New Trends in Trace Elemental Analysis Elsamoul Hamdnalla Thermo - - PowerPoint PPT Presentation

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Elsamoul Hamdnalla Thermo Fisher Scientific

New Trends in Trace Elemental Analysis

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During the past decade ICPMS has developed from a delicate research tool, intended for the well-trained scientist only, A more robust and well-established analytical technique for trace and ultra-trace element determination. ICPMS also shows a number of important limitations:

Introduction

into

 The occurrence of spectral interferences.  Solid samples have to be taken into solution prior to analysis  No information on the ‘chemical form’

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• For the analyst

For The Operation.

Challenges.

Speciation interference Isobaric and polyatomic interference

simplicity Design software

Sample Matrix

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ICP-MS Performance for All Applications

Thermo Scientific TM iCAP TM TQ ICP-MS Triple quadrupole ICP-MS Thermo Scientific TM iCAP TM RQ ICP-MS Single quadrupole ICP-MS Thermo Scientific TM ELEMENT TM 2/XR HR-ICP-MS High Resolution ICP-MS Thermo ScientificTM NEPTUNE Plus TM MC- ICP-MS Multicollector ICP-MS

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Redefining Trace Element Analysis -Triple Quadrupole ICPMS

All the Power, None of the Complexity

Triple quadrupole accuracy with single quadrupole ease of use

 Robust design for routine analysis  Advanced interference removal  Flexible for advanced applications  Integrated automation options  Unique ease of use

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Q3 Q2 Q1

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Inside TQ Technology

 Quick-connect, self-aligning sample

introduction system,

 Drop-down door for easy interface access.  Range of interfaces provide full instrument

flexibility, from maximum robustness to highest sensitivity.

 Zero user maintenance beyond the

interface.

 Highest data accuracy in complex

samples with the combined QCell and TQ functionality.

Q3 Q2 Q1

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Applications We Are Going to Focus on...

Environmental Analysis – As, Se Metallurgy Advanced Applications Speciation Analysis Nanoparticles Clinical Research - Ti

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Redefining Trace Element Analysis -Triple Quadrupole ICPMS Meeting human health and environmental challenges Advancing development in metals, materials and chemicals 8

• Clinical Research and Toxicology
• Metallopharmaceuticals
• Environmental Analysis/Monitoring
• Food Safety
• Material Analysis
• Nanoparticle Characterization
• Metallurgy
• Energy Production

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• Trace Elements play important roles for correct funtion of living beings

Determination of Trace Elements in Biological Samples

Matrix Characteristics Sample Preparation Urine Easy and pain-free to obtain Simple; Dilution High salt content Blood Contains protein bound metals Difficult; Microwave assisted digestion Viscosity, Precipitation Serum Reveals metal distribution in the bloodstream Simple; Dilution Salts, low molecular weightspecies Environmental Exposure: e.g. occupational health, work safety

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IntentionalExposure: e.g. orthopedic surgery, drug treatment

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• Ti may be released into the blood

stream following degradation of

• rthopedic or dental implants
• Low concentrations (less than

1 ng·mL-1)

• Isobaric interference of main

isotope 48Ti through 48Ca

• PO+, POH+, CaH+ interferences
• n other Ti isotopes
• Analytical methods need to be

 Robust to cope with sample matrix  Sensitive to enable detection of low levels  Specific to address Ti accurately despite interferences

Analysis of Ti in Serum

Analyte 48Ti+

114Cd+, 98Mo16O+

Product Ion 114[Ti(NH3)3NH]+

48Ti+ 114[Ti(NH3)3NH]+ 48Ca+, 96Zr++, 32S16O+, + 31P16O1H+, 24Mg2 Q3 isolates ions required for measurement (e.g. set to product ion mass for Ti+ at m/z114) Q2 pressurized with reactive gas to selectively generate reaction products (e.g. NH3 + Ti+  Ti(NH3)3NH+) Q1 set to analyte mass (e.g. Ti+ at m/z 48) to filter out unwanted ions

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Solution – use the iCAP TQ

Type As

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Method to remove

Se

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Method to remove Polyatomic Cl

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Ar

40

KED Ar

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Ar

40 2

KED, H

40Ca35Cl

Isobaric

+ 2

Nd

150 2

O

+ 2

Gd

156 2

O

150Sm2+ + 2

Dy

156

• Control ions entering the cell using Q1
• to efficiently convert As and Se

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Use O don‘t

++

the REE – 2 to AsO and SeO in Q react

• Selectively detect AsO and SeO free

3 interference, using Q

++

from REE ICP-MS using triple quadrupole technology – Thermo Scientific iCAP TQ ICP-MS

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• Interference removal capability

As and Se with REE Present - Results in Different Modes

• 1ppm Dy, Gd, Nd, Sm and Tb added
• Increased BECs observed for all

SQ- modes due to unresolved doubly charged REE interferences

• Hydrogen is suitable for removing Ar

based polyatomics, but is not capable of interferences

+ 2

fully removing REE

• mode shows

2

O

• TQ

dramatically lower BEC values for both As and Se

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Sample analysis results

Proving the Accuracy of the Sample Analysis

Spike recovery in REE matrix solution (1 ppb As and Se)

Analyte AGV-1 Sediment Arsenic 94.6 % 97.6 % Selenium 93.4 % 97.6 %

Spike recovery results in samples (1 ppb As and Se)

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Recovery of Ti in Serum using Different Measurement Modes

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10000 Reference Value Ti SQ-KED Ti SQ-NH3 Ti TQ-NH3 10 100 1000 Ti Concentration (µg·L-1)

Measured Ti Concentration in Ca-rich Blood Serum Samples

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Recovery of Ti in Serum using Different Measurement Modes

1 10000 Reference Value Ti TQ-NH3 10 100 1000 Ti Concentration (µg·L-1)

Measured Ti Concentration in Ca-rich Blood Serum Samples

Ti SQ-NH3

Single Quadrupole ICP-MS False positive results due to unresolved isobaric 48Ca Interference!

Ti SQ-KED

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Recovery of Ti in Serum using Different Measurement Modes

1 10000 Reference Value Ti SQ-KED Ti SQ-NH3 Ti TQ-NH3 10 100 1000 Ti Concentration (µg·L-1)

Measured Ti Concentration in Ca-rich Blood Serum Samples Triple Quadrupole ICP-MS Only by using triple quadtechnology can accurate results for Ti be

• btained!

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Accurate Multielemental Analysis with TQ-ICP-MS

• In Metals and Alloys
• Q1 separation of lower mass ions

enables effective and complete removal of all interferences on Selenium in Nickel alloys

• Only triple quadrupole ICP-MS is

capable of fully resolving all spectral interferences

• In Biological Samples
• High detection sensitivity allows

detection of low Titanium concentrations in complex biological samples

• Excellent agreement with certified

value obtained for Titanium in serum

• Full flexibility and usability of both single and triple quadrupole modes
• Full multielemental analysis with dedicated interference removal for difficult

analytes and comprehensive He KED in one run

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Redefining TQ-ICP-MS with Unique Ease of Use

Gas

M+ Product ion

Analyte Result

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Redefining TQ-ICP-MS with Unique Ease of Use

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• Speciation Analysis
• ChromControl plug-in for hardware

control

• Hyphenation of Gas Chromatography (GC )

using GCI-100 Analyte Advantage when using iCAP TQ Application

S, P Improved Interference Removal, lower background Speciation of Biomolecules like proteins, peptides or DNA As O

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As

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Sensitivity when analysing Higher As [KED]

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instead of All sample matrices: Food, Water, Urine etc. Se Higher Sensitivity when analysing SeO instead

• f Se [KED]; Reduced background on 80Se

All sample matrices

Advanced Applications using the iCAP TQ ICP-MS

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• Nanoparticle Analysis
• npQuant plug-in for Qtegra ISDS

Analyte Advantage when using iCAP TQ Application

Au, Ag No apparent advantage  High Detection Sensitivity Method Development, Validation Ti Increased specificity and lower background Environmental samples, Cosmetic products Others Improved interference removal is advantageous to reduce background and address particles more efficiently

Advanced Applications using the iCAP TQ ICP-MS

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Pharma Environment

iCAP TQ ICP-MS Application and Technical Notes

Metallurgy Clinical research

Proof data for you to use

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Which One Is Safer to Eat?

Total As concentration is not enough

As As As As As As HO-As-OH | OH O || H3C-As-CH3 | OH CH3 | H3C-As+-CH2CH2OH | CH3

What is the Speciation Analysis?

Is the analytical activity of identifying and/ or measuring the quantities of

• ne or more individual chemical species in a sample.

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Who Needs to Performs Speciation Analysis?

Industries Applications

Environmental

• Hexavalent chromium, arsenic and bromate

in drinking waters Food Safety

• Arsenic in fruit juices and rice grains
• Mercury in fish

Occupational Exposure and Consumer Goods

• Hexavalent chromium in toy materials

Pharmaceutical

• Mercury in herbal supplements

Petrochemical

• Sulfur/selenium in produced water

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Regulations

More regulations to come with ongoing assessments

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How Do You Perform Speciation Analysis? Separation Detection

Thermo Scientific™ Dionex™ ICS-5000+ HPIC™ System Thermo Scientific TM iCAP Q ICP-MS System

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Speciation Analysis Workflow

Detection Total element concentration is the sum of all species ↔ Preservation of original species distribution Loss of species during sample preparation Transformation of species Different separation mechanisms ↔ Ability to tackle several analytes with same instrumentation Ion chromatography: Analyte retention is achieved by interaction

• f charges with

stationary phase ICP-MS can only detect the element enclosed in a species ↔ Accurate and reliable quantification of different compounds containing the same element! Separation Sample Preparation

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Advantages of ICP-MS

• Measures almost the whole periodic table in any matrix
• Elemental concentrations
• High precision isotope ratio determinations
• Species information when coupled to separation devices

Highly versatile and sensitive detection technique

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Unique Advantages of IC Coupled to ICP-MS

• Separation of chemical species
• Completely metal-free flow path
• Less contamination
• Lowest chemical noise
• Better S/N
• Lower LOD
• Narrower bore columns (2 mm ID)
• Narrower peak shapes
• Better S/N

Metal-free flow path best suited for metal speciation applications

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Typical LC- and IC-ICP-MS Applications

Element Species Matrices Scientific Sector

Cr

Chromium III & VI Water, air particulates, cement Environment, industry, nutrition, occupational exp.

As

Organoarsenic compounds Fruit juice, fish, water, sediments, urine, hair Nutrition, environment, exposure

Se

Organoselenium Yeast, garlic, urine Agroindustry, nutrition, pharma, clinical

Hg

Inorganic mercury,

• rganomercury

Fish, sediments, water, urine, blood Environment, Clinical

Sn

Organotins Fish, sediments, water, plastics Environment, industry

Fe

Iron II & III Bacteria, soils, water Environment, clinical, nutrition

Cu, Zn, Cd

Phytochelatins, metallothioneins Plant tissues, brain & kidney tissue Agroindustry, clinical

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The Need for Chromium Speciation Analysis

• Chromium plating, dye manufacturing and preservation of wood and leather

materials

• US EPA and the EU have specify maximum chromium concentrations in

their drinking water directives

• Cr is found in more than one chemical form, each with different chemical

properties and behavior such as bioavailability and toxicity

• Cr (III) is essential to humans while Cr (VI) is highly toxic
• Total Cr content in drinking water does not provide sufficient information to

evaluate potential hazards to populations exposed to it

Application Example 1: Speciation Analysis of Cr (III) AND Cr (VI) in Drinking Waters using IC-ICP-MS

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The Need for Chromium Speciation Analysis

• Speciation analysis is challenging as stability of Cr species is easily

affected during collection and treatment.

• low pH values may lead to the degradation of Cr (VI) to Cr (III) due to the

increased redox potential,

• high pH values may lead to the precipitation of Cr (III) as Cr(OH)3
• An additional difficulty in the analysis of Cr by ICP-MS are the numerous

spectral interferences (e.g.35Cl16O1H+ or 40Ar12C+) on the most abundant chromium isotope, 52Cr

• Collision Cell Technology is required for accurate determinations

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Sample and Calibration Solution Preparation

• Standards were prepared using commercially available stock solutions

(1000 μg/mL) of each chromium standard in a 0.1 mol/L ammonium nitrate solution adjusted to a pH of 4

• Drinking water was collected in a PFA bottle previously rinsed with high

purity nitric acid

• The water was analyzed directly without dilution or pH adjustment in order

to keep the species unchanged before analysis

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Instrument Configuration

• Separations were carried out using

the Dionex ICS-5000+ /6000 ion chromatography system.

• Its metal-free solvent pathway is non-

contaminating and thus perfectly suited for elemental speciation studies

• A Dionex AG-7 anion exchange

column (2 x 50 mm) was used throughout this study.

• This column is a guard column but its

highly effective separation medium is able to completely separate both Cr species in less than three minutes.

• An iCAP Qc ICP-MS was used as a

high performing elemental detector of the Cr species eluted from the Dionex ICS-5000+ /6000 system:

• With the use of flatapole technology in the

QCell collision cell, the system offers the selectivity to suppress spectral interferences while maintaining the high sensitivity for trace metal detection using IC-ICP-MS.

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General Analytical Conditions

• iCAP Q ICP-MS equipped with a

PFA-LC nebulizer

• PFA-LC nebulizer with low dead volume and

LC fittings for chromatographic analyses.

• Single collision cell mode, with

kinetic energy discrimination (KED),

• He collision gas for interference-free

detection of 52Cr+ and 53Cr+

• Dionex ICS-6000 anion exchange,

isocratic elution with nitric acid

• Dionex AG-7 column elutes both

cations and anions

• Cr (III) is present predominantly as [Cr(H2O)6]3+
• and Cr(VI) as H2CrO4, HCrO4-, CrO4

2- or Cr2O7 2-

• depending on pH

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Method Development 0.2 mol/L nitric acid as mobile phase. 0.3 mol/L nitric acid as mobile phase. 0.4 mol/L nitric acid as mobile phase.

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Calibration

Overlay of 20 repeated injections of Cr(VI) and Cr(III)

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Conclusions

• The combination of the Dionex ICS-

5000+/ 6000 system with the iCAP RQc ICP-MS system yields a sensitive, robust IC-ICP-MS for the speciation analysis of trace levels of Cr (III) and Cr (VI) in natural waters

• This enables fast and reliable

speciation analysis of Cr species in water samples without prior incubation steps and with high purity nitric acid as mobile phase

• The short, but highly efficient Dionex

AG-7 column, provides complete separation of both species in under 150 s, enabling high sample throughput for the routine analysis of water samples

• Sub-ppt detection limits are achievable

due to the completely metal free pathway of the Dionex ICS-5000+ system and the high instrumental sensitivity offered by the iCAP Q ICP-MS system’s He KED mode

• The Dionex ICS-5000+ and iCAP Q

ICP-MS system provides a highly sensitive, routine IC-ICP-MS technique for the determination of trace metal species

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• Accurate trace elemental quantification enabled through improved

interference removal

• Simple method development – let Reaction Finder set up your method
• Higher productivity – Get the right result first time
• Lower LODs for challenging applications
• Reliable and consistent operation built on successful Platform
• More uptime – less cleaning and longer periods of uninterrupted analysis
• Less downtime for maintenance – easiest access to interface

Thermo Scientific iCAP TQ ICP-MS Delivering Quality ICP-MS Results

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• Automated solutions, with integrated software features & control
• Accelerate the TEQ workflow with intelligent dilution
• Unattended operation - leave personnel free to do more important tasks in the

lab

• Qtegra ISDS software providing intuitive workflows to streamline

efficiency

• Common platform to iCAP 7000 Series ICP-OES for reduced training and
• perator flexibility
• Plug-in based platform enables easy implementation of advanced applications

Thermo Scientific iCAP TQ ICP-MS Delivering Quality ICP-MS Results

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Thank you!