agilent e-seminar on emerging contaminants 9 to 12 march @ … · 2016-08-30 · agilent e-seminar...

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Agilent E-seminar on Emerging Contaminants

9 to 12 March @ 11am Singapore time

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Identifying inorganic contaminants in water sources using ICP‐MS

Publishers of Environmental ICP‐MS Methods

US Environmental Protection Agency

National Oceanographic and Atmospheric Administration

American Society for Testing and Materials (now international)

US Department of Energy (DOE)

Standard Methods

• Joint publication of the American Public Health Association (APHA), the American Water Works Association (AWWA), and the Water Environment Federation (WEF)

International Organization for Standards (ISO)

Environmental ICP‐MS Methods

USEPA methods

• 200.8 Metals in Waters by ICP‐MS• 200.10 Trace elements in marine waters by ICP‐MS• 1638 Trace elements in ambient waters by ICP‐MS• 1640 Trace elements in ambient waters by on‐line chelation ICP‐MS• 6020 Trace elements in wastes and waters by ICP‐MSOther ICP‐MS methods

• 172.0 (NOAA) Trace metals in marine sediments by ICP‐MS• 172.1 (NOAA) Trace metals in marine animal tissues by ICP‐MS• 3125 (Standard Methods) Metals in water by ICP‐MS• D5673 (ASTM) Metals in water by ICP‐MS• MM100 (DOE) Radionuclides by ICP‐MS• MM800 (DOE) Uranium in water by ICP‐MS

– www.nemi.gov (national environmental methods index)• ISO 17294 (ISO) Water Quality – Application of ICP‐MS; Part 2 Determination of 62

Elements

ICP‐MS methods specified for regulatory compliance

USEPA 6020(a) Trace metals in waters and wastes according to requirements of the Resource Conservation and Recovery Act (RCRA) as published in SW‐846

• Applicable to: Al, Sb, As, Ba, Be, Cd, Ca, Cr, Co, Cu, Fe, Pb, Mg, Mn, Hg, Ni, K, Se, Ag, Na, Tl, V, Zn

USEPA 200.8 Trace metals in drinking water according to requirements of the Safe Drinking Water Act as published in 40CFR part 141

• Applicable to: Al, Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Hg, Mo, Ni, Se, Ag, Tl, Th, U, V, Zn

Drinking Water Regulations

Element Typical conc in drinking water

Units WHO EC Directive 98/83/EC

SDWA Drinking Water in Japan

Drinking water in Thailand

Drinking water in Korea

Proposed Drinking water in China

Reqd detn limit

Method for measurement

Ag ---- ppb 10(2) <50 <1 GFAAS As 0.1 - 50 ppb 10(a) 10 10 10 50 50 <50 <1 HGAAS;GFAAS B 50 - 200 ppb 500(a) 1000 1000 300 <300 <30 ICP-OES Be ---- ppb 4 <2 <0.2 ICP-OES Cd 0.05 - 0.5 ppb 3 5 5 10 10 5 <10 <0.3 GFAAS Co ---- ppb <1000 <100 ICP-OES Cr 0.1 - 5 ppb 50(a) 50 100 50 (VI) 50 (VI) <50 (VI) <5 ICP-OES Fe 1 - 10,000 ppb 200 300(2) 300 500 300 <300 <20 ICP-OES Hg 0.01 - 0.05 ppb 1 1 2 0.5 2 1 <1 <0.05 CVAFS Mn 10 - 1000 ppb 50(a) 50 50(2) 50 300 300 <5 ICP-OES Mo 20 - 70 ppb 70 <500 <7 ICP-OES Ni 1 - 20 ppb 20(a) 20 20(2) 10 <20 <1 ICP-OES Pb 1 -30 ppb 10 10 15 50 50 50 <50 <1 GFAAS Sb 0.1 - 1 ppb 5(a) 5 6 2 <50 <0.2 GFAAS Se 0.1 - 0.5 ppb 10 10 50 10 10 10 <10 <1 HGAAS;GFAAS Ti ---- ppb <100 <10 ICP-OES Tl ---- ppb 2 <0.1 <0.01 GFAAS U 0.01 - 1 ppb 2(a) 30 2 <0.2 Fluorimetry V ---- ppb <50 <5 ICP-OES Al 0.01 - 100 ppm 0.2 0.02-0.2(2) 0.2 0.2 <0.2 <0.02 ICP-OES Ba 0.01 - 10 ppm 0.7 2 1 <0.7 <0.07 ICP-OES Ca 1 - 500 ppm 75 <7.5 ICP-OES Cu 0.01 - 1 ppm 2(a) 2 1.3 1 1 1 <1 <0.1 ICP-OES Mg 1 – 50 ppm 50 <20 <2 ICP-OES Na 10 – 100 ppm 200 200 <20 ICP-OES Zn 0.005 – 1 ppm 5(2) 5 1 <1 <0.1 ICP-OES

(a) Provisional Guideline Value(2) Secondary Standard (all others Primary

To meet the needs of all standards at the required detection limit, a lab requires:ICP-OES; GFAAS; HGAAS; CVAFS; Fluorimetry

What Advantages Does ICP‐MS Offer?

Low detection limits

• Everybody associates ICP‐MS with low detection limits

Wide dynamic range

• Few people appreciate that the dynamic range is very wide– 9 linear orders on the Agilent 7700 series– Quantify from ppt to 0.1% in the same acquisitions

Simple spectra

• Makes data interpretation much more easy

Removal of most interferences

• The He only ORS collision/reaction cell allows the measurement of elements in the most complex of samples

Isotopic information

• Isotope ratio screening; isotope dilution; stable isotope tracing

Unparalleled flexibility

• Laser ablation, chromatography, electrophoresis etc..

Spectral Lines in ICP‐OES

Wavelength (nm)

-9 10

-8 10

-7 10

-6 10

-5 10

Phot

ocur

rent

(Am

pere

s)

190 270 310 330230 250 290210 350

Pb 100mg/L

12

3

4

5 6

7 8

912

1110

Typical ICP‐MS Full Mass Spectrum

10 20 30 40 50 60 70 80 90100

110 120 130 140 150 160 170 180 190 200

210 220 230 240 250 260

500

1000

50

100

50

100

[1] Spectrum No.1 [ 200.458 sec]:SUIDO-QL.D [ｶｳﾝﾄ] [ﾘﾆｱ]

m/z->

m/z->

m/z->

2500

5000

200 202 204 206 208 210

[1] Spectrum No.1 [ 152.427 sec]:ICPDEMO.D [¶³ÝÄ] [ØÆ±]

10 ppb Pb

Mass (m/z)

Cou

nts

Spectral simplicity is a key ICP-MS benefit

Comparative Interferences ICP‐MS versus ICP‐OES

ELEMENT # emission lines # isotopes (natural) alkali metals

lithium 30 2cesium 645 1

alkali earthsmagnesium 173 3calcium 662 6

transition metalschromium 2277 4iron 4757 4

rare earthscerium 5755 4

If samples are rich in iron – there will be almost 5000 lines that will overlap other elements and cause interferences.

ICP‐MS is an inherently SIMPLER spectrum meaning fewer interferences

ICP‐OES

Pros

• multielement

• flexible element selection

• well documented methods

• good tolerance to dissolved solids

• average linear dynamic range

Cons

• detection limits for most elements

• spectral interferences

• sample consumption high (1 to 5 mL/min)

• element flexibility

– limited in older systems

– speed of analysis compromised in newer systems

• Difficult to differentiate against competing labs with similar technology

ICP‐MS

Pros

• excellent detection limits for most elements

• most elements in Periodic Table available

• good sample throughput• wide dynamic range (7 to 8 orders)• low sample volume consumption• flexible quantitation methods

– "semiquantitative"– external calibrations– isotope ratios

Cons

• dissolved solids/matrix effects ‐ need to dilute samples more than other techniques

• capital cost high (typically US$140k ‐190k)

• difficult to use (mainly perceived)• unreliable (mainly percieved)

Agilent 7700 ICP‐MS System in Detail

High matrix introduction (HMI) dilution gas inlet

Peltier‐cooled spray chamber

Off‐axis ion lens

Low‐flow Sample Introduction

Fast, frequency‐matching 27MHz RF generator

High‐performance vacuum system

Cell gas inlet

High‐frequency (3MHz) hyperbolic quadrupole

Fast, simultaneous dual mode detector (9 orders dynamic range)

High‐transmission, matrix tolerant interface

3rd generation Octopole Reaction System (ORS3)

All New Octopole Reaction System (ORS3)

The 7700 uses a completely new collision/ reaction cell

The ORS is an Collision/Reaction Cell (CRC)

• These devices remove residual interferences than can compromise detection limits

The ORS operates in either Collision or Reaction modes

• Giving the user complete flexibility to use either

• Most Agilent ICP‐MS users employ He only mode

– Extremely effective and requires no preknowledge of the sample

– Especially useful for LC‐ICP‐MS applications

Digested sample – full spectrum (acquisition time 90 seconds‐ He mode)

A LOT of magnesium and aluminium

Digested sample – full spectrum expanded verticallyInternal standards added on‐line

Digested sample– Qualitative Scan – transition metals The ORS removes all interferences, note

excellent isotopic template fit. This would be impossible using a reaction gas

Digested sample – rare earth elements

Excellent isotope pattern fits!

Antacid – heavy elements

Natural uraniumA little lead and bismuth

Thorium… what concentration?

1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 2 2 0 2 3 0 2 4 0 2 5 0 2 6 0

5 . 0 E 4

1 . 0 E 5

[ 1 ] S p e c t r u m N o . 1 [ 1 8 1 . 5 2 5 s e c ] : 0 0 2 S M P L . D # / T u n e # 1 [ C P S ] [ L i n e a r ]

m / z - > 0 6 0

[

Identification – real world sampleElemental 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

FeBr Ba

Ca

Li MoICs

Sr

Zn

Cu

SbSn

C Na

Mg

As

1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 2 2 0 2 3 0 2 4 0 2 5 0 2 6 0

5 . 0 E 4

1 . 0 E 5

[ 1 ] S p e c t r u m N o . 1 [ 1 8 1 . 5 3 1 s e c ] : 0 0 4 S M P L . D # / T u n e # 1 [ C P S ] [ L i n e a r ]

m / z - > 0 0 2

PbFeBr Ba

Li MoICs

Sr

Zn

Cu

SbSnAs

RbC Na

Mg

“Unknown” element

Ca

Identifying poisons (1:10 diluted urine scan)

• “Unknown” element spiked into urine sample

1 9 4 1 9 6 1 9 8 2 0 0 2 0 2 2 0 4 2 0 6 2 0 8 2 1 0 2 1 2 2 1 4 2 1 6

5 .0 E 4

1 .0 E 5

[1 ] S p e c t r u m N o .1 [ 1 7 5 .1 1 8 s e c ] :0 0 3 S M P L .D / T u n e # 1 [C P S ] [L in e a r ]

m /z - >

P b

2 0 4

0 5 S M P L .D # /

T l

Analysis of Toxic and Harmful ElementsIdentifying poisons (1:10 diluted urine scan)

• Confirmation (from isotopic template) of presence of Thallium (2ppb spike)– Can be quantified (semiquant) by reference to known concentration element

– Note 210Po would also be seen in this mass region of the screening acquisition

210Po

208Pb

205Tl

203Tl

7700x – Largest Analytical Range of any ICP‐MS

Calibration rangesHg (10 – 200ppt) – NoGas ModeAs (10 – 200 ppt) – He ModeSe (10 – 200 ppt) – He ModeNa (0.05 – 1000 ppm) – He Mode

Overall calibration range 10ppt (Hg, As, Se) to 1000 ppm (Na) in a single method‐ without attenuating ion transmission to increase working range

NaTypically, ICP‐MS cannot measure above 200ppm Na without changing quad resolution or ion lens settingsHgHg LOD on 7700x is about 2ppt –7700x can QUANTIFY at 10ppt!

7700x can do both of the above in the same run!

1000 ppm Sodium

As

Se

Hg

Na

10 ppt Mercury

These 4 plots were obtained under the same analytical conditionson the 7700x – only the gas mode (NoGas for Hg) changed

As

10 ppt Arsenic

Se

10 ppt Selenium

Good fit at 0.2ppm

Quantification

Concentration Measurements

• Semiquantitative Measurement

• External Calibration

• Standard Addition

• Isotope Dilution

Isotope Ratio

Note 2.44ppt Standard addition result for 40Ca – H2 cell gas mode

Pesticide Analysis with New Agilent Jet Stream Technology

Break for Questions

For questions,

a) type onto the Q&A box at any time during the presentation.

b) Dial *1 on your phone and wait for your name to be announced.

December 12, 2008

EPA 6020 Analysis of NIST Soil ExtractsCombining HMI with Discrete Sampling for Ultimate Performance* in High TDS Samples (up to 1% TDS)

Sample prep (NIST soil CRMs 2710 and 2711 – Montana soils)EPA 3051(1) Microwave assisted extraction using nitric plus hydrochloric acid

0.5g soil + 9ml HNO3 + 3ml HCl → 50ml final volume

Sample AnalysisAgilent 7700x ICP‐MS with ISIS‐DS for discrete sampling

Standard robust plasma conditionsStandard Ni conesStandard glass concentric nebulizerHelium + no gas modes

*Total run to run time 1.8 minutes/sample

(1) 3051a is not intended to provide “total” metals content due to insoluble silicates etc in soils.NIST provides “total” certified concentration which requires complete digestion using HF as well as median leachable recoveries by round robin using nitric/HCl digestion.

What is ISIS‐DS? Agilent Solution for Discrete Sampling

Fully integrated Agilent discrete sampling system for 7700 Series ICP‐MS

Uses 6 port valve with loop injection to:

• Virtually eliminate sample uptake and rinseout time resulting in very fast analyses

• Reduce total exposure of ICP‐MS cones and lenses to sample matrix resulting in improved short term and long term stability

• Minimize carryover due to elimination of peristaltic pump tubing from sample path

• Reduce sample introduction system maintenance and cleaning

to nebulizer

sample

carrier waste

ISIS P1

P2

ISTD

sample loop (load)

6‐port valve

ISTD mixing “tee”

to nebulizer

sample

carrier waste

ISIS P1

P2

ISTD

sample loop (inject)

6‐port valve

ISTD mixing “tee”

Test Sequence – 135 Total Analyses in 4.05 hours*

Sample block repeated 12 times

*Total run time:1.8 minutes per sample

CCV / CCB repeated every 10 samples

Performance – NIST 2710 Soil

NIST 2710 Montana Soil

Measured concentration

(mg/kg)%RSD (n=12)

NIST mean % recovery using

EPA 3050 of participating laboratories

Ratio Agilent recovery/NIST

recovery24 Mg 6280.4 3.9% 67.0% 109.9%27 Al 23980 3.4% 28.0% 133.0%39 K 6145.9 5.2% 21.0% 138.7%

42 Ca 3994.2 6.5% 33.0% 96.8%51 V 55.297 2.2% 56.0% 128.9%

52 Cr 23.646 0.9% 49.0% 123.7%55 Mn 7717.3 1.7% 76.0% 100.5%56 Fe 30382 1.5% 80.0% 112.4%57 Fe 30426 1.7% 80.0% 112.5%59 Co 8.217 1.5% 82.0% 100.2%60 Ni 12.012 2.1% 71.0% 118.3%

63 Cu 2743.1 1.3% 92.0% 101.1%66 Zn 6373.5 1.0% 85.0% 107.9%75 As 602.14 2.0% 94.0% 102.3%78 Se 0.997 6.4% N/A N/A95 Mo 17.248 2.9% 100.0% 90.8%

107 Ag 28.791 3.2% 79.0% 103.2%111 Cd 20.629 1.6% 92.0% 102.9%137 Ba 383.52 1.7% 51.0% 106.4%201 Hg 26.184 1.7% 98.0% 82.0%205 Tl 0.833 5.2% 48.0% 133.4%

208 Pb 4426.63 1.7% 92.0% 87.0%232 Th 9.446 2.4% N/A N/A238 U 17.299 2.7% N/A N/A

Recovery calculated as Agilent recovery of certified amounts compared with NIST round robin using similar “leachable”extraction procedure.




(mg/kg)%RSD (n=12)




recovery24 Mg [ 2 ] 6280.4 3.9% 67.0% 109.9%27 Al [ 2 ] 23980 3.4% 28.0% 133.0%39 K [ 2 ] 6145.9 5.2% 21.0% 138.7%

42 Ca [ 2 ] 3994.2 6.5% 33.0% 96.8%51 V [ 2 ] 55.297 2.2% 56.0% 128.9%

52 Cr [ 2 ] 23.646 0.9% 49.0% 123.7%55 Mn [ 2 ] 7717.3 1.7% 76.0% 100.5%56 Fe [ 2 ] 30382 1.5% 80.0% 112.4%57 Fe [ 2 ] 30426 1.7% 80.0% 112.5%59 Co [ 2 ] 8.217 1.5% 82.0% 100.2%60 Ni [ 2 ] 12.012 2.1% 71.0% 118.3%

63 Cu [ 2 ] 2743.1 1.3% 92.0% 101.1%66 Zn [ 2 ] 6373.5 1.0% 85.0% 107.9%75 As [ 2 ] 602.14 2.0% 94.0% 102.3%78 Se [ 2 ] 0.997 6.4% N/A N/A95 Mo [ 1 ] 17.248 2.9% 100.0% 90.8%

107 Ag [ 1 ] 28.791 3.2% 79.0% 103.2%111 Cd [ 2 ] 20.629 1.6% 92.0% 102.9%137 Ba [ 1 ] 383.52 1.7% 51.0% 106.4%201 Hg [ 1 ] 26.184 1.7% 98.0% 82.0%205 Tl [ 1 ] 0.833 5.2% 48.0% 133.4%

208 Pb [ 1 ] 4426.63 1.7% 92.0% 87.0%232 Th [ 1 ] 9.446 2.4% N/A N/A238 U [ 1 ] 17.299 2.7% N/A N/A

Very good run to run precision (n=12 distributed over the entire sequence)




(mg/kg)%RSD (n=12)




recovery24 Mg [ 2 ] 6280.4 3.9% 67.0% 109.9%27 Al [ 2 ] 23980 3.4% 28.0% 133.0%39 K [ 2 ] 6145.9 5.2% 21.0% 138.7%

42 Ca [ 2 ] 3994.2 6.5% 33.0% 96.8%51 V [ 2 ] 55.297 2.2% 56.0% 128.9%

52 Cr [ 2 ] 23.646 0.9% 49.0% 123.7%55 Mn [ 2 ] 7717.3 1.7% 76.0% 100.5%56 Fe [ 2 ] 30382 1.5% 80.0% 112.4%57 Fe [ 2 ] 30426 1.7% 80.0% 112.5%59 Co [ 2 ] 8.217 1.5% 82.0% 100.2%60 Ni [ 2 ] 12.012 2.1% 71.0% 118.3%

63 Cu [ 2 ] 2743.1 1.3% 92.0% 101.1%66 Zn [ 2 ] 6373.5 1.0% 85.0% 107.9%75 As [ 2 ] 602.14 2.0% 94.0% 102.3%78 Se [ 2 ] 0.997 6.4% N/A N/A95 Mo [ 1 ] 17.248 2.9% 100.0% 90.8%

107 Ag [ 1 ] 28.791 3.2% 79.0% 103.2%111 Cd [ 2 ] 20.629 1.6% 92.0% 102.9%137 Ba [ 1 ] 383.52 1.7% 51.0% 106.4%201 Hg [ 1 ] 26.184 1.7% 98.0% 82.0%205 Tl [ 1 ] 0.833 5.2% 48.0% 133.4%

208 Pb [ 1 ] 4426.63 1.7% 92.0% 87.0%232 Th [ 1 ] 9.446 2.4% N/A N/A238 U [ 1 ] 17.299 2.7% N/A N/A

Excellent dynamicrange – from 0.8mg/kg to > 30,000mg/kg




(mg/kg)%RSD (n=12)




recovery24 Mg [ 2 ] 6280.4 3.9% 67.0% 109.9%27 Al [ 2 ] 23980 3.4% 28.0% 133.0%39 K [ 2 ] 6145.9 5.2% 21.0% 138.7%

42 Ca [ 2 ] 3994.2 6.5% 33.0% 96.8%51 V [ 2 ] 55.297 2.2% 56.0% 128.9%

52 Cr [ 2 ] 23.646 0.9% 49.0% 123.7%55 Mn [ 2 ] 7717.3 1.7% 76.0% 100.5%56 Fe [ 2 ] 30382 1.5% 80.0% 112.4%57 Fe [ 2 ] 30426 1.7% 80.0% 112.5%59 Co [ 2 ] 8.217 1.5% 82.0% 100.2%60 Ni [ 2 ] 12.012 2.1% 71.0% 118.3%

63 Cu [ 2 ] 2743.1 1.3% 92.0% 101.1%66 Zn [ 2 ] 6373.5 1.0% 85.0% 107.9%75 As [ 2 ] 602.14 2.0% 94.0% 102.3%78 Se [ 2 ] 0.997 6.4% N/A N/A95 Mo [ 1 ] 17.248 2.9% 100.0% 90.8%

107 Ag [ 1 ] 28.791 3.2% 79.0% 103.2%111 Cd [ 2 ] 20.629 1.6% 92.0% 102.9%137 Ba [ 1 ] 383.52 1.7% 51.0% 106.4%201 Hg [ 1 ] 26.184 1.7% 98.0% 82.0%205 Tl [ 1 ] 0.833 5.2% 48.0% 133.4%

208 Pb [ 1 ] 4426.63 1.7% 92.0% 87.0%232 Th [ 1 ] 9.446 2.4% N/A N/A238 U [ 1 ] 17.299 2.7% N/A N/A

Excellent recovery of leachable metals when compared with NIST round robin results.

Some of Agilent values are slightly higher than round‐robin results, due to microwave extraction (EPA 3051a) versus hot plate digestion (EPA 3050)

Performance ‐ NIST 2711 Soil

NIST 2711 Montana

Soil


(mg/kg)%RSD (n=12)




recovery24 Mg [ 2 ] 8290.6 3.8% 77.0% 102.5%27 Al [ 2 ] 22701 3.3% 28.0% 124.2%39 K [ 2 ] 5831.1 5.4% 16.0% 148.8%

42 Ca [ 2 ] 21077 3.4% 73.0% 100.3%51 V [ 2 ] 59.77 2.6% 51.0% 143.6%

52 Cr [ 2 ] 28.78 2.0% 43.0% 142.4%55 Mn [ 2 ] 546.7 2.3% 77.0% 111.3%56 Fe [ 2 ] 25266 2.2% 76.0% 115.0%57 Fe [ 2 ] 25400 2.1% 76.0% 115.6%59 Co [ 2 ] 8.661 2.4% 82.0% 105.6%60 Ni [ 2 ] 17.35 2.2% 78.0% 108.0%

63 Cu [ 2 ] 110.0 2.1% 88.0% 109.7%66 Zn [ 2 ] 339.6 2.0% 89.0% 108.9%75 As [ 2 ] 96.76 2.3% 86.0% 107.2%78 Se [ 2 ] 1.628 8.8% N/A N/A95 Mo [ 1 ] 1.510 2.2% N/A N/A

107 Ag [ 1 ] 4.142 1.9% 86.0% 104.0%111 Cd [ 2 ] 40.24 3.0% 96.0% 100.5%137 Ba [ 1 ] 239.4 1.2% 28.0% 117.8%201 Hg [ 1 ] 5.901 1.3% N/A N/A205 Tl [ 1 ] 1.734 2.2% N/A N/A

208 Pb [ 1 ] 1129.9 1.0% 95.0% 102.4%232 Th [ 1 ] 10.26 1.9% N/A N/A238 U [ 1 ] 1.183 3.3% N/A N/A

Excellent precision (2‐3%) and dynamicrange (1.2 mg/kg to >25,000 mg/kg)

Note the isotopic agreement for Fe isotopes which suffer from different interferences


Break for Questions

For questions,



December 12, 2008

Agilent 7700 Series

ICP‐MS As A Detector – Interfacing Options

OptionalConventionalDetector(s)

GC

LC/IC

CE

ICP-MS

Laser Ablation

Laser

Sample

Ar Gas with ablated material

Agilent 7700 ICP‐MS

New Wave UP 213 Laser Ablation system

Laser Ablation ICP‐MS

Pulsed Nd:YAG laser is used to ablate solid samples into the plasma

Useful for solids

• No dissolution process required

• Useful for bulk analysis and feature analysis

Oxide levels are much lower

• Interferences less of a problem

Expensive !

Ar or He in

UV laser

TV

To ICPtorch

Lens

Sample

Mirror

Lens

Laser Ablation System

Bulk Analysis using Raster or Line or Feature Analysis using Single SpotRaster pattern is used to sample over a wide area of the sample surface

Laser ablates an area of the sample to give bulk analysis of homogeneous samples, such as pressed pellets, metals and fused glasses

Spot analysis is used to focus on features of interest ‐spots from 140um to 12um diameter shown

Can be used for bulk analysis, but will be affected by sample inhomogeneity and stable signal does not last as long as with line or raster

Why Speciation?

Almost all elements form species which can alter their toxicity and mobility

• CrIII vs CrVI; Inorganic As vs Organic As; Humic complexes …

Some species are specifically used for their toxic (or chemical) properties

• Organotin Species

– marine anti‐fouling paint; polymer stabilisers; fungicides• Organophosphorus Species

– pesticides; nerve agents

Whether natural or man‐made, these species can find their way into the drinking water, seawater and enter the food chain via marine life

Clearly, there is a requirement for the simple, selective, rapid, sensitive and accurate determination of these species

Why use ICP‐MS as Chromatographic Detector?

Sensitive

• sub ng/g (ppb) LODs

• generally superior to other detectors (MS, UV, MS‐MS) for organometallics

Multi‐elemental (simultaneous) determinations

• e.g. simultaneous speciation of As and Se species

Element specific

Isotopic measurements

• Use of species specific isotope dilution analysis (SS‐IDMS) → High precision, high accuracy measurements

• Verification of isotopic composition of target analyte

Connecting an LC to an ICP‐MS

nebulizer &spraychamber

gas controller

ICP torch Q‐pole mass filter

Ar gas

rotary pump

liquid chromatograph

Determination of just about any elemental species

Cr, As, Se, Sn, P, Br, Fe, Hg, Pb etc. etc. etc…..

Based upon their oxidation state and/or organic complex

Phenylarsonic acids using Agilent LC‐ICP‐MS

0.10 ng As0.25 ng As0.50 ng As1.00 ng As2.50 ng As5.00 ng As

Data kindly provided by Walter Goessler et. al. (U. Graz)

Intensity

Retention time [min]

0 5 10 15 20 25

0

5000

10000

15000

20000

25000

4‐APA

4‐HPA

2‐NPA

PA

3‐NHPA

4‐NPA

Phenylarsonic acids used for the control of parasites and as growth promoters in poultry – concerns are raised as to the safety in excretions

LC‐ICP‐MS – As Speciation

Data kindly provided by Walter Goessler et. al. (U. Gratz)

During storage of chicken litter, the phenylarsonic compounds are converted to arsenate, arsenite, methylarsonic‐ and dimethylarsinic acid, probably by bacteria, significantly increasing the toxicity.

Retention time [min]

0 5 10 15 20 25

Intensity

0

10000

20000

30000

Uncomposted Chicken Litter

3‐NHPA

4‐HPA

PA

4‐APA +As(V)

Composted Chicken Litter– expanded scale

As(V)

As(III)

DMA

MA

ICP‐MS as a Detector for Phosphorus‐Containing Herbicides

Phosphorus is traditionally difficult to analyze in an argon plasma

• High ionization potential (10.5 eV)

• Polyatomic interferences 14N16O1H+ and 15N16O+ overlapping its only isotope at m/z = 31

• A collision cell can eliminate these polyatomic species and obtain the highest signal‐to‐background ratio

Reversed phase ion‐pairing HPLC was used for the separation of Glufosinate and Glyphosate in Waters

• Tetrabutylammonium hydroxide is used as the ion‐pairing reagent

• Acetate buffer at pH 5

Preliminary Data on LC‐ICP‐MS Analysis of Phosphorus Containing Herbicides

Column: Zorbax SB‐C8, 4.6 x 150 mm, 5um

Mobile Phase: 50mM Ammonium Acetate/Acetic Acid Buffer (pH 4.7)5mM Tetrabutylammoniumhydroxide1% Methanol

Flow Rate: 1ml/min

10000

15000

20000

25000

30000

35000

1 2 3 4 5 6 7 8 9

AMPA

Glufosina

te

Glyph

osate

Retention Time (min)

ICPM

S Re

spon

se (C

PS)

Data courtesy Anne Vonderheide Uni Cincinnati

DL <100 ppt

P

O

CH 3

F

O CH

CH 3

CH 3

CH 3

CH 3

S oman (GD)

P

O

CH 3

F

O CH

CH 3

CH 3

S ar in (GB)

P

O

CH 3

S

O CH 2 CH 3

N

VX

N er ve Agent s

P

O

O

N

C N

TAbun (GA)

P

O

CH3

F

O

Cycl osar in (GF)

P

O

CH 3

S

O

N

CH 3

CH 3

Russian VX (RVX)

G-Type V-Type

P

O

CH 3

F

O CH

CH 3

CH 3

CH 3

CH 3

S oman (GD)

P

O

CH 3

F

O CH

CH 3

CH 3

S ar in (GB)

P

O

CH 3

S

O CH 2 CH 3

N

VX

N er ve Agent s

P

O

O

N

C N

TAbun (GA)

P

O

CH3

F

O

Cycl osar in (GF)

P

O

CH 3

S

O

N

CH 3

CH 3

Russian VX (RVX)

G-Type V-Type

31P Selective Detection

All these agents contain a P atom, so ICP‐MS can be used to identify and quantify the concentration of agent, based on the consistent (compound independent) response for 31P

Chemical Warfare Agent Analysis by ICP‐MS

From Doug Richardson, Univ Cincinnati

P

O

CH3

F

O CH

CH3

CH3

CH3

CH3

S oman (GD)

P

O

CH3

F

O CH

CH3

CH3

S ar in (GB)

P

O

CH3

OH

O CH CH3

CH3

IMPA

P

O

CH3

OH

O CH

CH3

CH3

CH3

CH3

PMPA

P

O

CH3

OH

OH

MPA

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

FastFast

S l owS l ow

P

O

O

N

CN

TAbun (GA)

P

O

CH3

F

O

Cycl osar in (GF)

P

O

CH 3

OH

O

CMPA (GF Acid)

P

O

O O CH 2 CH 3

NCH 3 CH 3

N a+

H2O

H2O

H2O

H2O

H2O

H2O Fast

EDPA (GA Acid)

H2O

H2O

H2O

H2O

H2O

H2O Fast

H2O

H2O

H2O

H2O

H2O

H2OS l ow

H2O

H2O

H2O

H2O

H2O

H2O

S l ow

P

O

CH3

F

O CH

CH3

CH3

CH3

CH3

S oman (GD)

P

O

CH3

F

O CH

CH3

CH3

CH3

CH3

S oman (GD)

P

O

CH3

F

O CH

CH3

CH3

S ar in (GB)

P

O

CH3

F

O CH

CH3

CH3

S ar in (GB)

P

O

CH3

OH

O CH CH3

CH3

IMPA

P

O

CH3

OH

O CH

CH3

CH3

CH3

CH3

PMPA

P

O

CH3

OH

OH

MPA

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

H2O

FastFast

S l owS l ow

P

O

O

N

CN

TAbun (GA)

P

O

O

N

CN

TAbun (GA)

P

O

CH3

F

O

Cycl osar in (GF)

P

O

CH3

F

O

Cycl osar in (GF)

P

O

CH 3

OH

O

CMPA (GF Acid)

P

O

O O CH 2 CH 3

NCH 3 CH 3

N a+

H2O

H2O

H2O

H2O

H2O

H2O Fast

EDPA (GA Acid)

H2O

H2O

H2O

H2O

H2O

H2O Fast

H2O

H2O

H2O

H2O

H2O

H2OS l ow

H2O

H2O

H2O

H2O

H2O

H2O

S l ow

G‐Type and V‐Type CWA Degradation Pathways


P

O

CH3

S

O CH2 CH3

N

VX

P

O

CH3 O CH2 CH3

OH

P

S

CH3 O CH2 CH3

OH

EMPA (VX Acid)EMPTA

H2O

H2O

H2O

H2O

H2O

H2O Fast FastH2O

H2O

H2O

H2O

H2O

H2O

P

O

CH 3

OH

O CH 3

CH 3

P

O

CH 3

S

O

N

CH 3

CH 3

Russian VX (RVX)

H2O

H2O

H2O

H2O

H2O

H2O Fast

IBMPA (RVX Acid)

H2O

H2O

H2O

H2O

H2O

H2O

S l ow

H2O

H2O

H2O

H2O

H2O

H2O

S l ow

P

O

CH3

OH

OH

MPA

P

O

CH3

S

O CH2 CH3

N

VX

P

O

CH3 O CH2 CH3

OH

P

S

CH3 O CH2 CH3

OH

EMPA (VX Acid)EMPTA

H2O

H2O

H2O

H2O

H2O

H2O Fast FastH2O

H2O

H2O

H2O

H2O

H2O

P

O

CH 3

OH

O CH 3

CH 3

P

O

CH 3

S

O

N

CH 3

CH 3

Russian VX (RVX)

H2O

H2O

H2O

H2O

H2O

H2O Fast

IBMPA (RVX Acid)

H2O

H2O

H2O

H2O

H2O

H2O

S l ow

H2O

H2O

H2O

H2O

H2O

H2O

S l ow

P

O

CH3

OH

OH

MPA

Left: G-Type CWA degradation pathways and products

Right: V-Type CWA degradation pathways and products

Elution Order1. MPA2. H2PO4

‐

3. EPA4. DMHP5. PPA6. EMPA7. IMPA8. DEHP9. IPHEP10. IBHMP

Right: Standards

Below: Unspiked and spiked Apple Juice

Column: Hamilton PRP-X100 Anion Exchange

0 5 10 15 20 25

0

10000

20000

30000

Res

pons

e (C

PS

)

Time (min)

31P

Apple Juice+ Spike (3ppm)

Apple Juice

Gradient Phenomenon

1

2

3 4

56

7 8 910

0 5 10 15 20 25

0

5000

10000

15000

20000

25000

30000

35000

Res

pons

e (C

PS)

Time (min)

31P

1

2

3

4

56

78

910

CWA Analysis in Natural Samples by LC‐ICP‐MS


Analytical Method Comparison

(1) Steiner, W. E.; Clowers , B. H.; Matz , L. M.; Siems , W. F.; Hill, H. H., Jr. Analytical Chemistry 2002 , 74 , 4343 ‐(2) Liu, Q.; Hu , X.; Xie , J. Analytica Chimica Acta 2004 , 512 , 93 ‐101(3) Wang, J.; Pumera , M.; Collins, G. E.; Mulchandani , A. Analytical Chemistry 2002 , 74 , 6121 ‐6125.

(1) Steiner, W. E.; Clowers , B. H.; Matz , L. M.; Siems , W. F.; Hill, H. H., Jr. Analytical Chemistry 2002 , 74 , 4343 ‐ 4352.(2) Liu, Q.; Hu , X.; Xie , J. Analytica Chimica Acta 2004 , 512 , 93 ‐101(3) Wang, J.; Pumera , M.; Collins, G. E.; Mulchandani , A. Analytical Chemistry 2002 , 74 , 6121 ‐6125.

* This Work – Ion Pairing Reversed Phase HPLC‐ICP‐MS

ng mL‐1

560 ‐ 1700 1

100 ‐ 1000 2

48 ‐ 86 3

0.139 – 0.263 *

Electrophoresis Microchip with Contactless

Conductivity Detector

LC‐ESI‐TOF

Ion Mobility Mass Spectrometry

Detection Limits (ppb)

Degradation Products

IP‐RP‐HPLC‐ICP‐MS

P

O

CH3

OH

OH

MPA

P

O

CH3

OH

OH

MPA

P

O

CH3

OH

O CH CH3

CH3

IMPA

P

O

CH3

OH

O CH CH3

CH3

IMPA

P

O

CH3 O CH2 CH3

OH

EMPA (VX Acid)

P

O

CH3 O CH2 CH3

OH

EMPA (VX Acid)


Method


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Agilent GC‐ICP‐MS Interface

Fully heated and insulated GC transfer lineModified torch with heated injector replaces standard demountable torch. “Silicosteel” transfer line and injector liner for inertnessGC capillary can be inserted to tip of injector or terminated in GC ovenGC effluent injected directly into base of plasma –essential for high boiling point compoundsSpecies decomposed to atoms ‐ atoms then ionized and passed into MS

Determination of Organotin Species in Sediment

200 250 300 350 400 450 500 550 600 650

2.5E5

5.0E5

[2] TIC:4-std3.d [Count]

sec->

TPhT590 sec

DPhT425 secTBT

328 sec

MPhT315 sec

DBT287 sec

TPrT264 sec

MBT243 sec

Retention time (sec)

Concentration PACS-2 CRM (pg l-1 Sn)Values MBT DBT TBT MPhT DPhT TPhT Certified (300) 1090±150 980±130 250±20

* 250±20* 250±20

* Found 947±27 914±74 947±28 230±17 219±17 228±30

(xxx) = non‐certified* = spiked species

Data Courtesy of Dr Olivier Donard, U. Pau, France

GC‐ICP‐MS for OT Speciation

Organotin compounds –Endocrine modulator

Mixed Siloxane Analysis by GC‐ICP‐MS

*MDL of approximately 0.5 pg Si *ORS H2 mode used for low Si DLs

GC‐ICP‐MS is an excellent detector for Si. H2cell gas used to remove N2 and CO polyatomics on 28Si, which are relatively low with GC anyway.

Consistent response for all Si compounds –same response factor

Siloxane standard mix.

All compounds between 30‐60 ppb as Si

Siloxane – Emerging concern

GC‐ICP‐MS of 17 PBDE Congener Mixture

Fast GC method allowed the difficult #209 congener (which decomposes at close to its boiling point) to be measured. The fast oven ramp would compromise the separation of some of the lower substituted congeners, but most congeners are not used commercially and column switching could be used to improve separation.

GC‐ICP‐MS calibration curves of individual PBDE congeners were linear from 1ppb to 1ppm and the lower detection limit is calculated at 150 ppt ‐ similar to µECD, even without extensive optimisation.

Data Courtesy of Steve Wilbur et al

17 PBDE Mix – each at 50ppb

PBDE – Emerging concern

CE‐ICP‐MS

Flow rates are low

Requires good optimised sample introduction at low flows

Requires very high sensitivity

• Or signals will not be measured accurately

Coupling is more difficult than with LC

Having good TRUE real time chromatography software is essential

time / s

intensity

/ cps

simultaneous separation of 12 different species of As, Se, Te and Sb

1 Arsenocholine

1

2

34 5

6

78 Selenite

8

9

10 Antimonate

10

11 Tellurite

11

2 Arsenobetaine3 Arsenite4 Dimethylarsinic acid5 Phenylarsonic acid6 Monomethylarsonic acid7 Arsenate

9 Selenate

12 Tellurate

AsSe

TeSb

12

Simultaneous separation of different species

Other valuable documents

Unique learning tool for ICP‐MS. A great reference for anybody interested in ICP‐MS. It has a great summary of the history and principlesof ICP‐MS. 5989‐3526EN 80 pages (2005)

As of Aug. 2008

Agilent’s ICP‐MS ‐ Sold in 70 countries

There are 192 countries in the world.36% (=69/192) is covered by Agilent.

Nigeria

South Africa

Jamaica

Puerto Rico

Chile

Peru

ColombiaVenezuela

Vietnam

Thailand

Qatar

Kazakhstan

Kuwait

IndiaVirgin Is.

Bulgaria

Trinidad

Ukraine

ICP‐MS in an Environmental Lab

Productivity

• Multielement• Wide dynamic range• Low detection limits

Sample Introduction Performance

• Well optimised sample introduction with lower polyatomics• Robust plasma and interface can handle samples with high TDS

Elimination of Interferences by CRC

• For those requiring low detection limits in complicated matrices

Friendly and intuitive software

• Faster learning curve for novices

Flexibility to meet future requirements

Agilent 7700 Series


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