Handling high matrix & challenging samples with Agilent ICP-MS Atomi… · Furnace AA Mono-element technique ppb 11/15/2016 Agilent ICP-MS Systems 3. Processes in ICP-MS Plasma Mostly

Handling high matrix & challenging samples with Agilent ICP-MS

Uwe Noetzel

Agilent Technologies

Waldbronn, Germany

Agilent’s History in ICP-MS30 Years of ICP-MS Innovation

1987 2000 20091994

First computer-controlled ICP-MS

PMS series

4500

7500Enabling high

sensitivity

metal analysis

Enabling

routine robust

ICP-MS analysis

Enabling control

of common

interferences

First benchtop ICP-MSCool plasma

Enabling ease

of use and

productivity

9 orders detectorORS cell

HMIISIS-DS MassHunter SW

Enabling controlled

reaction chemistry

8800 ICP-QQQ

2012

World’s first ICP-QQQ

2014

#1 selling ICP-MS !

77007900

UHMIODS detectorISIS 3

A new era in ICP-

MS performance

2015 2016

7800

Solution readyMethod automation

Enabling simplified

ICP-MS workflows

Flexible, high

performance MS/MS

New 8900 ICP-QQQ

Second generation ICP-QQQ

November 2016

Spectroscopy Seminar Greece

Page 2

Performances

Flame AA

MP-AES

ICP-OES

Working rangeppt %

ICP-MS

Furnace AA

Mono-element

technique

ppb

11/15/2016

Agilent ICP-MS Systems

3

Processes in ICP-MS Plasma

Mostly the same as ICP-OES

November 2016


4

General ICP-MS Components/Technology

1. The liquid

sample is mixed

with argon gas by

the nebulizer to

form an aerosol..

2. The smallest

droplets pass

through the spray

chamber and into

the ion source -

the plasma

3. The sample

is desolvated

and ionized in

the plasma

4. Ions are

extracted from the

plasma by

extraction lenses in

the interface region

5. Ion lenses focus and

collimate the ions. The Omega

lens bends the ion beam off-

axis to prevent photons

from striking the detector

7. The quadrupole mass

spectrometer separates ions based

on their mass to charge ratio. The

selected ions continue on to the

detector

8. Ions are measured

using a discrete

dynode detector

providing 9 orders of

linear dynamic

range6. Interference Ions

are removed from the

ion path by

reaction/collision/KED

effects in the cell

November 2016


5

3 Key Benefits of Agilent ICP-MS

1) Matrix Tolerance

Ultra High Matrix

Introduction System (UHMI)

Handles tough sample

matrices better than any

other ICP-MS. Highest total

dissolved solids(TDS)

capability up to 3% with

7800 and 25% with 7900

• Reduces sample prep time

and error

• Better long-term stability

Page 6November 15, 2016

November 2016


6

Processes in ICP-MS Plasma

November 2016


7

The key technology – HMI and UHMI- Aerosol Control

High matrix sample

Carrier Gas

Sampling Cone

Torch

Spray chamber

Nebulizer

Dilution Gas

Skimmer

Peristaltic pump Aerosol DilutionDilution gas reduces sample load on plasma.

Dilution factor is selectable from 1 to 1/100

Agilent’s patented HMI dilutes the sample in the gas

state, using aerosol dilution. This removes the main

problems of liquid sample dilution:

• Time / Reagents / Errors / Contamination

Agilent UHMI

November 2016Spectroscopy

Seminar GreecePage 8

Ultra HMI (High Matrix Introduction) system

November 2016


Carrier gas

Dilution gas

Carrier gas flow (L/min) Total gas

flow

7700 HMI 7900 UHMI

HMI-4 (HMI-L) 0.6 0.8 0.95

HMI-8 (HMI-M) 0.35 0.68 0.95

HMI-25 (HMI-H) 0.23 0.5 0.95

HMI-50 N.A. 0.4 0.95

HMI-100 N.A. 0.33 0.95

• Increased dilution range to x100 – even

higher matrix capability

• Less matrix loading to interface, so

better long-term stability

• UHMI maintains high carrier gas flow

through spray chamber, so faster gas

replacement and washout

9

HMI – a Patent by Agilent Technologies

November 2016

Ken Sakata


10

Lowest Oxide AND Double-Charged Ratios

Figure-of-Merit AgilentAgilent

HMIBrandX

Oxide ratio % CeO+/Ce+ < 1.2* 0.2 - 1.0 < 2.5

Double-Charged ratio

%Ce2+/Ce+ < 2* < 2 < 3

No other ICP-MS can achieve these

low Oxide AND double-charged ratios

HMI

* Demonstrated at Installation

November 2016


11

45Sc 52Cr 56Fe 63Cu 66Zn 111Cd 115In 136Ba

100

50

0

% Recovery of a 10ppb mixed standard spiked into undiluted NASS-5 Seawater

0.2% CeO+/Ce+ 1 % CeO+/Ce+ 2 % CeO+/Ce+

Greater Matrix Tolerance = Lower Oxides

November 2016


12

Expanding the ICP-MS application to High matrix sample types

• Marine organisms

• Sediments

• Groundwater

• Open ocean

• Coastal seawater

• Enclosed lakes and lagoons

- with salt levels far in excess of oceanic seawater. Also known as

hypersaline lakes, where the level of salinity may be many times

that of seawater

- See Agilent application note 5991-4257EN

November 2016


13


1) Matrix Tolerance 2) Interference Removal

Ultra High Matrix






capability up to 25%


and error


Octopole Reaction System

(ORS4) He Mode

He Mode effectively removes

common polyatomic

interferences in the samples

• Easy to use - He collision

mode only

• Effective for a wide range of

sample types

• Accurate measurements

Page 14 November 2016


14

He Mode – Quite Brilliant

Page 15


General ICP-MS Components/Technology

1. The liquid

sample is mixed

with argon gas by

the nebulizer to

form an aerosol..

2. The smallest

droplets pass

through the spray

chamber and into

the ion source -

the plasma

3. The sample

is desolvated

and ionized in

the plasma

4. Ions are

extracted from the

plasma by

extraction lenses in

the interface region

5. Ion lenses focus and

collimate the ions. The Omega

lens bends the ion beam off-

axis to prevent photons

from striking the detector

7. The quadrupole mass

spectrometer separates ions based

on their mass to charge ratio. The

selected ions continue on to the

detector

8. Ions are measured

using a discrete

dynode detector

providing 9 orders of

linear dynamic

range6. Interference Ions

are removed from the

ion path by

reaction/collision/KED

effects in the cell

November 2016


16

Polyatomic Interference Formation

40Ar 35Cl75As

75

November 2016


17

Helium interactions in an Octopole Reaction CellCollision: Energy discrimination

He

Collision

Ar

Cl

Ar

Cl

As

As

Electrical potential (Octopole)

Reaction 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.

Page 18 Spectroscopy Seminar Greece

Page 18

2E5

cps

45 50 55 60 65 70 75 80Mass

Blank Acid Matrices and IPA in No Gas Mode

No Gas Mode

Unspiked 5% HNO3 + 5% HCl + 1% H2SO4 + 1% IPA Matrix

Unspiked Matrix – ALL peaks are due to polyatomic interferences

Multiple polyatomic interferences affect almost every

mass – Interferences are matrix-dependent

Color of spectrum indicates which matrix gave each interfering peak

November 2016


19

45 50 55 60 65 70 75 80Mass

2E5

cps

He Mode

ALL polyatomic interferences are removed

in He Mode


ALL polyatomic interferences are removed in He Mode (same cell conditions)

Blank Acid Matrices and IPA in He Mode


November 2016


20

45 50 55 60 65 70 75 80Mass

2E5

cps

He Mode

Now we will add a 10 ppb spike


ALL polyatomic interferences are removed in He Mode (same cell conditions)

Blank Acid Matrices and IPA in He Mode


November 2016


21

2E5

cps

45 50 55 60 65 70 75 80Mass

10ppb Spike in 5% HNO3 + 5% HCl + 1% H2SO4 + 1% IPA Matrix

Consistent high sensitivity for all isotopes of all elements in He Mode

Matrix Mix with Spike (10ppb) in He Mode

He Mode

Good signal for all spike

elements at 10ppb Spike.

Perfect template fit for all

elements – no residual

interferences and no loss of

analyte signal by reaction

Consistent sensitivity and perfect template match for all elements

November 2016


22

2E5

cps

45 50 55 60 65 70 75 80Mass


He Mode

Let’s zoom for Fe and check the perfect template 56Fe/57Fe

Perfect agreement 56Fe/57Fe

ArO interference removed

40Ar

16O

November 2016


23

2E5

cps

45 50 55 60 65 70 75 80Mass


He Mode

Let’s zoom for Cr and check the perfect template 52Cr/53Cr

Perfect agreement 52Cr/53Cr

ArC interference removed

40Ar

12C

November 2016


24


1) Matrix Tolerance 2) Interference Removal 3) Dynamic Range

Ultra High Matrix






capability up to 25%


and error


Octopole Reaction System

(ORS4) He Mode

He Mode effectively removes

common polyatomic

interferences in the samples

• Easy to use - He collision

mode only

• Effective for a wide range of

sample types

• Accurate measurements

Wider Dynamic Range

10 orders dynamic range with

7800 and 11 orders with 7900:

0.1ppt(DL) to 10,000ppm

• Simplifies method

development

• Easy sample prep.

• Improves productivity



25

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

November 2016


26

Putting All Together the advantages of the Agilent ICP-MSsimple, one cell gas, interference-free ICP-MS for real world sample analysis

One Configuration (standard –

robust plasma conditions)

One gas mode* (helium

collision)

One method for waters,

soils, wastes, food, urine,

blood, serum…

28 elements in less than 3.5 minutes per

run

* Plus no gas mode for non-interfered elements



28

Agilent ICP-MS for Drinking Water Analysis

Graphite Furnace Atomic Absorption (GFAAS)(for trace metals – Cd, Cr, Ni, Ag, Pb)

Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES)(Al, Mn, Fe, Cu, Zn, Ba, B, Ca, Mg)

Hydride Generation/Atomic Fluorescence Detection(Hg, As, Se, Sb)

each with different sample preparation requirements

Agilent ICP-MS: The perfect replacement!

Inductively Coupled Plasma-Mass Spectrometry (ICP-MS)(Cd, Cr, Ni, Ag, Pb, Al, Mn, Fe, Cu, Zn, Ba, B, Ca, Mg, Hg, As, Se, Sb, U)

November 2016


29

High-Throughput Routine Analysis

November 2016


30

Elemental coverage, dynamic range

and multielement capability has

meant ICP-MS is widely accepted

in routine labs

Method Detection Limits - 3 (n = 10)in Parts Per Billion for Drinking Waters(in 1% HNO3/0.5% HCl)

•All elements except low mass non-interfered elements were run in helium mode

•Low mass, non-interfered elements run in no gas mode

•No correction equations used

Element MassMDL

(ppb)Cell mode Element Mass

MDL

(ppb)Cell mode

Be 9 0.005 No gas Zn 66 0.014 He

B 11 0.005 No gas As 75 0.011 He

Na 23 0.058 No gas Se 78 0.017 He

Mg 24 0.002 No gas Sr 88 0.002 He

Al 27 0.007 No gas Mo 95 0.006 He

K 39 0.076 He Ag 107 0.002 He

Ca 44 0.090 No gas Cd 111 0.002 He

V 51 0.014 He Sb 121 0.006 He

Cr 52 0.004 He Ba 137 0.005 He

Mn 55 0.008 He Hg 202 0.001 He

Fe 56 0.014 He Tl 205 0.002 He

Co 59 0.004 He Pb 208 0.001 He

Ni 60 0.014 He Th 232 0.001 He

Cu 63 0.002 He U 238 0.001 He



31

Analysis of Food CRM Digests Using Agilent ICP-MS with He Mode Only (single mode)Single sample preparation is required

•Food CRMs microwave digested with 6ml HNO3 + 2ml H2O2

•Final volume 100 mL

Single analysis by Agilent ICP-MS for all the analytes!

Full mass range scan of food

digest (e.g. microwave digestion)

Page 32 November 15, 2016

Agilent Spectroscopy Seminar Iceland

Few calibrations curves (prepared in 1% HNO3/0.5% HCl)

Na,

LD= 160 ppt

Mg,

LD= 31 ppt

As,

LD= 8 ppt

Cd,

LD= 0.7 ppt

Hg,

LD= 3 ppt

Pb,

LD= 1 ppt

Excellent measurement capabilities for all the range of masses

November 15, 2016November 15, 2016

Agilent Spectroscopy Seminar Iceland

Biological fluidsWhole blood, serum, urine, plasma

Traces elements measurements (toxic and essential ones)

in biological fluids

Samples simply diluted (10 to 20 times) with specific basic solution

containing:

• Butanol

• EDTA

• Triton X100

• Ammonia

More than 100 samples can be prepared per hour !

November 2016


34

Biological fluidsWhole blood, serum, urine, plasma

Diluent Stock Solution

November 2016


35

10 20 30 40 50 60 70 80 90 100110120130140150160170180190200210220230240250260

5.0E4

1.0E5

[1] Spectrum No.1 [ 181.525 sec]:002SMPL.D# / Tune #1 [CPS] [Linear]

m/z-> 10 20 30 40 50 60 70 80 90 100110120130140150160170180190200210220230240250260

5.0E4

1.0E5


m/z->

Analysis of Toxic and Harmful ElementsElemental Screening of 1:10 diluted Urine (with interference removal in He mode)

• Unique capability of ICP-MS to acquire a scan across the entire mass range in

about 2 minutes, screening elements from 1000’s ppm to sub-ppb levels

Pb

Rb

Fe

Br Ba

Ca

Li MoI

CsSr

Zn

Cu

Sb

Sn

C Na

Mg

As

10 20 30 40 50 60 70 80 90 100110120130140150160170180190200210220230240250260

5.0E4

1.0E5


m/z-> 10 20 30 40 50 60 70 80 90 100110120130140150160170180190200210220230240250260

2.5E5

5.0E5


m/z->

PbFe

Br Ba

Li MoI

CsSr

Zn

Cu

Sb

SnAs

RbC Na

Mg

C

a

Identifying poisons

• “Unknown” element spiked into urine sample

Unknown element

Presence of element can be confirmed by spectral

template

November 2016


36

10 20 30 40 50 60 70 80 90 100110120130140150160170180190200210220230240250260

5.0E4

1.0E5


m/z-> 10 20 30 40 50 60 70 80 90 100110120130140150160170180190200210220230240250260

5.0E4

1.0E5


m/z->

Analysis of Toxic and Harmful ElementsElemental Screening of 1:10 diluted Urine (with interference removal in He mode)

• Unique capability of ICP-MS to acquire a scan across the entire mass range in

about 2 minutes, screening elements from 1000’s ppm to sub-ppb levels

Pb

Rb

Fe

Br Ba

Ca

Li MoI

CsSr

Zn

Cu

Sb

Sn

C Na

Mg

As

10 20 30 40 50 60 70 80 90 100110120130140150160170180190200210220230240250260

5.0E4

1.0E5


m/z-> 10 20 30 40 50 60 70 80 90 100110120130140150160170180190200210220230240250260

2.5E5

5.0E5


m/z->

PbFe

Br Ba

Li MoI

CsSr

Zn

Cu

Sb

SnAs

RbC Na

Mg

C

a

Identifying poisons

• “Unknown” element spiked into urine sample

Unknown element

194 196 198 200 202 204 206 208 210 212 214 216

5.0E4

1.0E5

[1] Spectrum No.1 [ 175.118 sec]:003SMPL.D / Tune #1 [CPS] [Linear]

m/z->

Pb

194 196 198 200 202 204 206 208 210 212 214 216

2.5E5

5.0E5


m/z->

Tl

210Po

208Pb

205Tl

203Tl

Presence of element can be confirmed by spectral

template

November 2016


37

Speciation: HPLC-ICP-MS with Agilent 1260

November 2016


38

Arsenic concentration in food varies over 4 orders of magnitude(slide courtesy J. Feldmann, U. Aberdeen)

0.01 mg/kg 0.1 mg/kg 1 mg/kg

20-200

0.5-1,5

>500

0.001

0.05-0.09

0.005-

0.01 0.22-1.1

3.0

[Arsenic]

Schoof et al. 1999, Williams et al. EST 2005, Raab et al. 2004

11/15/2016


39

http://images.google.co.uk/imgres?imgurl=http://www.charlestonseafood.com/images/Amazon/Mussels-500.jpg&imgrefurl=http://www.charlestonseafood.com/mall/Shellfish.asp&h=363&w=500&sz=38&hl=en&start=2&tbnid=yagZTcASHiUN0M:&tbnh=94&tbnw=130&prev=/images?q=mussels&gbv=2&svnum=10&hl=en

http://images.google.co.uk/imgres?imgurl=http://www.charlestonseafood.com/images/Amazon/Mussels-500.jpg&imgrefurl=http://www.charlestonseafood.com/mall/Shellfish.asp&h=363&w=500&sz=38&hl=en&start=2&tbnid=yagZTcASHiUN0M:&tbnh=94&tbnw=130&prev=/images?q=mussels&gbv=2&svnum=10&hl=en

http://images.google.co.uk/imgres?imgurl=http://www.cellarking.co.uk/image/Real-ale-pint.jpg&imgrefurl=http://www.cellarking.co.uk/standard CX Cellar Cooler.htm&h=270&w=238&sz=29&hl=en&start=7&tbnid=Z1xTgedO0NoASM:&tbnh=132&tbnw=116&prev=/images?q=pint+of+ale&gbv=2&svnum=10&hl=en

http://images.google.co.uk/imgres?imgurl=http://www.cellarking.co.uk/image/Real-ale-pint.jpg&imgrefurl=http://www.cellarking.co.uk/standard CX Cellar Cooler.htm&h=270&w=238&sz=29&hl=en&start=7&tbnid=Z1xTgedO0NoASM:&tbnh=132&tbnw=116&prev=/images?q=pint+of+ale&gbv=2&svnum=10&hl=en

As Speciation - Toxicity

Toxic!

Non-Toxic

?

Courtesy Ute Kohlmeyer GALAB, Germany

Many As species

exist – the

inorganic As

species are known

to be toxic and

most organic

species are

relatively harmless

to humans.

The potential

toxicity of some

species, such as

the huge variety of

arsenosugars, has

not yet been

established.

Less-Toxic

11/15/2016


40

Certified urine: NIES CRM No.18

Certified urine : NIES CRM No.18, diluted 10 times

Retention Time / min0.0 2.0 4.0 6.0 8.0 10.0 12.0

2000

6000

10000

14000

18000

22000

26000

30000

34000

1/10 NIES No.18

1/10 NIES No.18 + 1ug/L

1/10 NIES No.18 + 5ug/L

Sig

na

l / co

un

ts

Found mg/L Found2 mg/L Recovery1 % Found3 mg/L Recovery2 %

Total As 0.137 ± 0.011

AB 0.069 ± 0.012 0.0658 0.0758 100.0 0.1164 100.5

DMAA 0.036 ± 0.009 0.0313 0.0407 98.5 0.0817 100.5

As(III) 0.0025 0.0123 98.4 0.0486 92.6

MMAA 0.0026 0.0131 104.0 0.0518 98.5

As(V) 0.0024 0.0121 97.6 0.0526 100.4

Found2: 1.0 µg/L each STD spiked 10 time dilution urine CRM

Found3: 5.0 µg/L each STD spiked 10 time dilution urine CRM

Certified Value

November 2016


Page 41

Agilent ICP-MS Software Development

ChemStation

MassHunter 1

MassHunter 2

MassHunter 3

MassHunter 4.x

November 2016


Page 42

Method Wizard – Automatic ModeCreate a new method with just a few clicks

November 2016


43

1. Click Automatic mode

2. Click on required elements

from the periodic table

3. Select Reference Stock

Solution from a list of

available standard mixes.

Method Wizard – Automatic Mode (2)

November 2016


44

1. Specify locations of Blank,

typical sample and Tune

solution

2. Choose fastest speed or

lowest possible DLs

3. Click and

MassHunter builds, tests

and runs your method.

Agilent ICP-MS Applications

November 2016


45

Controlling InterferencesComparing ICP-QMS and ICP-QQQ

November 2016


46

Works at least as well as Agilent ICP-QMS in He mode

Also works superbly with reactive cell gases:

• Double mass filter (MS/MS)

• Q1 allows only single m/z to enter cell

• Ions in the cell are independent of matrix

• Reactions are controlled and consistent even with unusual or variable samples

Market-leading He mode reduces polyatomic interferences effectively

Can use reactive gas, but reaction mode has limitations in ICP-QMS:

• Single mass filter, positioned after cell

• No mass selection before cell

• Ions in cell vary with sample composition

• Reaction chemistry varies, so ions passed to detector vary

Agilent

ICP-QMS

Agilent

ICP-QQQ

November 2016


47

8900 ICP-QQQ Key Product Hardware

Low flow

sample

introduction

system

High matrix

introduction

(UHMI)

technology

Fast, frequency-

matching 27MHz

RF generator Efficient twin-turbo

vacuum system

Dual conical Extraction and

Omega lens focuses ions

across the mass range

Up to 11 orders

dynamic range

electron

multiplier (EM)

detector

Analyzer quad Q2:

High frequency

hyperbolic quadrupole

– selects ions that

pass to detector

High-transmission,

matrix tolerant interface

First quad Q1: High frequency

hyperbolic quadrupole mass filter –

selects ions that enter the cell

4th generation collision/

reaction cell (ORS4)

with 4 cell gas lines

Peltier-

cooled

spray

chamber

Robust, high-temperature

plasma ion source

Agilent ICP-QQQ Features

November 2016


48

MS/MS reaction cell having high selectivity• MS/MS reaction cell removes the most challenging interferences.

• S, Si and P can be quantified below – 50ppt

High sensitivity and Low noise• Sensitivity of Agilent 8900 is twice the Agilent7900, 700Mhz/ppm for

Yttrium is spec. !!

• Random noise is extremely low, < 0.2cps.

Excellent Abundance Sensitivity• MS/MS scan achieves < 1x10-10 abundance sensitivity.

High matrix tolerance and Reliability • never compromises in matrix tolerance and reliability established with

Agilent 7900 series ICP-MS.

Summary

8900 ICP-QQQ – High-end ICP-MS

• Unique power of MS/MS

• For difficult interference problems

• Maximum sensitivity and flexibility

7800 ICP-MS – ICP-MS New Standard

• HMI – Proven robust performance

• Proven He mode performance

• 10 orders wide dynamic range

7900 ICP-MS – Class by itself

• Highest performance in a Single Quad ICP-MS

• UHMI – up to 25% TDS

• Fast TRA mode for Single nanoparticle research

November 2016


49

Documents

Handling high matrix & challenging samples with Agilent ICP-MS Atomi… · Furnace AA Mono-element technique ppb 11/15/2016 Agilent ICP-MS Systems 3. Processes in ICP-MS Plasma Mostly