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The world leader in serving science

Complete Inorganic Elemental Speciation Solutions for Environmental Applications

Mr. Kristan BahtenThermo Scientific, Sunnyvale, CA, USA

Dr. Shona McSheehyThermo Scientific, Bremen, Germany

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Metals in the Environment

Natural sources

Industrial sources

Geochemical cycling

Uptake in food chain Wastes

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Metals in the Environment

HgAs

Cr

Pb Sn

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Metals in the Environment and Speciation

HO-As-OH|

  OH

O||

H3C-As-CH3

|  OH

Environmental Fate

Mobility Toxicity

Bioavailability

Reactivity

[Cr(H2O)6]3+

H3C-Hg+Hg0

Cr2O72-

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Who Needs Speciation?

Industry Needs

Environment• Environmental concerns

• Mobility and reactivity

Food Safety• Toxicity

• Nutritional value

Occupational Exposure and Consumer Goods

• Toxicity• Mobility

Pharmaceutical• Toxicity• Activity

Petrochemical• Contamination• Remediation

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Legislation – the Principal Driving Factor

Industry Legislation

Environment

• TBT in natural waters• Waste water monitoring

• Hexavalent chromium in drinking waters• Geochemical processes

Food Safety• MeHg+ in fish

• Bromate in drinking waters

Occupational Exposure and Consumer Goods

• Hexavalent chromium in: toys, workplace air

Pharmaceutical• Characterisation of food

supplements• USP

Petrochemical• Sulfur, mercury remediation

• Contamination of processes/catalysts

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Why Use ICP-MS for Environmental Analysis?

• It can measure almost the whole periodic table in just about everything

• Information derived:• Elemental concentrations

• High precision isotope ratios

• Species concentrations

• Particle number and composition

• High matrix tolerance• Interference removal• High sensitivity• > 9 orders dynamic range

Thermo Scientific™ iCAP™ ICP-MS

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What is ICP-MS?

Inductively Coupled Plasma - Mass Spectrometry

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What is ICP-MS?

1. Sample introduction

Inductively Coupled Plasma - Mass Spectrometry

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What is ICP-MS?

2. Elements in sample ionized in Inductively Coupled Plasma

Inductively Coupled Plasma - Mass Spectrometry

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What is ICP-MS?

3. Sampling interface

Inductively Coupled Plasma - Mass Spectrometry

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What is ICP-MS?

4. Interference removal - CRC

Inductively Coupled Plasma - Mass Spectrometry

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What is ICP-MS?

5. Quadrupole Mass Spectrometer

Inductively Coupled Plasma - Mass Spectrometry

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What is ICP-MS?

6. Detector

Inductively Coupled Plasma - Mass Spectrometry

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How Can We Perform Speciation Analysis?

Separation Detection

Thermo Scientific™ Dionex™ ICS-5000+ HPIC™ System

iCAP Q ICP-MS System

Thermo Scientific™ TRACE 1310 Gas Chromatography

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Principle Steps of Speciation Analysis

Extraction DetectionSeparation

Sample containing various compoundsüPreservation of original species distributionûLoss of species during sample preparationûTransformation of species

Different separation mechanisms

Ion chromatography:Analyte retention is achieved by interaction of charges with stationary phase

ICP-MS detects the element enclosed in a species

Accurate and reliable quantification of different compounds containing the same element

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SEM Image of 4 µm Supermacroporous Bead

What are the Advantages of Ion Chromatography?

• Metal-free PEEK systems• Powerful separation chemistries• Reagent-Free™ Ion

Chromatography (RFIC™)• Extensive IC product line for full

flexibility

• Smaller particles provide better performance

• Fast run times with higher flow rates using 150 mm columns

• High resolution with standard flow rates using 250 mm columns

New High Efficiency Thermo Scientific™ Dionex™ IonPac™ 4 µm HPIC™ Columns

Benefits:

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Dionex Ion Chromatography System Portfolio

Thermo Scientific Thermo Scientific Dionex ICS-1100

Basic Integrated Ion Chromatography

System

Thermo Scientific Thermo Scientific

Dionex ICS-900 Starter Line Ion

Chromatography System

Thermo Scientific Thermo Scientific Dionex ICS-1600

Standard Integrated Ion

Chromatography System

Thermo Scientific™ Thermo Scientific Dionex ICS-2100 Reagent-Free Ion Chromatography

(RFIC) System

Dionex ICS-5000+ HPIC Ion Chromatography

System

Thermo Scientific

Thermo Scientific Dionex ICS-4000

Capillary HPIC Ion Chromatography

System

RFIC

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Speciation with IC-ICP-MS

• Fully integrated software:• Thermo Scientific™ Qtegra™ Intelligent

Scientific Data Solution ISDS with Thermo Scientific™ Dionex™ Chromeleon™ Chromatography Data System (CDS) plug-in drivers to control IC or HPLC

• No need for external hardware trigger

• Fully integrated chromatographic data processing software

• Automated peak integration, species quantification and internal standard correction

• Thermo Scientific Dionex IC systems are entirely metal-free (PEEK) • Simple hardware connection

IC-ICP-MS is the ideal choice for trace elemental speciation

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Data System

• Very simple hardware connection:

• Simple interchange between standard ICP-MS analysis and IC-ICP-MS

• No need to turn off plasma

• A single software interface for both the IC and ICP-MS:

• Chromeleon CDS software interface built into workflow

• Fully integrated analysis and automated shutdown

• No trigger cable needed• One sample driving both

devices

Inert tubing 0.125 mm i.d.

A Complete Integrated IC-ICP-MS System

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EPA Method 200.8 Determination of Metals and Trace Elements in Water and Wastes by ICP-MS

• EPA 200.8 used for the determination of twenty-two dissolved elements in ground, surface and drinking waters

• Method applicable to wide variety of samples

• Thousands of analyses required/week in a typical routine laboratory

IsotopeLCS

Certified Found Recovery  (µg/kg)$ (µg/L) (%)

9Be 0.005* 0.005 100.027Al 49.5 51.6 104.251V 0.317 0.333 104.9

52Cr 0.208 0.222 106.755Mn 4.33 4.45 102.856Fe 91.2 88.1 96.660Ni 0.476 0.462 97.1

63Cu 17.4 18.4 105.566Zn 0.845 0.925 109.575As 0.413 0.420 101.8

111Cd 0.006 0.006 104.3135Ba 14 14.4 103.0208Pb 0.081 0.081 100.0238U 0.093 0.092 98.9

  (ug/g) (mg/L) (%)23Na 5.38 5.58 103.725Mg 2.54 2.65 107.5

39K 0.839 0.892 106.343Ca 10.5 10.1 96.2

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Matrix Tolerance and the iCAP Q ICP-MS Interface

• Unique design with:

• Optimized thermal properties

• Adjustable matrix tolerance

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EPA Method 200.8 Determination of Metals and Trace Elements in Water and Wastes by ICP-MS

Internal standard recovery within EPA protocol defined limits of 60 -125 % of initial internal standard over complete 15 hour analysis

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Chromium in Drinking Water

• Current requirements in drinking water:

Legislation MCL (µg/L)

EPA National Primary Drinking Water Regulations

100 µg Cr/L

European Commission Directive 1998/83/EC

50 µg Cr/L

California Legislation PHG (µg/L)

California EPA (OEHHA ) 1999 2.5 µg Cr/L0.2 µg Cr(VI)/L

California EPA (OEHHA ) 2009 0.06 µg Cr(VI)/L

California EPA (OEHHA ) Dec 2010 revision

0.02 µg Cr(VI)/L

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Considerations for HPLC-ICP-MS Parameters

• The determination of Cr by ICP-MS is complicated by polyatomic interferences:

• 40Ar12C+ on 52Cr

• 37Cl16O+ on 53Cr

• IC and sample preparation parameters need to be chosen carefully due to the complex redox chemistry of Cr

Chemical forms of Cr as a function of pH and potential

HCrO4- CrO4

2-H2C

rO4

[Cr(H2O)6]3+

Cr3+

Cr(OH)3(s) Cr(OH)4-

Cr(OH)2+

Cr(OH)2+

Cr(OH)3°

Cr(VI)

Cr(III)

pH

0,7

964

6,5

Eh

Cr2O72-

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QCell - Interference Removal by Collision/Reaction Cell

• Collision/Reaction Cell • A multipole/flatapole enclosed in a

chamber• Controlled flow of gas into the cell• Interaction of ions with the gas

mainly by collisions• If reactive gas used, reactions occur

• All cells are reaction cells

M+ and XnYn’

+

M+ only out

• RF field produced by Flatapole• Advantages:

• Automatic low mass cut-off• High transmission• Non consumable

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QCell - Interference Removal by Collision/Reaction Cell

• Low mass cut-off:

• Prevents recombination of precursors in cell reduced BECs

Anal. LMCO Interferences Precursors

51V 35 35Cl16O, 37Cl14N, 34S16OH

H, N, O, S, Cl

56Fe 39 40Ar16O, 40Ca16O O, Ar, Ca

63Cu 45 40Ar23Na, 12C16O35Cl, 31P32S

C, N, O, Na, P, S, Cl, Ar

75As 47 40Ar35Cl, 40Ca35Cl, 40Ar34SH, 37Cl2H

H, S, Cl, Ca, Ar

2.5% HNO3 / 1.5% HCl

75As BEC: 8.5ppt, LoD: 0.4ppt

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QCell - Interference Removal by Collision/Reaction Cell

• Low mass cut-off:

• Prevents recombination of precursors in cell reduced BECs

Anal. LMCO Interferences Precursors

51V 35 35Cl16O, 37Cl14N, 34S16OH

H, N, O, S, Cl

56Fe 39 40Ar16O, 40Ca16O O, Ar, Ca

63Cu 45 40Ar23Na, 12C16O35Cl, 31P32S

C, N, O, Na, P, S, Cl, Ar

75As 47 40Ar35Cl, 40Ca35Cl, 40Ar34SH, 37Cl2H

H, S, Cl, Ca, Ar

2.5% HNO3 / 1.5% HCl

75As BEC: 8.5ppt, LoD: 0.4ppt

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Dionex ICS-900 IC System with iCAP Q ICP-MS

• Single channel• Isocratic elution

• AN 43098:Speciation analysis of Cr(III) and Cr(VI) in drinking waters

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Chromium Speciation in Drinking Water

Column Dionex IonPac AS7 (50 x 2 mm)Mobile Phase 0.4 M HNO3

Flow(mL/min) 0.4Injection vol (µL) 20

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IC-ICP-MS for the Speciation of Cr(III) and Cr(VI)

• Both chromium isotopes, 52, 53Cr, can be monitored

• Cr(III) and Cr(VI) are completely baseline separated

• Limits of detection: • 0.20 ng L-1 [Cr(VI)]

• 0.38 ng L-1 [Cr(III)]

• Isocratic chromatography performed in less than 3 minutes

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Speciation of Cr in Drinking Water

Analysis of locally sourced tap water (Bremen):

Only Cr(VI) was detected, concentration 42.5 ng L-1

Injection without further sample treatment

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Chromium Speciation Analysis of Drinking Water

• A sensitive and fast method based on ion chromatography for the speciation of Cr has been developed

• No need for the addition of EDTA or other charge pairing agents necessary, no additional sample preparation, no additional spectral interferences in the mass spectra

• The IC eluent, dilute HNO3, is relatively cheap, easily sourced and allows detection of Cr species in the single digit ppt range

• Reduced column dimensions allow reduction of the mobile phase flow rate to 0.4 mL min-1

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Dionex ICS-2100 IC System with iCAP Q ICP-MS

• Single channel – isocratic elution with mobile phase of choice

• Integrated RFIC – gradient elution with

• KOH – anion-exchange• MSA – cation-exchange

• Arsenic, Iodine, Chromium, Iron speciation

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Arsenic and Sulfur Speciation in Natural Waters

• Arsenic is ubiquitous in the environment

• Speciation is essential for understanding the mobility and toxicity of arsenic

• Thioarsenates have been identified in neutral to high pH and sulfidic conditions

D. Wallschläger, C. J. Stadey, Anal. Chem. 79 (2007), 3873-80

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Arsenic and Sulfur Speciation in Natural Waters

• Detection of S is hampered by spectral interferences• 16O2+, 16O18O+ etc.

• Use of CCT mode with O2 to convert As and S in AsO+ (m/z 91) and SO+ (m/z 48), resp.

Parameter Value

Column Dionex IonPac AS18 (2x250mm)

Mobile phase KOH, automatically generated using RFIC

Gradient Conditions

0-5 min: 12-44mM KOH8-10 min 44-52 mM KOH12-15 min 52-100mM KOH

Injected vol. 20 µL

32S+ + 16O2 → 32S16O+ + 16O

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Arsenic and Sulfur Speciation in Natural Waters

• Different As and S containing anions separated and individually detected

• Simultaneously, also metal based species as MoO42- can be detected

Instrumental Performance:

LOD [SO42-]:

4.8 ng g-1

BEC: 2.5 ng g-1

LOD [As(III)]:0.02 ng g-1

BEC: 0.08 ng g-1

48SO+ 91AsO+ 114MoO+

Standards

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Arsenic and Sulfur Speciation in Natural Waters

• Unknown As/S-species found in natural water samples • Stoichiometry determined using peak area

48SO+ 91AsO+ 114MoO+

Natural Water

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Arsenic and Sulfur Speciation in Natural Waters

• A multi-elemental speciation method has been developed for the simultaneous characterization of sulfur and arsenic containing species:

• A simple autotune procedure configures the instrument for optimal detection of sulfur and arsenic using reaction with O2 in Qcell

• RFIC with a KOH gradient significantly simplifies set-up and ensures separation of eight sulfur/arsenic containing species in under 15 mins

• Narrow bore column (2 mm i.d.) allows reduction of the mobile phase flow rate to 0.4 mL min-1

• Oxyanions containing other species can also be measured simultaneously

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IC-ICP-MS: A Powerful Tool for Elemental Speciation

• IC-ICP-MS is a fully integrated technique• One software, no triggering, simple hardware connection

• The completely metal free ICS product line eradicates possibility of contamination

• Large range of IC systems and columns• IC tailored for your application

• Flexibility and support for developing applications

• For many elemental speciation applications IC is the preferred chromatographic choice for ICP-MS: • Mobile phases are simpler/cleaner for lower interferences, lower

background and lower limits of detection

• Narrower bore columns (2 mm ID) for higher efficiency separation and lower mobile phase consumption

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iCAP Q ICP-MS for Environmental Analysis

• Proprietary interface designed for matrix tolerance

• Increases productivity by minimizing QC failure and increasing analysis periods between maintenance

• Collision Reaction Cell technology with

• Low mass cut-off for accurate analysis at low concentrations

• Single mode He-KED for simplicity and high throughput

• Flexibility of CCT mode for challenging applications

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iCAP Q ICP-MS for Environmental Analysis

• Minimal bench space requirements

• 66 cm wide• Easy to use and maintain

• Quick connect sample introduction system

• Pop out interface for easy access• Intuitive Qtegra software platform

• Common to iCAP ICP-OES

• Integrated Get Ready, Workflows and QC

• Fully integrated IC-ICP-MS package with full set of chromatographic data evaluation features

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Thank You!

WS71159_E 06/14S