Atomic spectroscopy

How to choose the right technique for your

application

AA, MP-AES, ICP-OES, ICP-MS…

Gregory LECORNETAtomic spectroscopyproduct specialist

LSAG EMEAI FY15Agilent Restricted

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Analysis

Measure the concentration of elements in samples

EnvironmentalFood &

Agriculture

Materials ScienceChemical &

Energy Pharmaceuticals

• Drinking and natural water • Feed and fertilizer • Mining and Metals • Petroleum refining

• Heavy metals (USP<232>/<233>)

• Soil and sediment • Nutrient elements• Toys and Consumer

Products• Alternative Energy

(Biodiesel)• Incoming raw material

testing

• Waste(solids/liquids/gases)

• Some trace toxic element apps

• Some semicon etc • Fine and Bulk Chemicals • QA/QC of Final Product

3

Atomic Spectroscopy Strategy - Markets

Goal of new instruments

Agilent’s philosophy has always been lowest running costswith highest performance … and it still is!

4

• Best detection limits• Best Stability• High matrix tolerance• Best tools for interference correction

Highest performance

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

Lowest running costs

The Agilent Atomic Spectroscopy Portfolio

Agilent’s 55 and 200 Series

Agilent’s 4200 Agilent’s 5100 Agilent’s 7800 Agilent’s 8800

FAAS + GFAAS MP-AES ICP-AES ICP-MS ICP-QQQ

• 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 or elements?

Many Samples or many elements• ICP-OES, ICP-MS, MP-AES

Few samples or few elements• FAAS, GFAAS

Detection limits?

Low Detection Limits (sub ppb, ppt)• ICP-MS, GFAAS

High DL’s (>1ppb)• ICP-ES, MP-AES, FAAS

Additional Clarifying Questions

Budget?

Capital budget?

Operating budget?

Overall Requirements?

Sample Types?

MP-AES, FAAS* up to 3% TDS

ICP-OES up to 25% TDS

GFAAS greater than 10%

ICP-MS has HMI and can dilute

Current Usage?

Regulated methods?

What techniques does the chemist

know?

Performances

Flame AA

MP-AES

ICP-AES

Working rangeppb %

ICP-MS

Furnace AA

Mono-element technique

Total cost

Flame AAAcetylene + nitrous

oxide + lamps

MP-AES

ArgonICP-AES

Total cost

Purchasing cost + operating cost (10 years)

ArgonICP-MS

Furnace AA Argon + lamps

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

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.

Conventional AA

Fast Sequential AA

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.

October 15, 2015

Confidentiality Label

13

Microwave Plasma Emission Overview

Ground State Excited State Emission

Sample

Microwave excited Plasma

Monochromator& Detector

Quantitation

Page 14

NitrogenPlasma

Optical Diagram

Cassette style Torch

Monochromator

Pre-optics

Detector• Monochromator Czerny-Turner

• Holographic grating: 2400 t/mm

• Focal length: 60 cm

• Resolution <0.05 nm

CCD Detector

• 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

Agilent 4200 MP-AESNitrogen Generator 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 Performance• Increased working

range• Lower detection

limits• Reduced

interferences

Reduced Running Costs• Runs on Air

with Nitrogen Generator

• Reduced reagent costs

Increased safety• No acetylene• No nitrous

oxide

Ease of Use• MP Expert• Simple sample

prep• No burner

change over

Waste waters

Waste waters

Determination of major and minor elements ingeological 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

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

Table 4. MP-AES and certified CRM results

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

Trace elements in geological samples

Trace level gold in cyanide leach

Analysis of high purity gold

Platinum group elements in ore grade material

Various elements in plating solutions. Environmental

Food & Agriculture

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

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

Analysis of raw chemicals for contaminant levels.

Chemical & Energy

Materials Science

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.

24 Years of Agilent ICP-OES Innovation

1991

1998-2000

2006

1995

High resolution radial

sequential ICP-AES

Liberty

Liberty Series II

710/720/730Worlds fastest simultaneous ICP-OES. Patented CCD

Introducing increased throughput via SVS2

Axial and Radial models available. Vacuum and gas purge optics.

#1 selling ICP-OES.

Vista Chip CCD detector

Agilent 5100 ICP-OES

• Lowest Cost of Ownership

• Enhanced Performance

• Simple Operation

2014

Vista PRO & MPX

High QE PMT detector.

First innovation

We have made the combination of all advantages

Horizontal torch and axial/radial view

+Best DL with axial

view

-Radial window gets

dirty

Vertical torch and radial view

+No EIE effect

High robustness

-Bad DL

Vertical torch and axial/radial view

Best DL with axial viewNo EIE effect with radial view

High robustnessLonger lifetime of torches

Key benefit : Enhanced performance

30 % NaClppb

Al 2Ba 15Ca 79Cd < 1Co < 1

Cr 2Cu 2Fe 17Mg 5Ni 11Pb 11Si 31Sr 14Zn 16

No salt deposition even after 3 hResult of 30% NaCl (Brine)

• 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

DSCHole

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

DSCHole

Reflexion < λ c at 420 nm < Transmission

165 nm 785 nm

SVDV

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Light from axial view

To optics

Reflexionλ < 420 nm

Transmission λ > 420 nm

Light from Radial view

Transmission λ > 420 nm

Reflexion λ < 420 nm

To optics

Light from axial view

Light from radial view

To optics

Reflexion λ < 420 nm

Transmission λ > 420 nm

5100 : the fastest ICP

5100

Fastest CCD

DSC Optics with 1 slit (167 – 785 nm)

Vertical torch

FASTEST ICP of the market

Cost of ownership - example

Cost of ICP 1 Cost of 10 years of argon consumption

Cost of ICP 2

Cost of of 10 years of argon consumption

Cost of 5100

Cost of of 10 years of argon consumption

Total cost

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

Agilent’s Fitted Background CorrectionEasily handles complex background structure

Pb 220 with FITTED background correction – 2000 ppm Al

Pb 220 with FITTED background correction – 1000 ppm Mo

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 complexspectral interferences

• Gives access to extra wavelengthsfor improved validation

• Allows resolution of interferencesas 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.

Table 1. Regulated levels of metals in biodiesel

Metal ASTM D6751mg/kg

EN 14214 – 2012mg/kg

Group I metals: Na & K 5 (combined) 5 (combined)

Group II metals: Ca & Mg

5 (combined) 5 (combined)

Phosphorus 10 4

Sulfur 15 10

Results and discussion

45

Spike recoveries

• Spike concentration approx 0.5 ppm for each of 6 elements

• Spike recoveries were all within ±5% of the 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.

Elements λ (nm) B100 Sample(ppm)

Spiked Solution(ppm)

Spike (% recovery)

Ca 422.673 0.005 0.52 105K 766.491 <MDL 0.49 97Mg 279.553 <MDL 0.5 100Na 588.995 0.005 0.49 97P 213.618 0.39 0.9 102S 181.972 0.26 0.79 103

Agilent 7800 ICP-MS10x 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 use ICP-MS ever.

8800 Triple Quad ICP-MSGround breaking technology that redefines application and performance possibilities.World’s first and only ICP-MS to deliver the unique power of MS/MS.

The Agilent ICP-MS Portfolio

High-end ICP-MS applications• Difficult interference problems• Maximum sensitivity and flexibility

Routine ICP-MS applications• Throughput and reliability• Ease of use

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

Why ICP-MS?

Flame AA

47

Furnace AA

- Long time of analysis

- High matrix effects

- Consumables : graphite tubes + argon

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,…

- Mono-elemental technique

- Consumables : acetylene, lamps

ICP-MS

- multi-elemental analysis

- Traces + major elements

Why ICP-MS?

Flame AA Furnace AA

Examples of Samples analyzed by ICP-MSEnvironmental Drinking Water, Ambient Water, Sea Water, Soils, Sludges, Solid Waste,Plant material, Agriculture,Speciation of Hg, As, Pb, Sn,…

Food AnalysisNutrition, SupplementsToxic element and species monitoring,QA/QC, Proof of origin

ClinicalBlood, Urine, Serum, Hair, Tissues,

PharmaceuticalRoutine heavy metal contamination,Drug discovery, Clinical trials

PetroChem/General ChemicalOils, Gasoline, Bioethanol, R&D, QA/QC

Metals IndustryProduct QC - high purity metals R&D - steels

SemiconductorProcess Chemicals, Photo resists & strippers,Contaminants in Si Wafers

NuclearCooling Water, Impurities in U Fuel, U Isotope Ratio Measurement,

GeologicalSoil, Rocks, Sediments, Isotope Ratio Studies, Laser Sampling

ForensicsGun Shot Residue,Materials Characterization, Place of Origin,Poisoning

Consumer GoodsTextiles, Toys

ArchaeologicalArtifact analysis, Proof of origin,Tooth, bone, shell, coral analysis

ICP-MS Schematic Diagram

Quadrupole

Cell Gas Inlet

Collision/Reaction cell

Octopole Reaction System (ORS)Torch

Electron Multiplier

Nebulizer

Spray chamber

Sampling cone

Skimmer cone

Ion lens

HMI – High matrix IntroductionHMI 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 MatricesIsotope Principal Interfering Species (mixed matrix)45Sc 13C16O2,

12C16O2H, 44CaH, 32S12CH,

32S13C, 33S12C47Ti 31P16O, 46CaH, 35Cl12C, 32S14NH, 33S14N49Ti 31P18O, 48CaH, 35Cl14N, 37Cl12C, 32S16OH, 33S16O50Ti 34S16O, 32S18O, 35Cl14NH, 37Cl12CH51V 35Cl16O, 37Cl14N, 34S16OH52Cr 36Ar16O, 40Ar12C, 35Cl16OH, 37Cl14NH, 34S18O53Cr 36Ar16OH, 40Ar13C, 37Cl16O, 35Cl18O, 40Ar12CH54Fe 40Ar14N, 40Ca14N, 23Na31P55Mn 37Cl18O, 23Na32S, 23Na31PH56Fe 40Ar16O, 40Ca16O57Fe 40Ar16OH, 40Ca16OH58Ni 40Ar18O, 40Ca18O, 23Na35Cl59Co 40Ar18OH, 43Ca16O, 23Na35ClH60Ni 44Ca16O, 23Na37Cl61Ni 44Ca16OH, 38Ar23Na, 23Na37ClH63Cu 40Ar23Na, 12C16O35Cl, 12C14N37Cl, 31P32S, 31P16O264Zn 32S16O2,

32S2, 36Ar12C16O,

38Ar12C14N, 48Ca16O65Cu 32S16O2H, 32S2H, 14N16O35Cl, 48Ca16OH66Zn 34S16O2,

32S34S, 33S2, 48Ca18O

67Zn 32S34SH, 33S2H, 48Ca18OH, 14N16O37Cl, 16O235Cl

68Zn 32S18O2, 34S2

69Ga 32S18O2H, 34S2H, 16O237Cl

70Zn 34S18O2, 35Cl2

71Ga 34S18O2H, 35Cl2H, 40Ar31P72Ge 40Ar32S, 35Cl37Cl, 40Ar16O273Ge 40Ar32SH, 40Ar33S, 35Cl37ClH, 40Ar16O2H74Ge 40Ar34S, 37Cl275As 40Ar34SH, 40Ar 35Cl, 40Ca 35Cl, 37Cl2H77Se 40Ar 37Cl, 40Ca 37Cl78Se 40Ar 38Ar80Se 40Ar2,

40Ca2, 40Ar40Ca, 32S2

16O, 32S16O3

New collision/reaction cell ORS4

• 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

US Patent: 5,939,718 A

Energy Energy

CellEntrance

CellExit

Energy loss from each collision with a He atom is the same for analyte and polyatomic ion, but polyatomics are bigger and so collide more often

At cell entrance, analyte and polyatomic ion energies overlap. Energy spread of both groups of ions is narrow, due to ShieldTorch System

Polyatomic ions

Analyteions

Polyatomic ions

Analyteions

Energy distribution of analyte and interfering polyatomic ions with the same mass

Bias voltage rejects low energy (polyatomic) ions

By cell exit, ion energies no longer overlap; polyatomics are rejected using a bias voltage “step”. Analyte ions have enough residual energy to get over step; polyatomics don’t (energy discrimination)

Principle of Helium Collision Mode and Kinetic Energy Discrimination (KED)

Helium interactions -2- Collision: Energy discrimination (ED)

He

Collision

Ar

Cl

Ar

Cl

As

As

Electrical potential (Octopole)

Cell

Electrical potential (Q-pole)

Molecular interference (ArCl) has larger cross

section than the analyte (As).

↓More frequent interactions with He.

↓A significant reduction in kinetic energy

relative to the analyte (As). Energy filtering can

be used to ensure only the analyte

enters the quadrupole analyzer.

75

40

35

Far Wider Measurement Range Than Any Other ICP-MS11 orders - low and high level calibrations in a single run

Cd (1ppt - 1ppb) and Na (100ppb - 10,000ppm (1%)) in the same run

Concentration range (11 orders) and upper measurement limit (>1%) are at least 10x better than any other ICP-MS

Both calibrations are linear.

Total concentration range covered from Cd blank (BEC of <0.1ppt) to Na top standard (1%) is 11 orders

Speciation with LC-ICP-MS and GC-ICP-MS

Emerging elements/compounds:• Pesticide and OP nerve agent residues• PBDEs• Nanoparticles

As Speciation using LC-ICP-MSAgilent Application Note: Routine Analysis of Toxic Arsenic Species in Urine Using HPLC with ICP-MS, 5989-5505EN, by TetsushiSakai and Steven Wilbur,

Agilent Technologies

Conventional “organo-metallic” compounds:• Inorganic vs organic arsenic• Organo-tin• Methyl-mercury, etc

Application Examples

Nanoparticles

Nanoparticles

8800 ICP-QQQ Key Product Hardware

60

High matrix introduction

(HMI) technology

Analyzer quad Q2: High frequency

hyperbolic quadrupole – selects ions that pass to detector

First quad Q1: High frequency hyperbolic quadrupole mass filter –

selects ions that enter the cell

3rd generation collision/ reaction cell (ORS3) with 4 cell gas lines

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