ar2, 40Ca2, 40Ar40Ca, 32
S2 16O, 32
S 16O3
New collision/reaction cell ORS4
US Patent: 5,939,718 A

• Superior interference removal in He mode

• No need for reactive cell gases
• Simplicity
• He mode is effective for all polyatomic interferences
• He is inert, so no new interferences are produced
• He does not react with analytes
• Eliminates safety issues related to reactive gases
• Low consumption, ~5 ml/min He
• No need for correction equation
Principle of Helium Collision Mode and Kinetic Energy
Discrimination (KED)

Polyatomic Energy distribution Polyatomic Bias voltage

ions of analyte and ions rejects low energy
interfering (polyatomic) ions
polyatomic ions
Analyte with the same mass Analyte
ions ions

Energy Energy

At cell entrance,
analyte and polyatomic
ion energies overlap.
Energy spread of both Energy loss from each By cell exit, ion energies no
groups of ions is collision with a He atom longer overlap; polyatomics
narrow, due to is the same for analyte are rejected using a bias
ShieldTorch System and polyatomic ion, but voltage “step”. Analyte ions
polyatomics are bigger
have enough residual
and so collide more
often energy to get over step;
Cell Cell polyatomics don’t (energy
Entrance Exit discrimination)
Helium interactions -2
- Collision: Energy discrimination (ED)
Molecular interference (ArCl) has larger cross
section than the analyte (As).
↓
More frequent interactions with He.
75 ↓
As A significant reduction in kinetic energy
relative to the analyte (As). Energy filtering can
be used to ensure only the analyte
He
Ar enters the quadrupole analyzer.
40 Cl
Collision As
35
Electrical potential (Q-pole)

Ar

Cl
Cell
Electrical potential (Octopole)
Far Wider Measurement Range Than Any Other ICP-MS
11 orders - low and high level calibrations in a single run
Cd (1ppt - 1ppb) and Na (100ppb - 10,000ppm (1%)) in the same run
Both calibrations are linear.
Total concentration range
covered from Cd blank (BEC
of <0.1ppt) to Na top
standard (1%) is 11 orders

Concentration range (11 orders)

and upper measurement limit
(>1%) are at least 10x better
than any other ICP-MS
Speciation with LC-ICP-MS and GC-ICP-MS
Conventional “organo-metallic” compounds: Emerging elements/compounds:
• Inorganic vs organic arsenic • Pesticide and OP nerve agent residues
• Organo-tin • PBDEs
• Methyl-mercury, etc • Nanoparticles

Application Examples As Speciation using LC-ICP-MS

Agilent Application Note:
Routine Analysis of Toxic
Arsenic Species in Urine
Using HPLC with ICP-MS,
5989-5505EN, by Tetsushi
Sakai and Steven Wilbur,
Agilent Technologies
Nanoparticles
Nanoparticles
8800 ICP-QQQ Key Product Hardware
First quad Q1: High frequency 3rd generation collision/
hyperbolic quadrupole mass filter – reaction cell (ORS3)
High matrix selects ions that enter the cell with 4 cell gas lines
introduction
(HMI)
technology

Analyzer quad Q2:

High frequency
hyperbolic quadrupole
– selects ions that
pass to detector

60
Which Applications Need ICP-QQQ?
• Environmental: As and Se analysis in presence of REE. REE++ overlap As+ & Se+.

• High purity chemical: Ti and Zn analysis in semiconductor grade H2SO4 / H3PO4.

S and P polyatomic ions such as SO+, PO+ and SO2+ overlap Ti+ and Zn+.

• Petro/organics – S, Si (and Mg, Cr) in fuels; abundance sensitivity separates 11B

• Material: P in Si matrix. SiH+ and SiH2+ overlap on P+.

• Metals: As in Co matrix. Fe and Ni in Ca matrix. MO+/MOH+ interference on Cd.

• Geology: REE analysis. BaO and REE-O ion overlap other REE.

• Food: Sulfur Isotope Ratio analysis.

• Clinical: Ti and Cr analysis in blood and serum. S , P and C matrix.

• Nuclear: 129Iodine analysis. 129Xe atomic isobar interference.

Questions