Agilent Atomic Spectroscopy solutions for routine...

1

Agilent Atomic Spectroscopy solutions for routine Food & Agriculture applications

AA, MP-AES, ICP-OES,

ICP-MS.

AGENDA

Agilent Atomic Spectroscopy instruments overview

Types of applications in Food & Agriculture

Examples of available applications

1957

Built

components for

world's first AA

(as Techtron)

1971

Applies for

patent on

Zeeman

background

correction

1985

SpectrAA

instruments

released with

central

instrument

control

1987

Introduction of

the first

computer

controlled ICP-

MS, the PMS

100

1991

Releases first

sequential ICP-

OES

1994

Launch of the

4500 Series, the

world's first

benchtop ICP-

MS

1997

Fast Sequential

AA reduces

analysis times by 50%

1998

Releases first

simultaneous

ICP-OES with

full wavelength

coverage

2000

Launch of 7500

Series ICP-MS

2004

Introduction of

200 Series AA

and GTA120

GFAA with

extended tube

life

2006

Launch of the

700 Series ICP-

OES - world's

fastest ICP-

OES

2009

Launch of the

Agilent 7700

Series, with HMI,

3rd generation

ORS, and

Masshunter s/w

2011

Agilent redefines

elemental

analysis with the

introduction of

the Agilent 4100

MP-AES

2012

Agilent releases

the world's first

triple quad ICP-

MS, the Agilent

8800 ICP-QQQ

Agilent Technology Leadership, the first 55 years…

And still leading the way with recent innovative releases!

Agilent 4200 MP-AES

Safer, more cost effective elemental analysis that is uniquely suited for a wide range of sample types and applications.

- Reduce your analysis cost

- Improve your laboratory safety

- Simplify your workflow

- Increase analytical performance

Agilent 7900 ICP-MS

The most robust, sensitive, and easy to use quadrupole ICP-MS ever.

- 10x better matrix tolerance – up to 25% total dissolved solids

- 10x better signal to noise performance – improved sensitivity and detection limits

- 10x wider dynamic range – up to 11 orders of concentration from ppt to 10,000s ppm

- Software so simple yet powerful it writes your methods for you

- Enhanced customer experience – better training, easier maintenance

The new Agilent 5100 ICP-OES!

The world’s most productive, high performance ICP-OES.

- World’s first and only non-sequential dual view instrument; Synchronous Vertical Dual View (SVDV)

- Highest throughput reduces your analysis cost

- Vertical plasma runs your toughest sample

- Dichroic Spectral Combiner (DSC) simplifies method development

The Agilent Atomic Spectroscopy Instrument Family

Agilent’s 55 and 200 Series includes the

world’s fastest flame AA and

the world’s most sensitive

furnace

Agilent’s 4200 MP-AES runs on air for the lowest cost of ownership and

improved safety

Agilent’s 5100 ICP-OES is the

world’s most productive, and

only Synchronous Vertical Dual

View ICP-OES

Agilent’s 7900 is the most

robust, sensitive, and easy to use quadrupole

ICP-MS ever

Agilent’s 8800 ICP-QQQ provides accurate

measurement of difficult and

interfered elements

Types of applications in Food & Agriculture

6

Typical ‘routine’ applications

Agriculture crop yield optimization

• Extractable elements in fertilizers

• High levels of active ingredients (N-P-K), low levels of secondary (Ca, Mg,

S), and micro nutrients (B, Cu, Fe, Mn, Zn)

• Extractable elements in soils (soil quality)

• Nutrient and micronutrient content to monitoring deficiencies

Plant materials and animal feed

• Nutrients for optimal livestock growth/development

• Contaminants and toxic elements that pass into the animal tissues

February 2, 2015

Agilent restricted

7

http://www.chem.agilent.com/en-US/Solutions/Food-Testing-Agriculture/Soil-Quality-Fertilizer-Analysis/Pages/default.aspx

http://www.chem.agilent.com/en-US/Solutions/Food-Testing-Agriculture/Soil-Quality-Fertilizer-Analysis/Pages/default.aspx


Food quality/nutrients

• Dairy, meat, fish, grain, vegetables, fruit, processed goods, etc

• Essential minerals at high levels (Na, Mg, P, S, Ca, Fe, etc)

• Essential elements at low levels (V, Cr(III), Co, Se, I, etc)

Food safety

• Dairy, meat, fish, grain, vegetables, fruit, processed goods, etc

• Toxic trace elements (As, Cd, Hg, Pb, etc)

• Chemical form can determine toxicity (Cr(VI), As(III & V), MeHg, etc)

• Elements that are toxic in excess (Al, Ni, Cu, Zn, Se, etc)

• Food profiling/authenticity

February 2, 2015

Agilent restricted

8


Other related samples

• Water for irrigation

• Food additives / flavors / colors

• Packaging materials

February 2, 2015

Agilent restricted

9

Examples of available applications

10

5100 ICP-OES Applications

February 2, 2015

Confidentiality Label

11

Food testing & agriculture

Neli Drvodelic

Agilent Technologies Melbourne, Australia

Publication number: 5991-4868EN

Publication date: July 2014

Analysis of bovine liver using the Agilent 5100ICP-OES

Measurement challenge

13

Challenge

How to improve sample throughput and reduce operating costs in a

food testing lab whilst maintaining analysis sensitivity and

precision.

Solution

When analyzing a Bovine Liver certified standard, the Agilent 5100

Synchronous Vertical Dual View ICP-OES delivered excellent linear

dynamic range for the major elements (Na and K, up to 500ppm),

and good agreement with certified reference values for major,

minor, and trace level elements. Sample throughput was increased

by the ability to measure both axial and radial views of the plasma

in a single measurement. This also reduced the argon consumption.

Introduction

ICP-OES is a common technique used to test food products for a range of elements including nutrients, micro-nutrients and toxic elements.

Food testing laboratories often measure samples with complex matrices, and high dissolved solids content. This can cause build up on an ICP torch, resulting in poor long term stability and accuracy, and more instrument downtime for cleaning.

These labs typically require ease of use without sacrificing measurement accuracy, and excellent linear dynamic range for both major and trace elements. Low cost of analysis and high sample throughput is also required, as is fast sample turn around.

14

Results and discussion

15

Recoveries• Majority of results were within 5% of the certified/reference concentration

Table 2. Results for NIST Bovine Liver 1577 SRM

Element (nm) MDL

(mg/kg)

Measured values

(mg/kg)

SD Certified value

(mg/kg)

SD Recovery(%)

K 766 7.8 9832 5.2 9700 0.06 101

Na 589 9.08 2410 2.9 2430 0.013 99

Fe 238 0.17 258 1.9 270 20 96

Cu 327 0.16 203 1.1 193 10 105

Zn 213 0.33 131 0.56 130 10 101

Mn 257 0.008 9.8 0.01 10.3 1 96

Cd 228 0.13 0.26 0.02 0.27 0.04 96

Element (nm) MDL

(mg/kg)

Measured values

(mg/kg)

SD Reference value

(mg/kg)

Recovery (%)

Ca 396 6 126 0.16 123 103

Mg 279 0.83 603 2.4 605 100

Mo 202 0.18 3.4 0.05 3.2 106

Sr 407 0.01 0.142 0.002 0.14 102

Table 3. Results for NIST Bovine Liver 1577 SRM. Certified values are not available for the elements listed.

16

Conclusions

Certified bovine liver samples were analyzed using the Agilent 5100

SVDV ICP-OES.

The study found that:

• The instrument had an excellent linear dynamic range, up to 500 ppm,

for Na and K, from a single reading

• Accuracy was within 5-6% of the certified values for major and trace

elements

• Spike recoveries ranged from 99-110% when a 100 ppb spike was

performed for elements that were below the limit of quantification.

• High sample throughput was observed, with quicker sample

measurement delivering considerable gas savings

• Vertical torch resisted contamination and build-up, even with high

dissolved solids high and delivered robust analytical performance

• Features such as the plug and play torch, and intuitive software

interface, improve ease of use ensure reproducible performance

To find out more, visit agilent.com/chem

Food testing

Neli Drvodelic

Agilent Technologies Melbourne, Australia



Analysis of milk powders based on the Chinese standard method, using the Agilent 5100 ICP-OES

Measurement challenge

18

Challenge

How to measure elevated levels of Na, K and Ca in milk powder, whilst

also accurately measuring trace levels of toxic elements.

Solution

The Synchronous Vertical Dual View mode of the Agilent 5100 ICP-OES

proved ideal for this application.

The major elements were measured using the radial view of the plasma

and the trace elements using the axial view. This could all be done in a

single measurement – resulting in short sample measurement times and

reduced argon consumption.

Introduction

ICP-OES is a common technique used to test food products for a range of elements including nutrients, micro-nutrients and toxic elements.

Food testing laboratories often measure samples with complex matrices, and high dissolved solids content. This can cause build up on an ICP torch, resulting in poor long term stability and accuracy, and more instrument downtime for cleaning.

19

These labs typically require ease of use without sacrificing

measurement accuracy, and excellent linear dynamic range for

both major and trace elements. Low cost of analysis and high

sample throughput is also required, as is fast sample turn

around.

Results and discussion

20

Recoveries

• Recoveries ranged from

92-107%

• Wide dynamic range for

elements at ppb levels and at

% levels – in a single reading

Table 3. Recoveries from the analysis of NIST Milk Powder 8435 SRM

Element

(nm)

Certified

value

(mg/kg)

Measured

value(mg/kg)

Recovery

(%)

K 766.491 13630 13070 96

Ca 315.887 9220 9750 106

P 213.618 7800 7160 92

Na 589.592 3560 3530 99

S 181.792 2650 2650 100

Mg 279.078 814 749 92

Zn 202.548 28.0 28.9 103

Sr 421.552 4.35 4.37 101

Fe 259.940 1.8 1.9 107

Cu 327.395 0.46 0.46 100

Mo 204.598 0.29 0.27 92

Mn 257.610 0.17 0.18 103

21

Conclusion

Certified whole milk powder samples were analyzed using the Agilent

5100 SVDV ICP-OES.

The study found that:

• Trace toxic and major nutrient elements were able to be measured in

a single measurement, without ionisation buffers

• Method detection limits were better than required by the method

• Excellent recoveries (92-107%) were achieved for all elements –

instrument was accurate over a large dynamic range

• High sample throughput was observed, with the quicker sample

measurement delivering considerable gas savings

• Vertical torch resisted contaminations and build-up, even with high

dissolved solids and delivered stable and robust analytical

performance

To find out more, visit agilent.com/chem

Example ICP-OES Applications (700 series)

February 2, 2015


22

• Elemental analysis of food (routine monitoring for food safety)

• “Fingerprinting” (Agilent package with MPP - chemometrics)

• Speciation

- LC-ICP-MS – As in juice

- GC-ICP-MS – pesticides, volatiles

- FFF-ICP-MS – nanoparticle characterization

Key ICP-MS Applications in Food Analysis

Importance of Food Applications – Public Interest

Huge public interest; major news items each week relating to food safety:

1. Nutrition (5 a day, Se supplementation)

2. Toxicity (As in apple juice and brown rice syrup)

3. Contamination (Hg in seafood, melamine in baby formula)

4. Adulteration and fraud (dilution, substitution, mislabelling; horse meat in “beef” burgers; smuggling, import tax avoidance)

5. Production, additives and packaging (nanoparticle leaching)

Trace elements are complementary to DNA testing – trace elements vary by region (and sometimes method) of production, so can differentiate cases where the same foodstuff has different value depending on where it came from: olive oil, honey, juice, wine…

Toxicity, bioavailability and nutrition all depend on chemical form of the element (speciation). Agilent is WW leader in speciation with ICP-MS

Agilent offers complete solution – separation (LC, GC, CE (FFF)), inorganic and organic mass spec, chemometrics, data security and reporting

7900 ICP-MS Applications

February 2, 2015


25

ICP-QQQ Extends Range of ApplicationsMore effective interference removal and higher sensitivity

• Accurate, low-level analysis of non-metals – Se & As

• Analysis of S, P, Cl… Quantitation of non-metal containing

biomolecules; enables monitoring of metabolic functions

Food testing

Kazuhiro Sakai et al

Agilent Technologies Japan


Publication date: May 2014

Method automation for analysis of trace elements in foods by ICP-MS

ExperimentalMethod building

28

Automatic mode

Based on the current instrument configuration and the

composition of the user’s own reference sample, which is

measured as part of the method setup, the Method Wizard

automatically selects the most appropriate:

• operating conditions (plasma mode and tuning conditions)

• analyte isotopes

• integration times

• cell gas modes

• internal standards

.

ExperimentalMethod building – Automatic mode

30

• Sample uptake and rinse times are calculated from the tuning solution

measurement.

• Total dissolved solids (TDS) level and major element composition are

derived from the results of the semi-quantitative analysis of the typical

sample.

• The measured TDS level is used to determine the appropriate plasma

mode (Low Matrix, General Purpose, UHMI-4, -8, -25)

• The major element composition is used to identify potential matrix-based

interferences and to select the most appropriate cell mode (no gas, He,

High Energy (HE)He, H2), isotope, integration time and ISTD for each

analyte.

Results and discussionAnalytical results

31

Accurate analytical results of food CRMs measured using method created by ICP-MS MassHunter's Method Automation function

Analyte UnitDORM-4 (fish protein) 7402-a (cod fish tissue) 7403-a (swordfish tissue)

Concentration Certified Concentration Certified Concentration Certified

9 Be [No gas] mg/kg 0.01 ± 0.00 N.D. (<0.0008) N.D. (<0.0008)

23 Na [No gas] g/kg 12.9 ± 0.3 3.4 ± 0.1 3.6 ± 0.2 3.57 ± 0.07 3.57 ± 0.12

24 Mg [No gas] g/kg 0.81 ± 0.01 1.29 ± 0.03 1.34 ± 0.03 1.60 ± 0.03 1.58 ± 0.04

31 P [HEHe] g/kg 7.6 ± 0.2 10.8 ± 0.1 12 14.5 ± 0.2 14.5 ± 0.4

34 S [HEHe] g/kg 8.7 ± 0.2 10.4 ± 0.1 8.43 ± 0.06

39 K [H2] g/kg 12.6 ± 0.6 21.3 ± 1.2 22.3 ± 1.0 25.5 ± 0.8 26.3 ± 1.1

40 Ca [H2] g/kg 2.18 ± 0.11 0.46 ± 0.03 0.52 ± 0.05 0.196 ± 0.014 0.189 ± 0.009

51 V [He] mg/kg 1.50 ± 0.01 N.D. (<0.014) N.D. (<0.014)

52 Cr [He] mg/kg 1.75 ± 0.09 1.87 ± 0.16 0.67 ± 0.00 0.72 ± 0.09 0.058 ± 0.001

55 Mn [He] mg/kg 3.02 ± 0.11 0.41 ± 0.03 0.41 ± 0.03 0.190 ± 0.004 0.201 ± 0.010

56 Fe [H2] mg/kg 339 ± 20 341 ± 27 11.2 ± 0.5 11.2 ± 0.9 13.6 ± 0.7 13.1 ± 0.5

59 Co [He] mg/kg 10.7 ± 0.09 0.030 ± 0.003 0.04 0.015 ± 0.001

60 Ni [He] mg/kg 1.26 ± 0.11 1.36 ± 0.02 0.40 ± 0.10 0.38 ± 0.05 0.076 ± 0.037

63 Cu [He] mg/kg 15.8 ± 0.1 15.9 ± 0.9 1.13 ± 0.02 1.25 ± 0.07 1.26 ± 0.02 1.31 ± 0.04

66 Zn [He] mg/kg 49.3 ± 0.5 52.2 ± 3.2 20.5 ± 0.2 21.3 ± 1.5 33.3 ± 0.2 33.6 ± 1.0

75 As [HEHe] mg/kg 6.73 ± 0.08 6.80 ± 0.64 36.4 ± 1.1 36.7 ± 1.8 6.77 ± 0.13 6.62 ± 0.21

78 Se [H2] mg/kg 3.47 ± 0.12 3.56 ± 0.34 1.8 ± 0.1 1.8 ± 0.2 2.11 ± 0.06 2.14 ± 0.11

88 Sr [He] mg/kg 9.72 ± 0.10 1.74 ± 0.03 2 1.08 ± 0.02 1.13 ± 0.03

95 Mo [He] mg/kg 0.261 ± 0.005 0.010 ± 0.006 0.01 N.D. (<0.0008)

107 Ag [He] mg/kg 0.022 ± 0.001 N.D. (<0.0050) N.D. (<0.0050)

111 Cd [He] mg/kg 0.304 ± 0.001 0.306 ± 0.015 0.009 ± 0.000 0.009 0.152 ± 0.003 0.159 ± 0.006

118 Sn [He] mg/kg 0.077 ± 0.004 0.056 ± 0.010 0.016 ± 0.002 0.036 ± 0.001

121 Sb [He] mg/kg 0.009 ± 0.000 0.014 ± 0.001 0.02 0.002 ± 0.001

137 Ba [He] mg/kg 5.01 ± 0.03 0.027 ± 0.002 2.4 ± 0.02

202 Hg [He] mg/kg 0.358 ± 0.004 0.410 ± 0.055 0.53 ± 0.01 0.61 ± 0.02 5.02 ± 0.02 5.34 ± 0.14

205 Tl [He] mg/kg 0.001 ± 0.002 N.D. (<0.010) N.D. (<0.010)

208 Pb [He] mg/kg 0.405 ± 0.007 0.416 ± 0.053 0.03 ± 0.00 0.04 0.006 ± 0.003

232 Th [He] mg/kg 0.177 ± 0.002 N.D. (<0.0008) N.D. (<0.0008)

238 U [He] mg/kg 0.056 ± 0.005 N.D. (<0.0010) N.D. (<0.0010)

Food testing

Wim Proper & Ed McCurdy

Eurofins Analytico; Agilent Technologies UK


Publication date: April 2014

Analysis of High Salt Matrices using the 7900 with UHMI

High Salt Matrix Analysis: ExperimentalAnalytical procedure

• For the performance tests on the high NaCl matrices (up to 25% NaCl),

UHMI-100 (~100x aerosol dilution) was selected because it gives the

maximum robustness and tolerance of exceptionally high matrix levels.

• The instrument settings used are shown in Table 1.

• All lens voltages were optimized using the ICP-MS MassHunter autotune

function. It is clear that most parameters are consistent for the two gas

modes used.

• Analysis of a range of trace elements of interest was performed in salt

matrices ranging from zero added NaCl to 25% NaCl solution.

• All samples were measured against simple aqueous calibration standards

(no NaCl matrix), prepared in the same acid mix as the samples (0.5%

HNO3 and 0.6% HCl).

34

Results and discussionEvaluation of UHMI matrix tolerance for high NaCl

35

Low level of matrix suppression (~50%) and no long-term drift for internal standard signal for sequence including

50 samples of 25% NaCl matrix

Aqueous standards

and rinse

25% NaCl Matrix

samples

Initial signal drop due to

sample transport and

nebulization effects

Results and discussionAccurate analysis in variable NaCl matrices

37

Left. Spike recovery for As, Cd,

Hg and Pb in variable NaCl

matrices up to 25% NaCl

Right. Spike recovery for interfered

elements V (ClO), Cr (ClOH), Ni

(NaCl) and Cu (ArNa) in variable

NaCl matrices up to 25% NaCl

Results and discussionAnalysis of commercial table salt samples

Commercial table salts were purchased and analyzed in order

to test the application of the method for trace element

characterization of food-grade salt.

Sea salts and rock salts were sourced from various countries.

The analytical results obtained are shown in Table 3 for

information; no reference or expected concentrations were

available for these salt samples.

For simplicity, only the elements that were found at significant

levels or showed a high degree of variation between the

samples are shown.

38

39

Units SICJ

Japan,

Mexico,

Australia

seawater

Japan, Izu,

seawater

Japan,

Mexico,

Australia

seawater

Japan, Seto,

seawater

Japan,

seawater

Mexico,

seawater

Germany,

rock

Li µg/L 14 60 140 40 160 44 1.4 100

Mg mg/L 51 430 1500 190 350 130 91 150

Al µg/L 0.22 0.13 0.38 0.15 0.23 0.16 0.048 56

S mg/L 59 520 2000 490 76 48 51 51

K mg/L 250 190 470 150 560 180 59 150

Ca mg/L 56 210 740 310 210 86 1.3 720

V µg/L 0.11 0.12 0.53 0.21 0.47 0.13 2.8 7.7

Cr µg/L 0.19 0.35 0.39 0.18 0.22 0.23 0.66 10

Mn µg/L 4 0.084 0.071 0.14 4.4 1.5 0.049 26

Fe µg/L 0.85 1.1 1.4 1.1 1.4 1 1 120

Cu µg/L 1.3 0.13 0.74 0.082 42 10 0.082 6.4

Zn µg/L 1.6 0.068 0.02 0.085 3.7 2.7 0.046 8.8

Ga µg/L 0.0079 0.021 0.04 0.033 0.017 0.013 0.0072 0.046

As µg/L 0.13 0.3 0.52 0.16 0.1 0.2 0.22 0.32

Se µg/L 1 0.6 0.43 0.56 0.71 0.45 0.66 0.8

Br mg/L 120 42 100 34 330 95 10 32

Rb µg/L 18 38 110 22 240 54 0.16 81

Sr mg/L 0.3 2.8 4 4.8 1.6 0.66 0.047 0.1

Zr µg/L 0.0093 0.0031 0 0 0 0 0.016 0.24

Mo µg/L 0.25 3.2 12 1.7 2.1 0.18 1.2 0.21

Ag µg/L 2.9 7.8 8.7 4 3.6 1.6 2.4 43

Table 3. Analytical results of commercial table salts produced in various countries from rock salt or sea salt


40

Units SICJ

Japan,

Mexico,

Australia

seawater

Japan, Izu,

seawater

Japan,

Mexico,

Australia

seawater

Japan, Seto,

seawater

Japan,

seawater

Mexico,

seawater

Germany,

rock

Cd µg/L 0.19 0.092 0.26 0.045 0.17 0.12 0.59 1.4

Sn µg/L 0.12 0.092 0.06 0.12 0.076 0.094 0.067 0.4

Sb µg/L 0.019 0.11 0.31 0.021 0.011 0.021 0.064 0.27

Te µg/L 2.9 0.96 1 1.1 4 1.5 0.7 0.72

I µg/L 0.82 38 43 41 160 41 85 120

Cs µg/L 0.098 0.13 0.33 0.081 1 0.22 0.019 12

Ba µg/L 0.97 12 17 11 5.1 1.9 0.51 3

W µg/L 0.25 0.016 0.022 0.02 0.069 0.07 0.11 0.069

Au µg/L 0.071 0.044 0.034 0.054 0.055 0.064 0.081 0.072

Hg µg/L 0.065 0.03 0.035 0.053 0.026 0.032 0.16 0.038

Pb µg/L 1.7 0.21 0.37 0.067 0.26 0.27 0.054 2

Table 3 continued. Analytical results of commercial table salts produced in various countries from rock salt or sea salt


Conclusion

The Agilent 7900 ICP-MS with UHMI allows ICP-MS to be used for the first

time for the direct analysis of trace elements in very high matrix samples,

without prior sample dilution. The new UHMI system extends the aerosol

dilution range up to a factor of 100, tolerating TDS levels of up to 25% (10

times higher than the previous generation HMI), a matrix level 100 times

above the accepted limit for conventional ICP-MS systems.

The 7900 ICP-MS with UHMI option was used to analyze a wide range of

elements in undiluted saturated salt water and various commercially

available table salts. The analysis demonstrates a level of matrix tolerance

that is unprecedented in ICP-MS. This capability extends the use of ICP-MS

for samples with a very high salt matrix, offering a possible alternative to AA

or ICP-OES techniques.

For additional information, please visit the Agilent 7900 ICP-MS or

Environmental, Food or Energy and Chemicals websites.

43

http://www.chem.agilent.com/en-US/products-services/Instruments-Systems/Atomic-Spectroscopy/7900-ICP-MS/Pages/default.aspx

http://www.chem.agilent.com/en-US/Solutions/Environmental/Pages/default.aspx

http://www.chem.agilent.com/en-US/Solutions/Food-Testing-Agriculture/Pages/default.aspx

http://www.chem.agilent.com/en-US/Solutions/Energy-Chemicals/Pages/default.aspx

ICP-MS and MPP for Region of Origin Analysis of Chinese Honey

Food testing

Hui Chen et al

Chinese Academy of Inspection and Testing



Mass Profiler Professional (MPP) and ICP-MSChemometrics Software for Trace Element Fingerprinting

February 2, 2015

Agilent restricted

45

ICP-MSCan analyse up to ~70 elements in a fast

screening scan (using He mode to remove

matrix-based polyatomic interferences)

Data are transferred to MPP

MPPFlexible chemometrics software can identify

main distinguishing parameters, apply

several different statistical processes and

filters, model population classification and

display results in easily interpreted graphical

plots

Honey Sample Collection, Preparation and Analysis

RF power (W) 1550

Sample depth (mm) 8

Carrier gas (L/min) 1.1

Plasma gas (L/min) 15

Spray chamber temp (oC) 2

He cell gas (mL/min) 4.3

Number of replicates 3

February 2, 2015

Agilent restricted

46

Samples and Sample Preparation163 honey samples including varieties produced from linden, vitex, rape, and acacia

plants were collected from beekeepers located in 4 geographical locations in China.

The honey samples were digested using a MARS 6 microwave oven (CEM Corp.,

USA). Full details are given in Ref. 1.

InstrumentationAn Agilent 7700x ICP-MS with standard glass concentric nebulizer, quartz double-

pass spray chamber, and nickel sampler and skimmer cones was used for the

analysis. The instrument conditions are given below

Results and discussion – MPP DataIdentification of Region (botanical origin) for Chinese Honeys

47

Ref: Chemometric Determination of the Botanical Origin for Chinese Honeys on the Basis of Mineral

Elements Determined by ICP-MS, Hui Chen, Chunlin Fan, Qiaoying Chang, Guofang Pang, Xueyan

Hu, Meiling Lu, and Wenwen Wang, J. Agric. Food Chem. 2014, 62, 2443−2448

Figure 1. Two first-component scores of honeys from different botanical origins: linden

(■), vitex (▲), rape (●), and acacia (◆) honey.

LC-ICP-MS for As Speciation in Apple Juice

Food testing

Tanoshima et al

Agilent Japan



LC-ICP-MS for As Speciation in Apple Juice

February 2, 2015

Agilent restricted

49

Routine LC-ICP-MS Method with simple

filtration sample prep

Linear calibrations for As(III) and As(V) shown

below. Excellent sensitivity and stability

Routine Arsenic Speciation in Apple Juice1ug/L Spike Stability and Overlaid Chromatograms (n = 7)

50

Retention Time (min) Concentration (ug/l)

Sample Name AB DMA As(III) MMA As(V) AB DMA As(III) MMA As(V)

Apple Juice 1 Spike #1 2.77 3.62 4.19 6.43 10.62 0.85 1.11 1.61 0.98 1.52







Average 2.78 3.61 4.18 6.41 10.65 0.87 1.13 1.63 1.00 1.56

RSD % 0.28 0.16 0.23 0.48 0.27 1.53 1.20 0.91 1.29 1.55

Excellent sensitivity

and stability

As Speciation in Six Apple Juice Samples

February 2, 2015

Agilent restricted

51

Fast analysis (<12

minutes) of total and

toxic inorganic (As(III)

and As(V)) species

Simple sample prep –

filtration. No sample

digestion, so avoid

contamination and

species conversion

Easy to screen for

high As levels

Total As and species

varies according to

region of production

and historical land use

4200 MP-AES Applications

February 2, 2015


52

4200 App Note Major elements in Fruit Juice…perfect for MP-AES

• Undiluted juice has 11% TDS (mainly sugars) with major

elements ranging from 20ppm (Na) -1100ppm (K)

• Diluted 20x and acidified 5% HNO3. (0.6%TDS)

• Dilution required due to high level of sugars slowly blocking

sample introduction components.

• Working range for the major elements for the MP-AES at the

20 x diluted levels was 1-55ppm. (This is much higher than

AAS)

February 2, 2015


53

New 4200 App NoteMajor elements in Fruit Juice…perfect for MP-AES

Apple Juice

T0840QC

Certified Value (mg/L) Found

(mg/L)

%Recovery

Assigned Value Range

Magnesium 49.0 40.3 – 57.8 49.9 ± 0.6 101.9

Sodium 21.2 16.9 – 25.4 22.2 ± 0.5 104.7

Potassium 1044 926 -1161 1039 ± 29.7 99.5

Grapefruit

Juice

T0842QC

Certified Value (mg/L) Found

(mg/L)

%Recovery

Assigned Value Range

Calcium 145.6 123.6 – 167.6 158.3 ± 3.2 108.7

Magnesium 92.5 77.5 – 107.4 91.1 ± 0.6 98.5

Potassium 1102 979 – 1225 1100 ± 14.7 99.8

February 2, 2015


54

Basic Cost Estimation applied to Fruit Juice App

February 2, 2015Confidentiality Label

55

Apple and Grapefruit Juice compared to AAS

On AAS, the reduced LDR means sample needs to be diluted further compared to MP-AES

On AAS, having to run Ca and Mg on the same sample means 2 different burners required and 3 different gases. Slow throughput will not be reduced even with FS when a burner change is needed.

On AAS, as easily ionisable Na and K need to be determined, will need to add ionisation buffer to each sample and standard.

CONCLUSION:

Using the MP-AES for the major elements in fruit juice is easier, faster and is done at lower running costs compared to FAAS.

Approx $32,000 per year savings on 500 samples per week, 3 elements compared to AAS.

February 2, 2015Confidentiality Label

57

Determination of major, minor and trace elements in rice flour using the 4200 (MP AES)

John Cauduro

2 February 2015

Page 58

Sample PreparationNIES CRM 10c Rice Flour

• Digested in Milestone Ethos microwave using preloaded

method

• 0.5g in 7 mL of HNO3 and 1 mL H2O2

• Digested, cooled then diluted to 25 mL

• Final total dissolved solids of 2%

No further sample preparation required

No modifiers or ionization buffers required

2 February 2015


59

ResultsCRM Recoveries

mg/kg in

solid

Ca

422.673

Cd

228.802

Cu

324.754

Fe

438.354

K

766.491

Mg

280.271

Mn

403.076

P

214.915

Zn

213.857

Mean 96.0 1.96 4.13 11.50 2700 1174 37.35 3139 22.02

SD 2.5 0.11 0.29 1.03 105 23 1.04 92 0.48

Certified

value95 1.82 4.1 11.4 2750 1250 40.1 3350 23.1

2SD

certified2 0.06 0.3 0.8 100 80 2.0 80 0.9

%

Recovery101.0 107.7 100.8 100.9 98.2 93.9 93.1 93.7 95.3

2 February 2015


60

• Accurate determinations over a wide concentration range

• All in one sample measurement

Conclusion4200 MP-AES is the Ideal FAAS Replacement

Improved Performance

• Increased working range

• Phosphorus

• Lower detection limits

Reduced Running Costs

• Runs on Air!

• No modifiers

Increased safety

• No acetylene

• No nitrous oxide

Ease of Use

• MP Expert

• Simple sample prep

• No burner change over

2 February 2015


61

Example 4100 MP-AES Applications (applicable to 4200 also)

February 2, 2015


62

February 2, 2015

Agilent restricted

63

Example AA Applications

02 February 2015


63

Conclusions:A portfolio to cover any Food & Ag applicationIn some cases, a sample/application may be suitable for more than one

technique, eg:

• Metals in wine: FAAS, MP-AES, ICP-OES or ICP-MS

• Heavy soil digest: ICP-OES, ICP-MS (UHMI)

Others requirements might also drive your choice, such as number of

samples, operating budget, and operator skill…

Regardless of your application needs and drivers, Agilent’s unique and

comprehensive Atomic Spectroscopy Portfolio provides the right solution for

your Food & Agriculture analysis requirements.

Agilent Atomic Spectroscopy solutions for routine...

Documents

Transcript of Agilent Atomic Spectroscopy solutions for routine...