Nuevo ICP-QMS 7900 de Agilent Technologies. Redefiniendo los límites de la técnica.

Rubén García

Especialista de Producto, Agilent

Technologies

Agenda ICP-MS Presentation

• Basic of ICP-MS

• High Matrix Interface

• Interference Removal with Collission Mode

• The New Agilent 7900 ICP-MS

Agilent Elemental Analysis Portfolio

AAFs

GFAAs

MP-AES

ICP-OES

ICP-MS

ICP-MS QQQ

What is ICP-MS?

Inductively Coupled Plasma Mass Spectrometry

Elemental analysis with:

• Wide elemental coverage (up to 75 elements)

• Very low detection limits (sub ppt level)

• Fast analysis times (all elements at once)

• Wide analytical working range (up to 11 orders)

- Simple spectra

• High matrix tolerance

• Isotopic information

7700x Detection Limits in Standard mode

Li Be B C

Na Mg Al Si P S Cl

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi

Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Th U

10 – 100 ppt

0.1-1 ppb

1-10 ppb

< 0.1ppt

0.1 – 1 ppt

1 – 10 ppt

26 Years of Agilent ICP-MS Innovation

1987 2000 2009 1994

First computer-controlled ICP-MS

PMS 100

4500 Series

7500 Series

7700 Series

Pioneering

ICP-MS

technology

Enabling routine

robust ICP-MS

analysis

Setting new levels

to ICP-MS

Performance

World's first benchtop system. Hyperbolic profile quad, motorized torch XYZ, cool plasma

Bringing ease of use

and reliability in ICP-

MS

9 orders detector range Octopole Reaction System

HMI, ISIS-DS, 3rd Generation ORS MassHunter SW #1 selling ICP-MS

A new era in ICP-MS

analysis

8800 ICP-QQQ

World’s first ICP-QQQ for unparalleled interference removal and sensitivity

2012

Introducing the All New 7900 ICP-MS

ICP-MS Redefined. Again.

7700 had:

Better matrix tolerance than any other ICP-MS

• More robust plasma (lower CeO/Ce ratio) than any other system under standard tuning conditions , plus HMI for routine analysis of % level dissolved solids

Best interference removal with Helium cell gas – eliminates need for reaction gases in all common applications

• 7700 ORS3 improvements - removes all polyatomics in He mode, giving accurate results in complex or variable sample types – impossible on ICP-MS systems that use reactive cell gases or mixtures

Wider dynamic range than any other quadrupole ICP-MS

• Full 9 orders dynamic range at the detector – linear to 500ppm without changing conditions or hardware

Why Introduce another new ICP-MS? Building on the success of the Agilent 7700 Series:

The Agilent HMI for Aerosol Dilution

Argon

Dilution Gas

The flow of fine aerosol from the

spray chamber is diluted with argon

before delivery to the torch.

The HMI allows manual or auto

setup of robust plasma

conditions for matrix tolerance.

Automatic Setup of Plasma Conditions

• Requires sophisticated software algorithm to map plasma conditions, and

hardware to allow conditions to be replicated.

• US Patent 7,671,329 B2

The Agilent HMI for Ease-of-Use

• And it is very easy to set up!

Lowest Oxide AND Double-Charged Ratios

Figure-of-Merit Agilent Agilent

HMI BrandX

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

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

Interference Removal

He mode on the

Agilent ORS still can’t

be matched by any

other ICP-MS

Interferences in Complex Matrices

Some manufacturers claim that ICP-MS

has only a few interferences, and that

reaction gases can be used to remove

them.

That’s true in a simple sample, but in a

complex sample there are many

interferences, and no reaction gas can

remove all of them

But He mode on the Agilent ICP-MS

can!!

Isotope 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, 31P16O2

64Zn 32S16O2, 32S2,

36Ar12C16O, 38Ar12C14N, 48Ca16O

65Cu 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, 40Ar16O2

73Ge 40Ar32SH, 40Ar33S, 35Cl37ClH, 40Ar16O2H74Ge 40Ar34S, 37Cl275As 40Ar34SH, 40Ar 35Cl, 40Ca 35Cl, 37Cl2H77Se 40Ar 37Cl, 40Ca 37Cl78Se 40Ar 38Ar80Se 40Ar2,

40Ca2, 40Ar40Ca, 32S2

16O, 32S16O3

Low flow sample

introduction system

High temperature 27MHz

plasma generator

Multi-element interference removal by

on-axis octopole reaction cell

High frequency hyperbolic

quadrupole

Fast simultaneous dual

mode detector

(9 orders dyn. range)

Agilent ICP-MS System with Collision Reaction Cell (CRC)

Helium interactions in an Octopole Reaction Cell Collision: 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.

2E5

cps

45 50 55 60 65 70 75 80 Mass

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

45 50 55 60 65 70 75 80 Mass

2E5

cps

He Mode

ALL polyatomic interferences are removed

in He Mode

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

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

Blank Acid Matrices and IPA in He Mode

Color of spectrum indicates which matrix gave each interfering peak

2E5

cps

45 50 55 60 65 70 75 80 Mass

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

9 Orders Dynamic Range Detector

Genuine 9 orders dynamic range so major elements at 100’s ppm can be measured in the same run as trace elements at ppt, without operator having to change conditions or hardware configuration.

Calibration shows Na in 1:10 and 1:5 diluted seawater – top point is 2360ppm

ICP-OES

Multi-element, ~2 min/ sample

10’s ppb to 1000’s ppm

Few Elements/Samples

ppt

ICP-MS – for trace elements and clean samples

Multi-element, ~4min/ sample

Single ppt to 10’s ppm

GFAAS

Single element, ~6min/ sample

10’s ppt to 100’s ppb

Many Elements/Samples

%

ppm

ppb Hydride/AFS

Few elements, ~2min/ sample

Single ppt to 10’s ppb

Range

Inorganic Analysis Techniques in a Typical Laboratory

7700 ICP-MS

Multi-element

Single cell gas mode and productivity tools reduce run time

HMI for samples with up to 2% dissolved solids

Single ppt (incl. hydride and Hg) to 100’s ppm (1000’s ppm

with HMI)

The Power of 10!

What if the world’s best quadrupole ICP-MS gets 10 times better?

The new Agilent 7900 opens up a new dimension

in ICP-MS capability.

7700 Series ICP-MS

How to Improve on the Best ICP-MS?

How about NEW

detector technology for

unprecedented

11 orders measurement

range and Fast TRA

Acquisition at 0.1msec

dwell time.?

How about a NEW Interface &

Ion Lens for up to 15x Signal

to Noise improvement?

How about a NEW ORS4

for ultra fast gas switching

in less than 3 seconds?

25% NaCl Brine Solutions Without Dilutions?

How about a NEW Ultra HMI for analysis of up to

25% NaCl brine solutions without dilutions?

11 Orders?

7900 ICP-MS Performance Highlights

Higher sensitivity & lower background than 7700x Comparison to 7700x actual performance

Plasma mode

Sensitivity (7900/7700x)

7Li 89Y 205Tl

No Gas

Normal x1.2 x1.9 x1.9

Low Matrix x1.0 x1.6 x1.6

General Purpose x1.0 x1.5 x1.8

HMI-high x1.3 x1.6 x1.8

Model Sensitivity [kcps/ppb] Off Mass Bkgnd [cps] S/N [x1E3]

7Li 89Y 205Tl 7amu 89amu 205amu 7Li 89Y 205Tl

7700x 100 320 320 0.7 1.5 5.4 140 210 60

7900 120 620 600 0.2 0.2 1.2 600 3100 500

7900/7700x 1.2 1.9 1.9 0.28 0.13 0.22 4 15 8

~2x higher sensitivity at mid- and high-mass

>3x to 5x lower background

Average ~10x better signal to noise (S/N)

Agilent 7900 Capable of Very High Sensitivity Tuned like competitor’s ICP-MS – CeO/Ce <2.5%

Calibration

Level Conc. Calc Conc. CPS Det. RSD

1 0 0 1 P 86.6

2 10 9.89 13676 P 0.6

3 50 49.984 69112 P 0.9

4 100 100.019 138295 P 0.4

Uranium calibration in No

Gas mode:

Ultra-high sensitivity

1.38 GHz/ppm

Ultra-low background:

MDL: 1.3ppq; BEC: 0.48ppq;

Want to Analyze Undiluted Seawater on ICP-MS?

27

From the Dead Sea?

NEW 7900 Ultra High Matrix Introduction (UHMI)

• Increased dilution range to x100 – even higher matrix capability

• Less matrix loading to interface, so better long-term stability

• Maintain high carrier gas flow through spray chamber,

so faster gas replacement and washout

7700 HMI 7900 UHMI

HMI-4 (HMI-L) 0.6 L/min 0.8 L/min

HMI-8 (HMI-M) 0.35 0.68

HMI-25 (HMI-H) 0.23 0.5

HMI-50 N.A. 0.4

HMI-100 N.A. 0.33

UHMI

Dilution

Port

Matrix Tolerance Vastly Superior to Any Other ICP-MS - Analysis of Brine (25% NaCl) with UHMI (HMI-50)

• Better DL than OES

• No maintenance required for cones after 8 hours continuous introduction.

50

60

70

80

90

100

110

120

130

140

150

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

25%

NaC

l + 1

00p

pb

9 Be [ no ]27 Al [ no ]51 V [ no ]51 V [ He ]52 Cr [ no ]52 Cr [ He ]55 Mn [ no ]55 Mn [ He ]56 Fe [ He ]59 Co [ no ]59 Co [ He ]60 Ni [ no ]60 Ni [ He ]63 Cu [ He ]66 Zn [ no ]66 Zn [ He ]68 Zn [ no ]68 Zn [ He ]75 As [ He ]78 Se [ He ]107 Ag [ no ]107 Ag [ He ]111 Cd [ no ]111 Cd [ He ]205 Tl [ no ]205 Tl [ He ]208 Pb [ no ]208 Pb [ He ]238 U [ no ]238 U [ He ]

4 hrs Quant Recovery

(25% NaCl matrix + 100µg/L spike)

OES

DL

(μg/L)

7900

DL

(μg/L)

Ag 0.7 0.07

Al 0.5 0.6

Be 0.07 0.03

Cd 0.4 0.16

Co 1 0.04

Cr 1 0.05

Fe 1.7 0.33

Mn 0.2 0.12

Ni 2.5 0.12

Pb 6 0.73

Se 10 1.2

Tl 9 0.22

V 1 0.09

Zn 0.5 0.39

7700: H2: 6.0 0 mL/min

10 sec.

7900: H2: 6.0 0 mL/min

2 sec.

Fast Cell Gas Switching – ORS4

NEW 7900 Orthogonal Detector System Improved dynamic range

Extended upper limit of detector range

Analog range increased from 3 Gcps 10 Gcps

Up to 11 orders dynamic range - ~0.1 cps to 10 Gcps

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

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 is 11 orders

Na

1%

Cd

BEC: <0.1ppt

Faster TRA mode for Transient Signal Analysis Minimum dwell time is shortened from 3 msec. on the 7700 Series

to 0.1 msec to allow faster sampling of transient signals.

0.1 msec This enables the

measurement of the

single NP peak signal

arriving on the detector.

30 nm Au Nanoparticle

New Integrated Sample Introduction System (ISIS 3) Fully compliant multi-mode EPA 6020 analysis* in <1 minute

7 port valve (incl.

online

ISTD port)

Piston

pump

3-way

valve

New features in ISIS 3

• Close-coupled valve – very short tube length so minimal stabilization/rinse delay

• Piston pump for faster sample uptake

• 3-way valve to switch between on-line ISTD or tune solution

• ISIS is now compatible with Startup auto-optimization functions and full autotune

* EPA 6020 includes 23 analytes, plus 8 recommended ISTDs, so up to ~30 analytes (2 gas modes gives optimum data in terms of sensitivity and interference removal)

New Integrated Sample Introduction System (ISIS 3)

Increase sample throughput: 30% faster

26+ elements analysis in soils, etc. (e.g. EPA 6020):

• 7700+ISIS 2: ~75 sec.

• 7900+ISIS 3: <60 sec.

MassHunter 4.1: Simpler and More Powerful Software Dashboard with Gadgets replaces old mixed UI concept

Instrument status monitor (right) can be

displayed on top of DA window, to show status

and access top level functions without the need

to open entire Top Level Application.

• Gadget icons are “live”; change appearance

depending on current status

• Also have short pull-down menus for quick

access to most common functions

Software so Powerful it Can Write Your Methods! A new era in simple method setup and ease of use

Method Wizard – Develops a complete method in three steps!

1. Select pre-set method template and choose matrix level

2. Confirm analytes and internal standards…

Software so Powerful it Can Write Your Methods! A new era in simple method setup and ease of use

Method Wizard – Develops a complete method in three steps!

3. Choose whether to optimize method for speed or DLs

…and click “Optimize”

Select “Speed” or “Low DL”

The new batch is ready to run It can be edited or save as a template for future use

unit DL BEC

Speed Low DL Speed Low DL

Be ppt 2.7 0.3 0.5 0.2

V ppt 1.4 0.0 0.3 0.0

Cr ppt 4.2 1.7 27.8 22.8

Co ppt 1.4 0.4 5.3 5.5

Cu ppt 3.7 2.2 9.3 8.8

As ppt 7.2 0.8 1.4 0.6

Mo ppt 0.8 0.3 0.7 0.4

Ag ppt 1.3 0.7 6.8 5.8

Cd ppt 0.0 0.0 0.0 0.1

Sb ppt 0.2 0.1 0.3 0.2

Ba ppt 7.4 1.8 21.7 17.6

Pb ppt 1.9 0.5 3.6 3.0

U ppt 0.0 0.0 0.0 0.0

Acquisition time

Speed: 2.4min

Low DL: 5.7 min

Remote Monitor App (iOS and Android devices) View instrument status and perform basic system control

An Industry First!

Improving Installation & Familiarization Installation

• Intuitive Installation Checkout

• Site Prep tool for Software Installation

Familiarization tools

• Familiarization Tutorials

- Familiarization Guide

- Familiarization Video

- Familiarization Slide Set

Plus:

Remote Advisor Now available

for ICP-MS!

Familiarization Tutorial – Over 20 Video Clips Videos show key theory and detailed operation

ICP-OES

Multi-element, ~2 min/ sample

10’s ppb to 1000’s ppm

Few Elements/Samples

ppt

ICP-MS – for trace elements and clean samples

Multi-element, ~4min/ sample

Single ppt to 10’s ppm

GFAAS

Single element, ~6min/ sample

10’s ppt to 100’s ppb

Many Elements/Samples

%

ppm

ppb Hydride/AFS

Few elements, ~2min/ sample

Single ppt to 10’s ppb

Range

Inorganic Analysis Techniques in a Typical Laboratory

7700 ICP-MS

Multi-element

Single cell gas mode and productivity tools reduce run time

HMI for samples with up to 2% dissolved solids

Single ppt (incl. hydride and Hg) to 100’s ppm (1000’s ppm

with HMI)

Agilent 7900 Multi-element

Faster analysis with ISIS3 and fast cell gas switching

UHMI for samples with up to 25% dissolved solids

Single ppt (incl. hydride and Hg) to 10,000’s ppm with new 11

orders concentration range detector

Eliminates the need for additional techniques for high-matrix

levels and high concentration/major elements

Raise Your Expectations A New Dimension in Quadrupole ICP-MS

Making the world’s best selling ICP-MS ten

times better

• 10x Higher Matrix Tolerance (25%TDS)

• 10x Wider Dynamic Range (11 orders)

• 10X Better Signal-to-Noise

• Plus SW so powerful it can write methods

for you

ICP-MS Redefined. Again.

10x