Analysis of pesticide residues The LCMS-8045 workhorse ......Stainless steel is used in the pro -...

Soil pollution

Analysis of pesticide residues

Boosts productivity

The LCMS-8045 workhorse system with key features of UFMS

New solutions for tomorrow

Shimadzu European Innovation Center

Pharmaceutical

Plastics and Rubber

CONTENT

Clinical

Chemical, Petrochemical,Biofuel and Energy

Pesticides: killers of bee colonies 2

Investigating soil pollution –Analysis of pesticide residues in soils using supercritical fluids 6

New formaldehyde determinationmethod 8

How reliable are additively manu -factured alloys under very high cyclefatigue (VHCF) loading? 10

Colorful packaging – with big know how – Risks from printed food packaging 12

TOC determination of a PFOS solution 15

Complete solution for mycotoxinanalysis 16

E-cigarettes – Heavy metals ine-liquids and e-vapors 18

Arsenic in Beer? Determination of heavy metals in beer using ICP-MS spectrometry 22

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On the safe side with MCERTS accreditation – Online TOC-4200reveals its strengths during fieldtests 26

New solutions for tomorrow –Launch of Shimadzu EuropeanInnovation Center 28

LATEST NEWS

MARKETS

Boosts productivity –The LCMS-8045 workhorse systemwith key features of UFMS to improvethroughput 21

Safety of people in modern transport – One metal shaving, and five minutes are enough 25

PRODUCTS

SHIMADZU NEWS 1/2017

Food, Beverages, Agriculture

Environment

Automotive

Pesticides: killers ofbee coloniesUltra-sensitive and rapid assay of neonicotinoids,fipronil and some metabolites in honey by UHPLC-MS/MS

Table 1: List of commercial neonicotinoids

Acetamiprid

Clothianidin

Imidacloprid

Thiacloprid

Thiamtehoxam

Dinotefuran

Nitempyram

Commercialized by Scotts & Bayer Cropsciences

Commercialized by Bayer Cropsciences

Commercialized by Bayer

Commercialized by Bayer

Commercialized by Syngenta

Commercialized by Mitsui Chemicals

Commercialized by Jiangsu Sword Agrochemicals

Figure 1: Overview of the UHPLC-MS/MS system

N eonicotinoids are a classof insecticides widely usedto protect crop areas such

as corn, canola and soybean aswell as fruit and vegetables.These substances have an influ-ence on the central nervous sys-tem of insects, causing paralysisand death. The first neonicoti-noid, imidacloprid, was discov-ered by Shinzo Kagabu (BayerCropScience, Japan). Their sys-temic distribution with high effi-ciency against sucking insects andlong residual activity has madethem very popular within theglobal pesticide market. Nowa -days, there are roughly ten mole-cules classified as neonicotinoids(please see table 1).

Use of these compounds hasrecently become controversial asthey are believed to be a cause ofhoneybees Colony Collapse Dis -order (CCD). Since pollination isessential for agriculture, extensive

risks to bees in the use of neoni-cotinoids. Three types of insecti-cides are involved: clothianidin,imidacloprid and thiamethoxam.They may have acute and chroniceffects on survival and develop-ment of bee colonies, their be -havior and larvae.

Following this, the EuropeanFood Safety Authority (EFSA)limited the use of thiamethoxam,clothianidin and imidacloprid.Some European countries havebanned or restricted the use ofneonicotinoids.

In order to better understand theeffect of these compounds onbees and their contamination inpollen and honey, a highly sensi-tive assay method was necessary.For this purpose, an UHPLC-MS/MS analysis was developedincluding the controversial andwell-known fipronil compound.Fipronil is a broad-spectruminsecticide of the phenylpyrazolechemical family and disrupts theinsect central nervous system inthe same manner as other neoni-cotinoids.

studies have been conducted toevaluate the impact of neonicoti-noids on bee health.

The European Food SafetyAuthority (EFSA) has identified

Acetamiprid

Fipronil sulfone

Acetamiprid-N-desmethyl Chlothianidin Dinotefuran Fipronil

Imidacloprid Nitenpyram Thiacloprid Thiamethoxam

0.00

%

100.00

0.00

%

100.00

0.0

%

100

0.00

%

73.21

0.00

%

100.00

2.10 2.20 2.30 2.40 2.10 2.20 2.30 2.40 2.00 2.15 2.25 2.30 1.50 1.60 1.70 1.80 3.00 3.10 3.20 3.30

0.00

%

100.00

0.00

%

100.00

0.00

%

100.00

0.00

%

100.00

0.00

%

100.00

3.05 3.15 3.25 3.35 2.00 2.10 2.20 2.30 1.55 1.65 1.75 1.85 2.25 2.35 2.45 2.55 1.80 1.90 2.00 2.10

SystemColumnColumn temperatureMobile phases

Flow rateGradient

Injection volume

Parameter

Nexera X2ACE Super C18 100 x 2.1 mm 2 µm30 °CA: Water + 0.05 % ammoniaB: Methanol + 0.05 % ammonia0.6 mL/min5 % B to 100 % B in 3 min. 100 % B to 5 % in 0.1 min.Total run time 6 min.1 µL (POISe mode with 10 µL of water)

Value

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

1 2 3 4 5 6 7 8 9 10

Are

a ra

tio

Concentration ratio

y = 0.042735x - 0.000002R2 = 0.999818 R = 0.999909

Curve fit: Default (linear)Weighting: Default (1/x)Zero: Defould (not forced)

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Table 2: UHPLC parameters

Materials and Methods

Standards and Reagents

All of the analytical standardswere provided by Sigma-Aldrich.The Internal standards thiameth -oxam-d3, imidacloprid-d4 andchlothinidin-d3 were purchasedfrom Sigma-Aldrich. The solventsused, including water and mobilephase additive, were of UHPLC/MS quality (Biosolve).

Sample Preparation

Compound extraction was per-

formed using a QuEChERS meth -od (Quick, Easy, Cheap, Effective,Rugged and Safe) with an addi-tional dispersive Solid PhaseExtraction (dSPE) step. 5 g ofhoney (± 1 %) were weighed in a 50 mL polypropylene tube. 5 µL of internal standard solutionat 5 µg/mL of each compound inacetonitrile was added to the hon -ey and dried for ten minutes. 10 mL of ultra-pure water weresubjoined, and the samples wereho mogenized by vortex mixing for one minute. 10 mL of acetonitrilewere then added followed by vor-tex mixing for one minute.

Salts mix (4 g MgSO4, 1 g SodiumCitrate, 0.5 g Sodium Citratesesquihydrate, 1 g NaCl; BiotageQ0020-15V) were added to thesamples. After manual shaking,samples were centrifuged at 3,000 gfor five minutes at 10 ºC.

The supernatant (6 mL) was trans-ferred into a 15 mL tube contain-ing 1,200 mg MgSO4, 400 mg PSAand 400 mg C18 (Biotage Q0050-15V). After centrifuging at 3,000 gand 10 ºC for five minutes, thesupernatant was transferred intoinert glass vial for analysis(Shimadzu LabTotal 227-34001-01).

UHPLC-MS/MS Conditions

Analysis was performed using aNexera X2 UHPLC system cou-pled with LCMS-8060 triple

quadrupole mass spectrometerwith Heated ESI in positive andnegative ionization (figure 1).Mobile phase composition wasoptimized to generate the highestsensitivity. Ion source parameters(gas flows, temperatures) were alsooptimized using the Interface Set -ting Support Software (ShimadzuCorp.) �

Figure 2: Chromatogram of the target compounds at their lower limit of quantification

Figure 3: Calibration curve of clothianidin

7 to 16 msec depending upon the number of concomitant transitions to ensure to have at least 30 points per peak (max total loop time 115 msec).1 msec.Q1: Unit Q3: UnitHESI: 400 °C DL: 200 °C Heater block: 400 °CInterface: 10 L/min Nebulizer: 3 L/min Drying: 5 L/min

Polarity++++––+++++++

SystemIonization modeAcquisition modeMRM transitions

Dwell time

Pause timeQuadrupole resolutionTemperatureGaz flow

LCMS-8060Positive HESIMRM

NameAcetamipridAcetamiprid-N-desmethylClothianidinDinotefuranFipronilFipronil sulfoneImidaclopridNitenpyramThiaclopridThiamtehoxamThiamethoxam-D3Imidacloprid-D4Clothianidin-D3

MRM quan.223.1 > 126.0209.1 > 126.0250.1 > 169.1203 .0 > 114.0435.0 > 330.0451.0 > 415.0256.1 > 175.1271.0 > 126.0253.1 > 126.0292.1 > 211.1

295.1 > 214.05260.1 > 179.1

253.1 > 132.05

MRM qual.223.1 > 56.1

211.1 > 128.0250.1 > 132203.0 > 87.0

435.0 > 250.0451.0 > 282.0258.1 > 211.1271.0 > 225.0253.1 > 90.1

292.1 > 181.1––––––

ISTD group2231332311123

Parameter Value

Acetamiprid

Fipronil sulfone

Acetamiprid-N-desmethyl Chlothianidin Dinotefuran Fipronil

Imidacloprid Nitenpyram Thiacloprid Thiamethoxam

0.0e02.0e44.0e46.0e48.0e41.0e51.2e51.4e51.6e51.8e52.0e5

0.0e0 0.0e0 0.0e0 0.0e0 0.0e01.0e22.0e23.0e24.0e25.0e26.0e27.0e28.0e29.0e21.0e31.1e3

2.0e34.0e36.0e38.0e31.0e41.2e41.4e41.6e41.8e42.0e4

1.0e3

2.0e3

3.0e3

4.0e3

5.0e3

6.0e3

7.0e3

2.0e3

4.0e3

6.0e3

8.0e3

1.0e4

1.2e4

1.4e4

1.6e4

2.0e1

4.0e1

6.0e1

8.0e1

1.0e2

1.2e2

1.4e2

1.6e2

1.8e2

0.0e0 0.0e0 0.0e05.0e21.0e31.5e32.0e3

0.0e02.0e04.0e06.0e08.0e01.0e31.2e31.4e31.6e31.8e32.0e32.2e3

2.5e33.0e33.5e34.0e34.5e35.0e3

5.0e2

1.0e3

1.5e3

2.0e3

2.5e3

3.0e3

3.5e3

5.0e21.0e31.5e32.0e32.5e33.0e33.5e34.0e34.5e35.0e35.5e36.0e3

2.10 2.20 2.30 2.40 2.10 2.20 2.30 2.40 2.00 2.10 2.20 2.30 1.50 1.60 1.70 1.80 3.00 3.10 3.20 3.30

3.10 3.20 3.30 3.40 2.00 2.10 2.20 2.30 1.60 1.70 1.80 1.90 2.25 2.35 2.45 2.55 1.80 1.90 2.00 2.10

Real Samples Analysis

Nine honey samples purchased atthe local supermarket or used asraw materials in cosmetics (orangetree honey) were assayed as un -knowns. All honeys tested showedconcentrations far below the maxi-mum allowable residue limit. Butthanks to the very high sensitivityreached, even low concentrationsof neonicotinoids were quantified.Results are presented in table 7.

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4 SHIMADZU NEWS 1/2017

Results

Calibration

The calibration curves were pre-pared in acetonitrile in order toobtain final concentrations rangingfrom 2.5 pg/mL (2.5 fg on col-umn) to 5 ng/mL. These concen-trations correspond to 5 ppt and10 ppb in honey respectively. Atypical calibration curve is shownin figure 3 (page 3).

Recovery

An “all-flowers” honey from thelocal supermarket was extractedwith or without spike at 50 ppt. A blank extract (no honey) wasprepared to evaluate losses or non-specific interactions. Results arepresented in table 5.

All calculated recoveries were with -in acceptance values of 70 - 120 %from EU SANTE/11945/ 2015.

Stability

The thyme honey sample with nodetectable target compound wasspiked at 50 ng/kg with all com-pounds prior to extraction. Theextract obtained was then consecu-tively injected 150 times in thesystem.

The results presented in figure 5show excellent stability of the sig-nal even at these low concentra-

Figure 4: Chromatogram of a sample honey (pyrenees)

Table 3: MS parameters

Provence creamyItaly creamyPyrenees liquidFrench-Spanish creamyThyme liquidLemon tree creamyOrange tree liquidFlowers creamyFlowers liquid

Honey

––––––––––––––––––

Dinotefuran

0.0520.040––

0.032––––

0.024––––

Nitenpyram

0.005––

0.015-––––

0.0200.0180.0160.006

Acetamiprid-N-desmethyl

––––

0.004––––––––––––

––––––––––––––––––

Fipronil Fipronil sulfone

Provence creamyItaly creamyPyrenees liquidFrench-Spanish creamyThyme liquidLemon tree creamyOrange tree liquidFlowers creamyFlowers liquid

Honey

––0.150.380.27––1.71.20.140.34

––––––––––––––––––

Acetamiprid Clothianidin

0.200.170.0430.047––

0.150.620.0550.11

Imidacloprid

––––

0.0200.020––

0.033––

0.390.010

Thiacloprid

0.010––––––––––––––––

Thiamethoxam

Injection number

Peak area

0

100,000

200,000

300,000

400,000

500,000

600,000

700,000

0 20 40 60 80 100 120 140

Acetamiprid

Acetamiprid-N-

desmethyl

Chlothianidin

Dinotefuran

Fipronil

0.005

0.005

0.020

0.010

0.001

Fipronil sulfone

Imidaclorpid

Nitenpyram

Thiacloprid

Thiamethoxam

0.001

0.020

0.020

0.005

0.005

Compound LOQ (µg/kg) Compound LOQ (µg/kg)

Acetamiprid

Acetamiprid-N-

desmethyl

Chlothianidin

Dinotefuran

Fipronil

78.8 %

93.4 %

70.6 %

76.5 %

78.1 %

Fipronil sulfone

Imidaclorpid

Nitenpyram

Thiacloprid

Thiamethoxam

74.2 %

83.2 %

87.0 %

82.2 %

75.6 %

Compound Recovery Compound RecoveryAccuracy (%)

0.005

0.010

0.050

0.100

0.500

1.000

5.000

10.000

110

96.0

100

98.4

97.0

99.0

98.4

101

Standard (ng/g)


APPLICATION

tions. This demonstrates thatexcellent sensitivity can be main-tained over a long series of realsample analysis thanks to the ionsource ruggedness.

Conclusion

A method for ultra-sensitive assay,covering most neonicotinoids ofinterest including fipronil in honeywas set up. Sample preparationwas simple but provided excellentrecoveries, whatever the honeytype. The injection mode usedprevented the use of tedious evap-oration/reconstitution or dilutionsteps.

The sensitivity obtained enabledassay in real samples at very lowlevels far below the regulatedresidue levels. This method can bea very efficient support tool forbetter understanding of the impactof neonicotinoids on honey beecolonies.

LiteratureApplication note C140: Ultra-Sensitive

and Rapid Assay of Neonicotinoids, Fipronil

and Some Metabolites in Honey by UHPLC-

MS/MS [LCMS-8060]

EU SANTE/11945/2015: Guidance document

on analytical quality control and method

validation procedures for pesticide residue

analysis in food and feed.

https://ec.europa.eu/food/sites/food/files/

plant/docs/pesticides_mrl_guidelines_wrk-

doc_11945.pdf

Table 4: Concentration for calibration and

accuracy

Table 5: Measured recoveries in honey

Table 6: Limits of quantification in honey

Table 7: Honey samples results (concentrations in µg/kg)

Figure 5: Stability of peak areas in real honey samples

Further information

on this article:

• Application:

Ultra-Sensitive and

Rapid Assay of Neo-

nicotinoids Fipronil and Some Meta bo -

lites in Honey by UHPLC-MSMS

http://ec.europa.eu/food/sites/food/files/plant/docs/pesticides_mrl_guidelines_wrkdoc_11945.pdf



I ntensive agriculture and itsassociated use of pesticideshave resulted in the presence

of pesticide residues in our entireecosystem. In 2006 and 2007,about 2.4 megatons of pesticideswere used worldwide to protectfruits and vegetables from insectinfestation. However, not all cropprotection agents act only on tar-geted pests. Often, beneficialinsects are also non-selectivelyaffected.

When resistant insecticides andfungicides get into human andanimal foods via water and air,additional health risks arise. Theserange from simple skin and eyeirritation to nervous system dam-age, hormone-like effects or possi-bly even certain kinds of cancer.

selective as possible and targetonly specific pests. In addition, itshould be quickly biodegradablewithout leaving any residues. Asthe group of pesticides includemany different compound classes,they differ strongly in terms oftheir chemical structure and char-acteristics, which makes the analy-

The ecological footprint of the ideal pesticide

This is why, in the developmentand regulatory approval of newpesticides, their ecological foot-prints are essential in terms of sta-bility and decomposition studies.The ideal pesticide should be as

APPLICATION


Investigating soil pollutionAnalysis of pesticide residues in soils using supercritical fluids

Figure 1: Sample preparation for SFE

Mix soil sample with drying

agent

Transfer to extrac -

tion vessel

Loading the rack-changer

sis of these types of compoundsrather complex.

For the determination of pesticideresidues in soils, an initial extrac-tion step is required. Typically,this step is carried out using liq-uid-liquid extraction. This is,however, time-consuming – alsodue to the use of special reagentsand laboratory equipment.

The analysis is often complicatedby contamination due to the pres-ence of metal ions or other ioniccompounds. Also challenging isthe sensitivity of certain pesticidesto external influences such as oxi-dation, exothermic reactions orother effects that result in partialdecomposition of the analytesduring liquid-liquid extraction.


APPLICATION

Supercritical fluids for automated extraction of pesticides from soils

To avoid these problems, extrac-tion using supercritical carbondioxide (CO2) offers a gentle alter -native to the conventional liquid-liquid extraction. Supercritical fluids combine the properties ofgases and liquids: They have a lowviscosity while exhibiting highdiffusivities – just like gases.

However, they also possess a highsolubility, just like liquids. CO2(at or above its critical tempera-ture and critical pressure) is themost commonly used supercriticalfluid for chromatographic purpos-es because it is highly inert, non-toxic and inexpensive, in additionto having suitable physico-chemi-cal properties and being easilyavailable.

Supercritical fluid extraction(SFE) using supercritical CO2therefore combines the good solu-bility properties of liquid-liquidextraction with the excellent diffu-sion properties of gases, so thatthe sample to be extracted is opti-

Table 1: Analytical conditions of the extraction

mally permeated and the analytescan be extracted efficiently. Byusing carbon dioxide, the need forlarge amounts of organic solventsis eliminated, thereby reducingsolvent waste.

Extraction of pesticides without the need for samplepretreatment

Shimadzu’s Nexera UC SFE sys-tem was used for the extraction ofpesticides. The analytical condi-tions are presented in table 1. Incontrast to the traditional liquid-liquid extraction, no complexsample preparation is necessary,except for the addition of a dryingagent to bind residual moisture. A typical sample preparationworkflow is shown in figure 1.

By expanding the autosamplerwith a rack changer, automatedpreparation and processing of upto 48 samples is possible. In thisway, the analysis is not only muchmore time-efficient and possibleovernight or during the weekendbut, in addition, human errorsduring sample preparation are alsominimized.

0500,000

1,000,0001,500,0002,000,0002,500,0003,000,0003,500,0004,000,0004,500,0005,000,0005,500,0006,000,0006,500,0007,000,0007,500,0008,000,0008,500,000

10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5

Minutes

Figure 2: MRM-chromatograms of the pesticides

For the actual extraction, the ex -traction vessels can be heated upto 80 °C. Meanwhile, the trappingcolumn can be rinsed and equili-brated (see figure 3A).

Using supercritical carbon dioxideand optionally additional organicmodifiers, the analytes are extract-ed from the sample and retainedon a trapping column (B).

If necessary, further rinsing stepsfor the purification of the extracton the column can be implement-ed (C).

The extract is then released fromthe column by an eluent and col-lected in the fraction collector(D).

By using the trapping column,multiple extraction steps are pos-sible without diluting the sample

unnecessarily, as the release onlytakes place after addition of theeluent.

Conclusion

Extraction using the Nexera UCdemonstrates that the complexsample preparation usually neededfor the analysis of pesticides insoil samples can be avoided. Theuse of supercritical carbon dioxideensures an efficient extraction andalso minimizes the amount oforganic solvents used. Autosam -pler and rack-changer automatethe analysis. Their use precludesthe influence of human error. Inthis way, the Nexera UC offers asimple and fast method for samplepreparation prior to residue analy-sis and provides a reliable investi-gation of pesticide pollution insoil samples.

A

B

C

D

Figure 3: Exemplary scheme of the extraction process

Extraction solvent

Flow rateExtraction programmExtraction temperatureBack pressureTrapping columnColumn temperatureEluent

A: CO2

B: Methanol5 mL/min4 min (static → dynamic)40 °C150 barShim-pack VP-ODS (50 mm x 4.6 mm, 5 µm)40 °CAcetonitrile / Hexane 50 /502 mL/min, for 2 min

System Nexera UC SFE System

APPLICATION


Fully automated analysis with the barrier ionizationdischarge detector

New formaldehydedetermination method

T he fully automated processpresented in this article isbased on headspace sampling

with subsequent gas chromato-graphic separation of the compo-nents. A helium plasma is used fordetection, achieving a detectionlimit of less than 0.2 mg/L.

Formaldehyde (systemic chemicalname according to IUPAC: me -tha nal) has the shortest chainlength of all aldehydes. With amolar mass of 30.03 g/mol and aboiling point of -19 °C, this gas is highly soluble in water. Origi -nally, formaldehyde was used

mainly as a preserving agent. The use of formaldehyde as a com -ponent in wood adhesives in -creased significantly, for instancein furniture making and interiorconstruction.

Formaldehyde has been classifiedas category 1B according to theCLP regulation as of June 2014.The potential hazard is thereforeclassified as ‘probably carcino-genic to humans’ [1]. Today,formaldehyde is a widely usedchemical. It is used as startingmaterial for various polymers, to treat clothing, and it serves as

a preserving agent in various pro -ducts.

New method without derivatization

Due to formaldehyde’s toxicity,there are defined limit values forall application areas that shouldnot be exceeded. Various methodshave been established to controlthese limit values. The methodpresented here does not includethe otherwise typical derivatiza-tion step. The sample is simplytransferred to a headspace vial andhermetically sealed. In the subse-quent step, the sample is in -cubated at 80 °C for 20 minutes.

An equilibrium is reached be -tween the aldehyde concentrationin the liquid and gas phase accord-ing to the partition coefficient.The autosampler withdraws 1 mLof the gas phase and transfers thevolume onto the gas-chromato-graphic separation column.

A complete separation of the airand water peaks is critical forquantification of the formalde-hyde. In addition to formalde-hyde, this method is also suitablefor measuring other analytes with-in one step, such as longer-chainaldehydes (shown here up tobutyraldehyde).

Detection is carried out using abarrier ionization discharge detec-tor (BID) from Shimadzu (figure 1).The BID operates with a heliumplasma that ionizes the sample.The ionization energy is so high(17,7 eV) that virtually all sub-stances are detected and the detec-tor , can therefore be consideredto be universal (with the exceptionof helium and neon).

Figure 1: Schematic representation of the BID detector. A helium plasma is generated in the upper zone (shown in red).

The emitted photons ionize the sample (lower zone). The sample cannot reach or contaminate the plasma zone due to the

inner flow architecture and flows sideways.

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Shimadzu NEWS, Customer Magazine of Shimadzu Europa GmbH, Duisburg

PublisherShimadzu Europa GmbHAlbert-Hahn-Str. 6 -10 · D-47269 DuisburgPhone: +49 - 203 - 76 87-0 Fax: +49 - 203 - 76 66 [email protected]

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CopyrightShimadzu Europa GmbH, Duisburg, Germany – March 2017.

Windows is a trademark of Microsoft Corporation. ©2017

Apple Inc. All rights reserved. Apple, the Apple logo, Mac OS and iOS are trademarks of Apple Inc.


APPLICATION

Robust, maintenance-freedetector

Two new designs make this detec-tor extremely robust and mainte-nance-free. On the one hand, thehelium plasma is shielded fromthe electrodes by a dielectric bar-rier, preventing them from beingattacked by the plasma. On theother hand, the flow architectureseparates the plasma generationzone from the ionization zone(figure 1).

This prevents possible contamina-tion of the plasma by the sample.To check the suitability of thedetector for formaldehyde detec-tion, a concentration range of 0.5to 50 ppm of the aldehyde inwater was calibrated. A 30 mmShimadzu Rt-U-Bond PLOT col-umn with an internal diameter of0.53 mm and film thickness of 20 µm was used as a separationcolumn. Details of the measuringmethod are summarized in table 1.

Result

The result of these measurementsis presented as a chromatogram(figure 2). Measurement tookabout 15 minutes. Formaldehydewas separated sufficiently fromthe air and water peaks – a prereq-uisite for accurate quantification.

Formaldehyde eluted after about1.5 minutes. The detection limit ofthis method was 170 µg/L (ppb)for formaldehyde. Longer-chainaldehydes can be detected at a sig-nificantly higher sensitivity due tothe increased detector response.Details of the statistical evaluation(correlation coefficient, rel. stan-dard deviation and method detec-tion limit (MDL)) for the individ-ual components can be found intable 2. The relative standard devi-ation is, with 6.6 % at a concen-tration of 0.5 ppm for formalde-hyde, somewhat higher than forthe other components. This is dueto the fact that because of the con-stant background, it is a challengeto create a formaldehyde-freesample. Moreover, formaldehydeis so volatile that sample prepara-tion is a critical step in which ana-lyte can easily be lost. Lastly, thechromatographic separation alsoplays a role. As can be seen in fig-ure 2 (below), the formaldehydepeak sits on the shoulder of the airpeak, which somewhat deterio-rates the precision of the peak areacalculation.

Conclusion

The method is highly suitable fordetermination of formaldehyde aswell as other short-chain aldehy-des, without requiring any further

sample preparation steps. By com-bining the HS-20 headspace auto -sampler with the BID detector, allsteps are fully automated, makingthe analysis robust and simple.Reproducibility is very good,while the detection limit is out-standing.

Literature[1] Umweltbundesamt, https://www.umwelt

bundesamt.de/themen/gesundheit/umwel-

teinfluesse-auf-den-menschen/chemische-

stoffe/formaldehyd

Table 1: Details of the instrument and method parameters

Table 2: Statistical data of the method. Correlation coefficient of the calibration, relative

standard deviation at a concentration of 0.5 ppm, as well as the calculated detection limit

of the investigated components

mV

0250500750

1,0001,2501,5001,7502,0002,2502,5002,750

1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 0.0 10.0 11.0 12.0 13.0 14.0 min.

mV

b)

-60.0-57.0-55.0-52.5-50.0-47.5-45.0-42.5-40.0-37.5

0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 2.25 2.50 2.75 3.00 min.

Figure 2: Chromatogram of the standard solution with 10 ppm (above). Below is a section

of the same chromatogram for the formaldehyde peak at about 1.5 minutes.

Incubation temperature Incubation timeAgitation strengthPressure in sample vialSample temperatureSample volumeInjector temperaturePartition coefficientGas and flow rateOven program time DetectionDetector temperature

80 oC20 minutes3 (of 5)90 kPa (relative)150 °C1 mL150 °C1 : 3Helium 60 cm/sec15.25 minHelium ionization (BID)180 °C

Instruments Tracera and HS-20

FormaldehydeAcetaldehydePropionaldehydeButyraldehyde

0.99920.99980.99970.9988

6.6 %1.5 %1.3 %2.3 %

0.170.020.030.05

Components R2 RSD (at 0.5 ppm) MDL (ppm)

http://www.umweltbundesamt.de/themen/gesundheit/umwelteinfluesse-auf-den-menschen/chemische-stoffe/formaldehyd




http://www.shimadzu.eu

APPLICATION


Ultrasonic fatigue testing systems USF-2000 and USF-2000A

How reliable are additivelymanufactured alloys under very high cycle fatigue (VHCF)loading?

S elective laser melting (SLM)technology for additivemanufacturing has advanced

in recent years. Since the additivemanufacturing process offers ahigh level of design freedom, it isused to create lightweight struc-tures. It is possible to optimizetheir topology and in this way tocreate new designs with signifi-cantly lighter components.

How ever, prior to using SLM com -ponents in the automotive andaerospace industry and for thesake of safety and cost-effective-ness, the required fatigue strengthmust be guaranteed.

Process- and microstruc -ture-based assessment of performance

Although the performance ofSLM components is given understatic loads, their fatigue strengthis greatly reduced due to process-induced porosity. Even a (resid-ual) porosity of less than 0.4 %seriously affects reliability underfatigue loading [1,2].

In order to prevent fatigue failureof SLM-manufactured structures,a microstructure-based process-specific characterization of theperformance has to be carried out.

Using new test methods based onultrasonic fatigue, failures withvery high cycle fatigue (VHCF)for loads below the so-called‘fatigue limit’ were determined[3, 4]. Moreover, in the HCF toVHCF range, some alloys withbody-centered cubic (BCC) andface-centered cubic (FCC) latticesystems show a shift in crack initi-ation from the surface to the innervolume of the material [5].

Production and HCF fatigueproperties of SLM-AlSi12

Using a commercial SLM system,samples of the aluminum alloyAlSi12 were manufactured in aninert argon gas environment.Quasi-static tensile strength testswere performed in accordancewith ISO 6892-1: 2009. Evaluationof the HCF fatigue behavior wasperformed under load increaseand constant amplitude tests witha frequency of 20 Hz.

The process optimization results,tensile and HCF fatigue character-istics as well as the measurementand test methodology used toevaluate process-induced damage

and its effect on the characteristicshave been described in literature[1, 2, 6]. These studies serve as thebasis for determining the effects ofprocess-induced defects on theVHCF fatigue behavior until 1E9cycles.

New experimental metho-dology with ultrasonic fatigue –testing system USF-2000

Tests to determine fatigue strengthin the VHCF range were per-formed using Shimadzu’s USF-2000 ultrasonic fatigue test-ing system at a frequency of 20 kHz and a load ratio of -1, i.e.fully-reversed (without meanload). Figure 1 shows an overviewof the USF-2000 testing system.

Samples with the geometry shownin figure 2 were clamped at thethreaded end of the testing systemand were free to move at the bot-tom end. In the testing system, apiezoelectric crystal is used as anactuator and oscillates at 20 kHz.

The design is such that maximumstress is experienced at the middleof the sample and maximum dis-

Figure 1: Shimadzu’s USF-2000 ultrasonic fatigue testing system (in standard configuration)

Figure 2: Sample geometry in mm for AlSi12 aluminum alloy


APPLICATION

placement occurs at the free endof the sample.

To eliminate temperature increasesinduced by deformation at hightest frequency, the samples weretested at a suitable pulse-pauseratio and were in addition cooledusing compressed air. To deter-mine the fatigue strength at 1E9cycles, the staircase method wasused. If a sample fails, the stress inthe following test will be lowered;if the limited number of cycles is

attained, the load will be increasedin the following test. Sample fail-ure in the testing system is detect-ed by means of the change in theresonance frequency and the testis terminated automatically.

Microstructure and VHCF fatigue properties of SLM-AlSi12

Two batches of AlSi12 alloy weretested: for batch I, base plate heat-ing (BPH) was omitted in theSLM system; whereas batch IIsamples were manufactured usinga heated base plate at 200 °C.Figure 3 shows microstructuralimages of the two batches.

There is a clear difference in thepore fraction of the samples with-out and with BPH, i.e. sampleswith BPH do not exhibit large-size, fatigue-critical gas pores. Thereduction of large pores is attrib-uted to the degassing process inthe manufacturing chamber due topreheating. Figure 4 shows exem-plary Woeh ler (S,N) curves forboth AlSi12 batches in the rangeof high to very high cycle fatigue.The test results illustrate that afatigue fracture in the VHCFrange can occur for both batches

and that the fatigue strength ofsamples with BPH is about 45 %higher than that of samples with-out BPH.

New experimental metho-dology with ultrasonic fatigueand mean load application –testing system USF-2000A

To determine the fatigue strengthin the VHCF range under con -currently applied mean stress,Shimadzu’s USF-2000A ultrasonic

fatigue testing system is used (fig-ure 5). In addition to the abovere sults under fully-reversed load-ing, i.e. at a load ratio of -1, theinfluence of static mean stress onthe VHCF fatigue strength can becharacterized for different loadratios.

Summary and outlook

Developments in ultrasonic vibra-tion testing systems significantly

Figure 5: Shimadzu’s ultrasonic fatigue

testing system USF-2000A (with mean load

application)

Figure 3: Microstructural images for AlSi12 samples of batch I without base plate heating

(BPH) (a) and batch II with BPH (b)

advance the state of the art. Thisallows detailed testing under real-istic operational conditions andlifetime in the context of safetyand cost-effectiveness. Very pow-erful tools are now available forreliable determination of the effectof SLM processing parameters onthe resulting functional perform-ance in a wide range.

AuthorsM.Sc. Shafaqat Siddique, Dipl.-Phys. Gerrit

Frieling, Prof. Dr.-Ing. Frank Walther

Technische Universität Dortmund

Fachgebiet Werkstoffprüftechnik (WPT)

Baroper Str. 303, D-44227 Dortmund

www.wpt-info.de

References[1] Siddique, S.; Imran, M.; Walther, F.:

Very high cycle fatigue and fatigue crack

propagation behavior of selective laser

melted AlSi12 alloy. International Journal

of Fatigue 94 (2017) 246-254.

[2] Siddique, S.; Walther, F.: Fatigue and frac-

ture reliability of additively manufactured

Al-4047 and Ti-6Al-4V alloys for automo-

tive and aerospace applications.

Innovative Design and Development

Practices in Aerospace and Automotive

Engineering, Eds.: R. P. Bajpai, U.

Chandrasekhar, ISBN: 978-981-10-1770-4

(2016) 1925.

[3] Pyttel, B.; Schwerdt, D.; Berger, C.: Very

high cycle fatigue – Is there a fatigue

limit? International Journal of Fatigue 33

(2011) 49-58.

[4] Benedetti, M.; Fontanari, V., Bandini, M.:

Very high cycle fatigue resistance of shot-

peened high strength aluminium alloys.

Experimental and Applied Mechanics 4

(2013) 203-211.

[5] Morrissey, R.J.; Nicholas, T.: Fatigue strength

of Ti-6Al-4V at very long lives. Interna tio -

nal Journal of Fatigue 27 (2005) 1608-1612.

[6] Siddique, S.; Imran, M.; Rauer, M.;

Kaloudis, M.; Wycisk, E.; Emmelmann, C.;

Walther, F.: Computed tomography for

characterization of fatigue performance of

selective laser melted parts. Materials &

Design 83 (2015) 661-669.

60

105

Number of cycles to failure, Nf

Stress amplitude, �

a

45

75

90

105

MPa

135

106 107 108 109

Figure 4: Woehler (S,N) curves for AlSi12 samples of batch I without BPH and batch II

with BPH

APPLICATION


Colorful packaging – with big know howRisks from printed food packaging

P lastic packaging is used forall types of food, althoughnot all packaging materials

are the same. Food packagingmust meet many requirementsspecified by producers and con-sumers. The main purpose of foodpackaging is to protect foods fromharmful environmental influencessuch as light, oxygen and micro-bial decay to ensure a long shelflife. Safety, transport propertiesand recyclability play an impor-tant role as well. Apart from this,however, packaging also serves asan advertising space and should beboth appealing to the consumerand easy to handle.

In order to meet these various re -quirements, food packaging mate-

rials are increasingly complex instructure [1].

Identification of printed filmsusing FTIR spectroscopy

The analysis of transparent, color-less plastic packaging materialsused in the food industry was dis-cussed in the Shimadzu News

3/2016 (page 6 - 9). This studyfocused on the analysis of 32 dif-ferent packagings of different ori-gin using FTIR spectroscopy. Themeasuring technology appliedallowed a non-destructive analysisof surfaces of up to 2 µm layerthickness.

The present article focuses on theinvestigation of food packagingsand their printed informationincluding for instance, companylogos, product information andmarketing-relevant designs.

A total of 50 samples were ana-lyzed, among which were two dif-ferent categories of packagings,each revealing different types ofprinted information:

1. surface prints2. under-surface prints

Analysis performed in two steps

The surface print group includes15 of the 50 samples collected (30 %). They are characterized bythe printed information which hasbeen applied to the top polymerlayer. The group of under-surfaceprints dominates with 35 out of 50 samples (70 %) and includespackagings where the printedinformation is protected from theoutside by an additional polymerlayer.

In the first step, the plastic com-position of all samples was deter-mined using FTIR spectroscopy.The absorption was measuredusing Shimadzu’s IRTracer-100equipped with a diamond ATRunit. This method is based on thefact that the IR beam penetratinginto the sample leads to attenua-tion of the intensity of the reflect-ed light compared to that of theincident light.

Selected colored areas larger than1 cm were subsequently analyzedusing the EDX-8000P specificallyfor the presence of inorganic com-ponents, which are frequentlyused in pigments and fillers.Energy-dispersive X-ray fluores-cence analysis makes it possible todetermine elements from carbonto uranium while also accuratelydetecting concentrations in thelower ppm range. The analysis isnon-destructive and, just likeFTIR spectroscopy, requires nosample preparation.

A total of 199 IR spectra and 60EDX spectra were recorded in thecourse of these analyses. As anexample, the analysis results forten selected samples are presented

Figure 1: Image of sample no. 01

SHIMADZU NEWS 1/2017 13

in table 1. Samples for which themain components could not beunequivocally identified are desig-nated as ‘unknown’.

A detailed look at a sample

As an example, sample no. 01 willbe further discussed below. It is afilm imprinted with three colorsof ink, serving as the outer pack-aging of a chocolate bar. Spectraof the colored areas on the outersurface of the film were measuredusing the IRTracer-100.

The spectra in figures 2 and 3 sug-gest that the outer surface of thefilm contains imprinted cellulosefibers. In addition to the cellulosefibers, the spectrum of the redimprinted area also points to thepresence of cellulose nitrate. Thiscompound is often applied as abinder for liquid printing inksthat are used for imprinting pack-aging materials. Therefore, the redcolor is a surface print.

In the second step, EDX analysisis used to draw conclusions on theelement composition. The red areaon the film was examined first,followed by the back side of thefilm. As can be seen in figure 4(page 14), the film does not con-tain any significant amounts ofmetals, meaning that the red ink isan organic compound.

Subsequently, the metal film onthe inner surface of sample no. 01was examined. The film was sepa-rated from the glued-on cellulosefiber layer and analyzed separate-

ly. Since the metal film consists ofthe light element aluminum, thespectrum was recorded in the vac-uum with an excitation energy of15 kV. This prevents absorption ofX-ray fluorescence radiation byair and increases the intensity ofthe aluminum signal.

In addition to aluminum, thereare, however, also large amountsof iron that could be detected atan excitation energy of 50 kV.

To prevent contamination of thechocolate, the aluminum film isadditionally coated with a poly-mer layer as apparent from the IR spectrum of the separated alu-minum film, that prevents contactof the aluminum with the choco-late bar and subsequent contami-nation of the chocolate.

It is important to ensure thatfoods are not contaminated withaluminum as this poses a healthrisk (see paragraph: Health risksresulting from aluminum?).

Printing inks and packagingmaterials

Among the 15 samples with sur-face prints, nine samples containcellulose nitrate. The other print-ing inks contain, in some cases,acrylate, polystyrene or other notyet identified components. Figure6 (page 14) presents an overviewof the imprinted packagings of the50 samples investigated. The non-identified components are notshown.

Polypropylene (PP) is the mostfrequently used imprinted packag-ing material. More than 50 % ofthe samples contain PP, whilepolyethylene (PE) and polyethyl-ene terephthalate (PET) occur inonly 20% of the samples. Interest -ingly, only one imprinted packag-ing appears to be made of poly-styrene (PS).

Of the 50 packagings investigated,17 are composed of two or moremain components. It should be

noted that only surfaces with alayer thickness of 2 µm were beinginvestigated. It cannot be ruledout that further components maybe identified upon investigatingcross sections of packaging films.Conversely, this means that recy-cling of polymers represents a realchallenge because of the complexi-ty of packaging materials.

Risks from printing inks in food packagings

Inks used for imprinting card-board and plastic food packagingshave long been the focus of ana-lytical control labs because harm-ful substances in printing inks canmigrate into packaged food prod-ucts. �

APPLICATIONAbs.

cm-1

0.00

0.05

0.10

0.15

0.20

0.25

0.30

4,400 3,600 2,800 2,000 1,600 1,200 800 400

Foil, printed, white, outside bar

Figure 2: FTIR spectrum of the white layer of sample no. 01: cellulose

Abs.

cm-1

0.000

0.025

0.050

0.075

0.100

0.125

0.150

0.175

0.200

0.225

4,400 3,600 2,800 2,000 1,600 1,200 800 400

Foil, printed, red, outside bar

Figure 3: FTIR spectrum of the red imprinted layer on the external surface of sample

no. 01: cellulose nitrate/cellulose

01

02

03

04

05

06

07

08

09

10

No.

Chocolate bar

Fruit jellies

Fruit

Nuts

Rusks

Coffee

Coffee

Carrots

Croissants

Snickers

Sample

Cellulose, Acrylate

PP

PP

PE

PP

PP

PP

unknown

PE

PP

Internal surface

Nitrocellulose /

Cellulose

PP

PP, PA

PET

PP

PP

PP

unknown

PET

PA

External surface

Surface print

Under-surface print

Surface print

Under-surface print

Under-surface print

Under-surface print

Under-surface print

Under-surface print

Under-surface print

Under-surface print

Imprint

––

symbol

––

07 PET, Alu, PE

––

––

––

compostable

07

––

Recyclingsymbol

Si, Ti, S, Al, Fe

Ti, Al, Si, P

Ti, Al, Si, P

Al, Ti, Fe, S, Si

Ca, Ti, Si, Al

Ti, Al, Si, P, S

Ti, Al, Si, P, S

Ti, Si, Al

Ti, Si, Al, S

Ti, Si, Al, P, S, K

EDX (>10 ppm)

Table 1: Identified main polymers of ten printed food packagings and their inorganic components

APPLICATION


According to the Switzerland-based health website (“German:Zentrum der Gesundheit”) about100,000 substances migrate frompackaging to foods [4].

Health risks resulting from aluminum?

Aluminum can enter the humanbody via drinking water as well asvia foods and their packagings.Aluminum, distinguished by itslight weight, is used in beveragecans and canned foods, caps forglass bottles, Tetra Paks, packag-ings for ready-made meals andfoils to protect foods from envi-ronmental influences. A disadvan-tage is, however, that under theinfluence of acidic beverages suchas fruit juices and caffeine-con-taining soft drinks, but also salt,aluminum is soluble and can mi -grate into foods and beverages.

Aluminum is suspected of causingkidney damage, having a negativeimpact on bone development andis associated with cancer andAlzheimer’s disease. Qualitativeand quantitative analysis of alu-minum in food packagings can becarried out using Shimadzu’sEDX-8000P energy-dispersive X-ray fluorescence spectrometer.

Summary and outlook

FTIR enables surface analysis ofall types of packaging materials.EDX complements FTIR identifi-cation and is suitable for detectionof critical substances, for instanceRoHS elements. Both FTIR analy-sis and EDX spectroscopy allownon-destructive and fast analysisof the plastic materials.

The present studies have focusedon transparent, colorless andimprinted food packagings. Non-transparent, colored packagingswill be addressed in followinginvestigations, in which harmfulsubstances such as heavy metalsand organic substances like miner-al oils are analyzed. Mineral oilsresidues can be differentiated intomineral oil saturated hydrocar-bons (MOSH) and mineral oilaromatic hydrocarbons (MOAH),which are suspected of causingorgan damage or cancer.

Mineral oils can migrate directlyinto foods from freshly ink-print-ed paper and plastic packagings,especially when the packagings areimprinted.

The analysis of MOSH/MOAHcontamination in foods and foodpackagings is performed usingchromatographic methods like theHPLC-GC-FID method des -cribed in the draft version of DINEN 16995:2016-05 [4].

This method will be discussed in asubsequent article in the ShimadzuNews 2/2017.

In accordance with the relevantregulations, materials that comeinto contact with foods may notcontain any substances or compo-nents that can migrate into foodsin harmful quantities. Packagingmaterials must also not lead toany unacceptable changes in thefood or cause any odor or tasteimpairment.

Food contact materials must,there fore, be produced accordingto good manufacturing practice[3].

Harmful substances in foods

Today, harmful substances arefound in a multitude of foods thatcan be introduced into the foodsalong the entire production andretail chain. Possible sources areprimarily packaging materials, butalso fuels, exhaust gases, lubricat-ing oils, dust-binders, anti-stick-ing agents and many more.

The multitude of contaminationsources present great challengesfor the analysis and quantificationof harmful substances in foods.

Literature

[1] Lebensmittelbedarfsgegenstände,

BM für Ernährung und Landwirtschaft:

http://www.bmel.de/DE/Ernaehrung/

SichereLebensmittel/Lebensmittelbedarfs

gegenstaende/Lebensmittelbedarfsgegen

staende_node.html (06.07.2016)

[2] https://www.zentrum-der-gesundheit.de/

schadstoffe-in-verpackungen-ia.html

(03.08.2016)

[3] Fachgruppe Druckfarben im Verband der

deutschen Lack- und Druckfarbenindustrie

e.V.: „Merkblatt: Flüssige Druckfarben“

http://www.lackindustrie.de/druckfarben/

allgemeine-informationen/Seiten/

Uebersichtsseite.aspx (20.12.16)

[4] DIN EN 16995:2016-05 – Entwurf: Titel

(deutsch): Lebensmittel- Pflanzliche Öle

und Lebensmittel auf Basis pflanzlicher

Öle – Bestimmung von Mineralölen aus

gesättigten Kohlenwasserstoffen (MOSH)

und aus aromatischen Kohlenwasser -

stoffen (MOAH) mit on-line HPLC-GC-FID;

Deutsche und Englische Fassung prEN

16995:2016

0

20

40

0.0 2.0 4.0

[keV]

[cps/uA] C-Sc

Figure 5: EDX spectrum of the separated

aluminum film of sample no. 01 (excita-

tion energy 15 kV)

Pre

valence

0

5

10

15

20

25

30

PP PE PET PA PS

28

1210

6

1

Figure 6: Prevalence of various polymers in the tested samples

Figure 4: EDX spectrum of the red imprinted layer of sample no. 01

(excitation energy 50 kV)

[cps/uA] AI-U

[keV]

1.00

2.00

3.00

4.00

5.0 10.0 15.0


APPLICATION

Summary

The results clearly show that wet-chemical oxidation is not suffi-cient to break down highly stablecompounds such as PFOS. Suchcompounds require the strongoxidizing power of catalytic com-bustion at 680 °C offered by theTOC-L series.

This underlines the different ap -plication areas of both analyzers.The strengths of the TOC-Vseries (wet-chemical oxidation) liein the extremely low detectionlimit and excellent reproducibilityin the lower ppb range. For thisreason, the TOC-VWP/WS is par-ticularly suitable for determina-tion in the ultra-trace range.

The advantage of the combustionmethod is its high oxidizingpower, particularly when highlystable compounds and/or particlesare present in the sample. In addi-tion, simultaneous TOC/TNbmeasurements can be performed.

The application range of theTOC-L series is therefore moreversatile and encompasses allTOC regions (except for theultra-trace region < 20 µg/LTOC).

P erfluorooctane sulfonate(PFOS) is a man-madeorganic straight-chain com-

pound consisting of an 8-carbonchain with fluorine atoms bondedto each carbon and a sulfonic acidterminal group. The specific char-acteristic of PFOS is that the per-fluorinated group is non-polar,whereas the polar anionic group ishydrophilic. It is a surfactant thatdissolves readily in both oil andwater.

and subsequently diluted to ob -tain a solution of 5 mg/L PFOS(equivalent to 0.961 mgC/L) and10 mg/L PFOS (equivalent to1.921 mgC/L). Surfactants likePFOS are prone to foaming, sothe difference method was usedfor TOC determination.

Measurement system:TOC-LCPH with standard catalystMeasurement method: Differencemethod (TOC = TC-IC)Calibration curve: TC: 0 - 3 mg/L(2 points)IC: 0 - 3 mg/L (2 points)

TOC determination of PFOSusing the TOC-VWS

Measurement system: TOC-VWSMeasurement method: Differencemethod (TOC = TC-IC)Calibration curve: TC: 0 - 3 mg/L(2 points)IC: 0 - 3 mg/L (2 points)

was determined using Shimadzu’sTOC-LCPH and TOC-VWS ana-lyzers.

Two methods for TOC determination

Shimadzu offers two TOC sys-tems featuring different oxidationmethods. While the TOC-VWP/WSuses wet-chemical oxidation, theTOC- LCPH applies the catalyticcombustion method at 680 °C.With their wide measuring rangesfrom 0.5 µg/L up to 30,000 mg/L,they support many applications,from ultrapure water to heavilycontaminated waters (for instancein cleaning validation, extractionsolutions or wastewater).

TOC determination of PFOSusing the TOC-LCPH

For sample preparation, PFOSwas dissolved in ultrapure water

PFOS is an extremely stable com-pound due to its strong carbon-fluorine bonds and is thereforepersistent in the environment,bio-accumulative and toxic tomammalian species. In October2006, the European Parliamentrestricted use of PFOS to a limit-ed number of application areas.

Due to its structure, PFOS is agood example for highlighting thedifferences in oxidizing powerbetween the wet-chemical oxida-tion method and the combustionmethod used in TOC determina-tion. For this application, theTOC content of a PFOS solution

TOC determination of a PFOSsolution Comparing wet-chemical oxidation with the combustion method

Figure 1: TOC-L

Figure 2: Perfluorooctane sulfonate

Table 1: TOC determination results using the difference method

Table 2: TOC determination results of PFOS using the TOC-VWS

10 mg/L PFOS5 mg/L PFOS

1.921 mg/L0.961 mg/L

1.898 mg/L0.959 mg/L

0.058 mg/L0.038 mg/L

1.840 mg/L0.921 mg/L

95.8 %95.8 %

SampleTOC

(theoretical)TC-measurement

resultIC-measurement

resultTOC calculated

(TC-ICRecovery

10 mg/L PFOS5 mg/L PFOS

1.921 mg/L0.961 mg/L

0.085 mg/L0.079 mg/L

0.077 mg/L0.064 mg/L

0.008 mg/L0.014 mg/L

0.4 %1.5 %

SampleTOC

(theoretical)TC-measurement

resultIC-measurement

resultTOC calculated

(TC-ICRecovery

Detection:Fluorescence: RF-20AXS: Ex: 365 nm and 320 nmEm: 450 nm and 465 nmPDA: D2 at 190 - 500 nm,

Reference at 350 nm

Sample preparation

Two batches of beer, apple juiceand grape juice were the object ofthis investigation. The sampleswere prepared as non-spiked orspiked with mycotoxins. 4 g of thebeverages were mixed with 21 mLacetonitrile. The mixtures were

APPLICATION


Detection of the mycotoxins wasconducted using a combination offluorescence and photodiode array(PDA) detection.

Investigation of mycotoxins in juice and beer

This method was applied to dif-ferent non-spiked and spiked beverage samples. In all spikedbeverage samples, the mycotoxinswere successfully identified de -spite the complexity of the matri-ces. All ten mycotoxins were suc-cessfully separated from eachother and detected by fluores-cence detection and PDA

Analytical conditionsInstrument: LC-2040C 3D

(Shimadzu)Column: Shim-pack GIST

C18 (3.0 mm x 75 mm I.D., 2 µm);Shimadzu

Mobile phase: A: 20 mmol/L sodium

phosphate bufferpH 2.5 (10 mmolNaH2PO4 and 10 mmol H3PO4)

B: AcetonitrileC: MethanolFlow rate: 1.0 mL/minInjection vol.: 10 µLOfen temp.: 55 °C

I t is hazardous to health, it isgenotoxic and carcinogenic. It is one of the most dangerous

substances in food: Aflatoxin B1.Of all types of aflatoxins, Aflatox -in B1 is the most common onepresent in food products [1]. It ispart of mycotoxins, which are sec-ondary metabolites produced byfungi [2]. Analysis of mycotoxinsin food is therefore essential inorder to assure healthy nutritionfor humans and animals.

Aflatoxins are produced by fungalmolds of the Aspergillus species,which prefer a warm and dampclimate. They are often associatedwith commodities produced in thesubtropics and tropics, like pea -nuts, cotton, spices or pistachios.Furthermore, they can be pro-

erties make the investigation infood crucially important as con-sumers need to be protected fromthese toxic substances. Sensitivemethods for the analysis of myco-toxins are required.

Complete solution

The Shimadzu „Mycotoxin Scree -ning System i-Series SolutionPackage“ is a one package singlesolution. The system simultane-ously investigates ten differentmycotoxins in only 14 minutes.This i-series instrument special-izes in identification of mycotox-ins in grain, such as wheat flourand rice flour, as well as in applesand milk. Sample preparation,analysis and evaluation are easycomprehensible, explained pro-gressively, and represent an easy-to-use solution for users.

Neither in-depth analytical norchromatographic knowhow arenecessary to operate the system.An additional benefit is the com-bination of a fluorescence detectorwith a PDA detector (Photo DiodeArray). This prevents a complexderivatization, and the mycotox-ins can be identified easily andefficiently.

AFB1, AFB2, AFG1, AFG2, AFM1,OTA, ZON, DON, NIV and PATwere investigated. For this ap -proach, the five analytes mostcommonly tested in malt productswere extracted and analyzed inspiked and non-spiked beer sam-ples from different batches, aswell as PAT in apple juice andgrape juice. EU limit values are:Aflatoxins (B1, B2, G1 and G2:total: 4 to 15 µg/kg; AFB1: 2 to 12 µg/kg); AFM1: 0.05 µg/kg;OTA: 2 to 10 µg/kg; PAT: 25 to 50 µg/kg; DON: 500 to 1,750 µg/kg; NIV: not specified; ZON: 20 to 400 µg/kg.

duced by fungal infestation duringor after harvest of grain and canend up in processed products suchas beer, brewed from malt.

Ochratoxin is produced by Peni -cillium and Aspergillus species. It is a contaminant in beveragessuch as beer and wine. Patulin,produced by P. expansum, Asper -gillus, Penicillium and Paecilo -myces fungal species, is oftenfound in moldy fruits and vegeta-bles. Zearalenone is produced byFusarium species and may bepresent in crops; AFM1 is oftenfound in milk products.

Mycotoxins are not destroyed bytemperature treatment, and arebarely influenced by cooking,freezing or digestion. These prop-

Complete solution formycotoxin analysisMycotoxin Screening System analyzes ten different mycotoxins in only 14 minutes

Table 1: EU residue limits for mycotoxins

Table 2: LC gradient program

Minutes

mV

0

25

50

75

5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5

Fluorescence detector

Minutes

mAU

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

1.00 1.25 1.50 1.75 2.00 2.25 2.50 2.75

PDA detector

Figure 1: Mycotoxins detected by fluorescence and PDA detection

EU residue[µg/kg]

not deter-mined

NIV

500 -1,750

DON

2 - 12

AFB1

20 - 400

ZON

2 - 10

OTA

25 - 50

PAT

0.05

AFM1

02.32.316.56.51

10.010.01

59

151535355

00

152015150

t [min] B [%] C [%]


APPLICATION

Table 3: Absolute LODs and LOQs of the mycotoxins, determined using fluorescence and PDA

detection. Error for the LOQs was below 10 % for all analytes.

100,000

75,000

50,000

25,000

0

10,000

20,000

30,000

40,000

50,000

60,000

70,000

80,000

0

0.25 0.50 0.75 1.00 1.25 1.50 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5

5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.50.25 0.50 0.75 1.00 1.25 1.50

uV

Data 1: grape juice_043.Icd PDA Ch1 220 nm, 4 nmData 2: grape juice spiked_044.Icd PDA Ch1 220 nm, 4 nm

Data 1: Beer_charge1_046.Icd Detector B:Ex: 365 nm, Em: 450 nmData 2: Beer_charge1_spiked_046.Icd Detector B:Ex: 365 nm, Em: 450 nm175,000

150,000

125,000

100,000

75,000

50,000

25,000

0

200,000

150,000

100,000

50,000

0

uV

uVuVMinutes Minutes

Minutes

–––––Ohne Mykotoxine –––––Mit Mykotoxinen versetzt

Minutes

Figure 2: Comparison of pure and spiked beverage samples: apple juice, grape juice and two different batches of beer

cleaned with a multifunctionalcolumn (MultiSep 228, cartridgetype). 4 mL of the elution werecollected and evaporated to dry-ness with nitrogen gas. The sam-ples were then re-dissolved in a400 µL water/acetonitrile (95/5,v/v) solution and used directly foranalysis. A standard mixture con-taining ten different mycotoxins(AFB1, AFB2, AFG1, AFG2,AFM1, OTA, ZON, DON, NIVand PAT) was prepared.

EU maximum residue limits,LODs and LOQs

The EU maximum residue limitsfor mycotoxins as specified by EUstandards are the strictest in theworld [3-5]. To check whether thefood samples investigated containmycotoxins within the EU maxi-mum residue limits, standardswith the mycotoxins were pre-

pared using the same concentra-tion as that of the EU control cri-teria. A simple and fast one pointcalibration was enough to assesscompliance with the criteria. A batch was created with the cali-bration standard and the foodsamples, and the results show ifthe peaks of the mycotoxins in thefood samples were below or abovethe criteria.

In this study, all measured samples(apple juice, grape juice and twobatches of beer) either containedno mycotoxins or were in a rangefar below the EU criteria. Thesame, spiked samples showedmycotoxin concentrations abovethe EU criteria.

For all mycotoxin standards,LODs and LOQs were deter-mined as shown in table 2. Limitof Detection (LOD) and Limit of

Quantitation (LOQ) were lowand at least half of the EU maxi-mum residue limits.

Figure 3 compares the differentbeer batches. The beer sample ofbatch 2 showed small peaks forAFG2, AFB2, AFB1 and OTA.Even though the concentration ofthe mycotoxins is far below theEU maximum residue limits, thisis a clear indication of the pres-ence of mycotoxins in the beer ofbatch 2.

The limits of detection (LOD) aswell as the limits of quantificationof each mycotoxin have been de -fined and are listed in table 3.According to the regulations ofsample preparation, LOD andLOQ are below the EU maximumresidue limits.

Conclusion

The level of these mycotoxins wasbelow the European regulation.The results show that differentbatches of the same beer show dif-ferences in mycotoxin content.Within this study, a fast, safe andeasy method was shown for the

analysis of mycotoxins in bever-ages. A further advantage, espe-cially for food quality controlanalysis, is the simultaneous sepa-ration of all ten mycotoxins injust 14 minutes.

Literature[1] European Food Safety Authority

(http://www.efsa.europa.eu/de/topics/topic

/aflatoxins)

[2] Richard JL, J. Food Microbiol. 119 (1-2):

3-10 (2007).

[3] EU: Commission Regulation (EC)

No 1881/2006 of 19 December 2006

(con solidated version 2010-07-01).

Setting maximum levels for certain

contaminants in foodstuffs.


No 165/2010 of 26 December 2010

amending Regulation (EC) No 1881/2006.


contaminants in foodstuffs as regards

aflatoxins.


No 105/2010 of 5 February 2010

amending Regulation (EC) No 1881/2006.


contaminants in foodstuffs as regards

ochratoxin A.Minutes

uV

0

5,000

10,000

15,000

20,000

25,000

5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5

Figure 3: Comparison of non-spiked beer batch 1 and non-spiked beer batch 2

LOD [pg]LOQ [pg]

80200

NIV

1020

DON

0.0250.075

AFG2412

AFG10.00020.0005

AFB20.00250.0075

AFB12575

ZON

0.10.3

OTA

1350

PAT

0.250.75

AFM1

Data 1: Beer_charge1_046.Icd Detector B:Ex: 365 nm, Em: 450 nmData 2: Beer_charge2_051.Icd Detector B:Ex: 365 nm, Em: 450 nm

Data 1: apple juice_039.Icd PDA Ch1 220 nm, 4 nmData 2: apple juice spiked_040.Icd PDA Ch1 220 nm, 4 nm

Data 1: Beer_charge2_051.Icd Detector B:Ex: 365 nm, Em: 450 nmData 2: Beer_charge2_spiked_052.Icd Detector B:Ex: 365 nm, Em: 450 nm

APPLICATION


E-cigarettes – Heavy metals in e-liquids and e-vaporsICP-OES technology meets Tobacco Products Directive (TPD) regulations

manufacturers all over the world,so there is a need for quality con-trol in order to avoid unexpectedharm or toxic effects.

Besides possible organic degrada-tion products, the presence oftrace elemental impurities in some

T he manufacture of e-liquidsis growing rapidly and expo-nentially in Europe, especial-

ly in UK, France and Germany.Unlike conventional cigarettes, E-cigarettes do not burn tobaccoto deliver flavor. Instead, theycontain a liquid-based flavorant

(e-liquid) that is thermally vapor-ized by an electric element andinhaled by the smokers.

E-liquids are usually made ofnicotine, propylene glycol, glycer-ine and flavorings. Their composi-tions vary between and within

e-liquids or e-vapor aerosol hasbeen previously reported. Each e-liquid component can contain ele-mental impurities and be a sourceof contamination. E-cigaretteshave several metal components indirect contact with the e-liquid,e.g. clearomizer, the tank attached

Figure 1: ELDA staff next to the ICPE-9820

Table 1: Measurement conditions

Wavelenhgt /nmView modeTorchRadio frequency powerPlasma gasAuxiliary gasCarrier gasExposure timeCondition

AxialMini torch1.20 kW10 L /min0.60 L /min0.70 L /min30 secWide range

396.153 193.759 226.502 267.716 224.700 259.940 184.950 231.604 220.353 271.581 371.030

Al As Cd Cr Cu Fe Hg Ni Pb Sb Y


APPLICATION

to the e-cigarette battery to holde-liquid. So potential toxins canalso leach out of device materialsdepending on the composition.

Tobacco Products Directive(TPD)

In May 2016, the Tobacco Pro -ducts Directive 2014/40/EU(TPD) came into force definingregulations covering e-cigarettes(Article 20). Article 20 of the TPDplaces an obligation on the manu-facturers and importers of elec-tronic cigarettes and refill contain-ers to submit a notification to thecompetent authorities of theMember States of such productsthey intend to market. The notifi-cation must list ingredients andemissions which result from theuse of the products.

Depending on the material com-position of the e-cigarettes, infor-mation on aluminum, chromium,iron, nickel and tin emissionsshould be provided. If other met-als such as lead and mercury arepresent in the e-cigarette compo-nents, information on these metalsshould be included as well.

By May 2017, all products sold tocustomers must be fully compliantwith TPD.

Each EU Member state can placefurther restrictions, but they allhave to comply with the centralrules of Article 20 of the TPD.Norm XP D90-300-2 AFNOR(France) defines maximum con-centration of heavy metals in e-liquid as follows: lead (Pb) 10 mg/L, arsenic (As) 3 mg/L,cadmium (Cd) 1 mg/L, mercury(Hg) 1 mg/L, antimony (Sb) 5 mg/L.

Simultaneous determination of heavy metals

For simultaneous quantitativedetermination of heavy metals ine-liquids and e-vapor, ICP-OES(inductively coupled plasma –optical emission spectrometry) isthe method of choice. Shimadzu’sICPE-9820 achieves a broad dy -namic range from ppb to percentorder due to axial and radial plas-ma observation capabilities, �

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Concentration (ppb)

Intesity

0.0

4.5

0 25 50 75 100

2.5

5.0

7.5

10.0

12.5

15.0

Concentration (ppb)

Intesity

0.0

0 25 50 75 100

0.025

0.050

0.075

0.100

0.125

0.150

Concentration (ppb)

Intesity

0.000

0 25 50 75 100

2.5

5.0

7.5

10.0

12.5

Concentration (ppb)

Intesity

0.0

0 25 50 75 100

2.5

5.0

7.5

10.0

12.5

15.0

Concentration (ppb)

Intesity

0.0

0 25 50 75 100

1

2

3

4

5

Concentration (ppb)

Intesity

0

0 25 50 75 100

0.5

1.0

1.5

2.0

2.5

Concentration (ppb)

Intesity

0.0

0 25 50 75 100

0.1

0.2

0.3

0.4

0.5

Concentration (ppb)

Intesity

0.0

0 25 50 75 100

0.1

0.2

0.3

0.4

0.5

0.6

Concentration (ppb)

Intensity

0.0

0 25 50 75 100

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Concentration (ppb)

Intensity

0.0

-0.1

0 25 50 75 100

Al 396.153 nm (1)

r = 0.99998

As 193.759 nm (1)

r = 0.99949

Cd 225.502 nm (1)

r = 1.00000

Cr 267.716 nm (1)

r = 1.00000

Ni 231.604 nm (1)

r = 1.00000

Fe 259.940 nm (1)

r = 0.99999

Cu 224.700 nm (1)

r = 0.99999

Hg 184.950 nm (1)

r = 0.99976

Sb 217.581 nm (1)

r = 0.99995

Pb 220.353 nm (1)

r = 0.99998

Figure 2: Calibration curves of metals obtained by ICPE-9820

APPLICATION


ICPE-9820 under the measure-ment conditions listed in table 1(page 19).

Results

After building calibration curvesover six concentration levels, ana-lytical quantitative determinationis performed for aluminum, arse -nic, cadmium, chromium, copper,iron, mercury, nickel, lead andantimony. This approach targetsall metals likely to be found in e-liquids and in the aerosols of moste-cigarettes.

Figure 1 shows all calibrationcurves using multi-element stan-dards from 5 µg/L to 100 µg/L,which yielded excellent linearityfor simultaneous ICP-OES. Manye-liquids were tested with differ-ent nicotine strengths.

Table 2 shows selected results formetal quantity in e-liquid and e-vapor at high nicotine strength

0.5 g of e-liquid sample is weighedand filled up to 25 mL with 2 %nitric acid, with addition of 50 µLof 50 ppm yttrium as an internalstandard. The aliquot is analyzedby ICPE-9820 with low-flowmini-torch, reducing plasma gasconsumption to 10 L/min and less.

For metal emission analysis of e-cigarettes, the resulting aerosolis collected by an LM4E smokingmachine with electrostatic precipi-tation, customized for e-cigarettes,which models human puffingbehavior.

E-cigarettes were puffed based onthe CORESTA recommendedmethod N˚ 81 with the followingpuffing regime: 55 mL puff vol-ume, three second puff duration,30 seconds puff interval and a rec-tangular wave puff profile.

Electrostatic precipitate is washedtwice with 2 % nitric acid to ob -tain a total volume of 25 mL. In ternal standard is added as well.The aliquot is analyzed by

high sensitivity and high samplethroughput.

ICPE-9820 is equipped with vacu-um high performance optics anduses a 1024 x 1024 pixel CCD(Charge Coupled Device) detector.

This system allows simultaneousacquisition of spectral data overthe entire wavelength range from167 nm to 800 nm; all elementinformation and wavelengths areavailable to users without the needfor any additional measurement.Because of the ICPE-9820’s so -phisticated vacuum technology,purging is no longer required,thus completely eliminating anyadditional operating cost such asargon consumption.

Sample Preparation

Because of the high viscosity andthe organic matrix, e-liquids sam-ples were diluted and measure-ment was conducted using the cal-ibration curve method with aninternal standard.

ELDA Ltd. is the leading manufac-turer of e-liquids for electronic cigarettes in Europe. Together withhis co-owner, Dario Marenic, Presi -dent of the Managing Board of thecompany, started his vision by find-ing the highest quality and richaromas, and designing and creatingformulas that have become thebest recipes in the world.

In 2016, ELDA won numerousawards: At the VaporFair exhibitionin Frankfurt, Germany, ELDA wasthe proud bearer of awards for the best vapor product; at theExpovape fair in Madrid, Spain,they were also awarded for themost innovative product of theentire e-liquid industry; the VapeExpo in Moscow, Russia awardedthem for the best European e-liquid. With these awards, recog-nition has been granted for the

best e-liquid manufacturer in theentire industry. Also in 2016, thecompany opened a new productionfacility and laboratory for completeanalysis of e-liquid and electroniccigarettes on the basis of whichthey ensure, in cooperation withShimadzu, fulfillment of the highcriteria of the new TPD legislation.

According to ELDA, there has beenno legislation of e-cigarettes for a long time. ”It is good that thismarket is becoming more regulat-ed. Because we have an ICPE-9820among other Shimadzu instru-ments, we are happy that we canuse reliable instruments to gatherinformation on elemental impuritiesin the e-liquids and emissions testsfor the purpose of quality control,with the desire to protect our endusers.”

Table 2: Selection of results for metals quantitation by ICPE-9820;

ND (not detected)

(18 mg/mL). Metal quantities for a given e-liquid are all within pre-vious reported data and the maxi-mum concentration defined by theAFNOR standard.

Conclusion

The ICPE-9820 is ideally suited toimplementation of the TPD, pro-viding users with a simple andreliable metal analysis in a singlerun in just a few minutes.

Also, the mini-torch and vacuumoptics ensure that operating costsremain at a minimum level. E-liquids manufacturers need toimprove quality control of theproducts in order to protect con-sumers from potential adverseeffects. Further investigationsusing this analytical techniqueshould provide more informationon emissions tests related to mate-rial composition of the e-ciga-rettes.

ElementAlAsCdCrCuFeHgNiPbSb

Metal quantity (µg/L)142.00ND

24.0516.5577.00162.50ND

51.00NDND

Metal quantity (µg/10 puff)0.015ND

0.0030.0010.0080.053ND

0.0040.002ND

Sample E-liquid, nicotine content 18 mg/mL

E-vapor, nicotine content 18 mg/mL

0

0.5

1

1.5

2

12,00011,00010,0009,0008,0007,0006,0005,0004,0003,0002,0001,0000

Area ratio

Number of injections

Area ratio %RSD = 3.42 %

Column replaced after 7,500 injectons

5 ng/mL alprazolam spiked in protein-crashed human plasma extracts (IS: 5 ng/mL alprazolam-d5) m/z 309.15 > 105.1

480 injections/daysperformed for 25 days

Figure 2: LCMS-8045 instrument stability test


PRODUCTS

Boosts productivity

T he LCMS-8045 triple quad -rupole mass spectrometer isthe new member of the well

renowned UFMS (Ultra-FastMass Spectrometry) range. It isbased on the UFMS platform withHeated ESI, fast polarity switch-ing and fast scanning speed. TheLCMS-8045 addresses laborato-ries performing demanding rou-tine quantitative analyses, e.g. infood safety, environmental testingand analytes in clinical samples.The system offers an optimumbalance in sensitivity, robustnessand cost-effectiveness.

The LCMS-8045 features a modi-fied ion sampling device and colli-

Analyses around the clock

The new LCMS-8045 constitutesthe heart of the successful UFMSrange and provides a very cost-effective solution for all routineapplications laboratories.

The LCMS-8045 is the workhorseinstrument in the Shimadzu LC-MS/MS lineup, designed to ana-lyze samples around the clock.The heated ESI probe, high-tem-perature heating block, heateddesolvation line, drying gas andfocusing optics all act to maximizesensitivity while minimizing con-tamination.

This means continuous operationin the laboratory with reliabledata collection, even for complexmatrices like biological fluids orfoods.

These include a unique scan speedof 30,000 u/sec without the loss of mass accuracy, and a polarityswitching time of 5 msec, whichensures higher throughput andhighly reproducible data even forthe most demanding matrices.

The LCMS-8045 is operated usingShimadzu’s LabSolutions softwareplatform, either in standalonemode or in a client/server envi-ronment. It is an intuitive packagethat enables simplified instrumentcontrol, diverse data handling andintegration with regulatory com-pliance requirements like FDA 21CFR part 11.

Numerous options are available toaddress specific customer require-ments, for example application-specific method packages (lipidsmediators, pesticides, veterinaryproducts ...), libraries and open-access quantitative analysis soft-ware.

In case new challenges or applica-tions requiring higher sensitivityarise, the LCMS-8045 can beupgraded to the high-sensitivityLCMS-8060.

Figure 1: Combination of Shimadzu Nexera with LCMS-8045

sion cell technology, resulting ingreater efficiency and high quanti-tative accuracy and reliability. Inaddition, the ion source features acable-less, tubeless housing, andthe desolvation capillary can bereplaced without breaking vacu-um. This leads to increased dura-bility, easier maintenance and alower total cost of ownership.

Higher throughput even for the most demanding matrices

As part of the Shimadzu Ultra-Fast Mass Spectrometer series, the LCMS-8045 features an arrayof ultra-fast technologies.

Further information

on this article:

• www.shimadzu.eu/

lcms-8045

The LCMS-8045 workhorse system with key features of UFMS to improvethroughput

APPLICATION

B eer is probably one of theoldest alcoholic drinks inthe world. In fact, Chinese

and Egyptians already made beerin 4000 years BC. In Europe, beerwas the Celts’ famous beveragethroughout the ancient times.

In order to assure standards re -garding quality, freshness, appear-ance and flavor, much regulationexists in Europe since the earlyXVIth century (“Reinheitsgebot”in 1516 in Germany; royal decreeof 1495 in France ...). LouisPasteur, one of the most famous19th century scientist, started hiscareer by researching beer processimprovement. Nowa days, withwide interest in the diversity andvariety of beers, more than 6,500breweries exist in Europe.

The quality standards for beeranalysis are defined by the CentralEuropean Commission for Brew -

anthropogenic sources such asenvironmental pollution and agri-cultural treatment by fertilizers,pesticides and fungicides.

Metal content in beer

Last but not least, the metal con-tent in beer can be influenced dur-

Determination of trace metals inbeers is relevant as they may beessential or toxic in the humanbody, and also have an influenceon the brewing process. The ele-ment distribution, however, showssignificant differences based onthe natural sources of soil, water,cereal, hops and yeast as well as

ing Analysis (MEBAK) and theEuropean Brewery Convention(EBC), representing technical andscientific interests of the brewingsector in European countries.These regulations include thedetermination of numerous ele-ments (e.g. Arsenic (As), Calcium(Ca), Copper (Cu), Sodium (Na),Potassium (K) ...), anions (such asnitrate and sulfite) as well as or -ganic components (ethanol, glyc-erine) and others (pesticide resi -dues) [1]. In order to maintain thehighest level of quality, somechemical investigations have to beperformed, using different analyti-cal techniques to quantify all thepotential contaminants.

Constant control of beer

Nowadays, the health effects oftrace elements and the maximumconcentration of trace elements inbeers are controlled continuously.


Arsenic in Beer?Determination of heavy metals in beerusing ICP-MS spectrometry

kcps

E1

E1

As. 75

kcps As. Shift-16

u

u

0

5

10

0

10

15

49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69

65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85

Figure 2: Development Assistant window in LabSolutions ICP-MS software for 75As in beer

sample. Dark curve corresponds to DBG mode and blue to DBN measurement mode.

Figure 1: ICPMS-2030


APPLICATION

ing production, beer processing,conservation and bottling. Thisinfluence is greater than expectedbecause during the beer-makingprocess both raw and processedproducts are often in long contactwith materials such as stainlesssteel, copper, glass and otherequipment.

The determination of copper isimportant because high concentra-tions are disadvantageous to thecolloidal stability and taste of thebeer. The same goes for zinc,which is an essential trace elementfor yeast that influences metabolicprocesses such as protein synthe-sis and nucleic acid metabolism.Typical concentration levels of copper and zinc in beer are 0.2 mg/L [2].

fossilized remains of diatoms, atype of hard-shelled algae thatlived millions of years ago.

Diatomaceous earth finds wideuse in filtering of beer and wine,and is an ingredient in other products as discussed by Profes -sor Mehmet Coelhan from theResearch Center Weihenstephanfor Brewing and Food Quality [3].

For simultaneous quantitativedetermination of the inorganicelements in beer, ICP-MS is themost preferable tool for qualitycontrol because of its high sensi-tivity (trace detection), widedynamic range and high samplethroughput. The ShimadzuICPMS-2030 is an easy to operateand fast system meeting theserequirements.

Furthermore, the determination ofarsenic, antimony, cadmium andlead is important because theseelements are toxic when present inbeer or the brewing water.

The source of these elements inbeer and other alcoholic beveragescould be the contamination of rawmaterial or technological process-es.

Arsenic released by Kieselguhrfiltering material

Arsenic is released into beer froma filtering material called Kiesel -guhr, or diatomaceous earth,which is used to remove yeast,hops and other particles and givethe beer a crystal clear appearance.Diatomaceous earth consists of

Table 1: ICPMS-2030 measurement parameters

Figure 3: Calibration curves obtained using 1 % HNO3 and 5 % EtOH. DBN analysis

are made without gas in collision cell. DBG analysis are purged with He gas in collision

cell (KED).

Furthermore due to the uniqueEco-Mode associated with Mini -torch, ICPMS-2030 can drasticallyreduce running costs by as muchas half.

The octopole collision cell assureshigh accuracy for all measure-ments of elements. Using heliumgas and Kinetic Energy Discrimi -nation principle (KED), this cellsuppresses most of the spectro-scopic interferences (polyatomicinterferences).

The efficiency of suppression ofinterferences and enhancement of sensitivity is improved by acooled cyclonic chamber and wellcontrolled torch positioning. �

0 10 20 0 1 2

0

5

10

15

20

25

Intensity

Concentration (µg/L)

0.00

0.50

0.25

0.75

1.00

1.25

1.50

Intensity


0 100 200 0 1 2

0

100

200

300

400

500

600

Intensity


0.00

0.500.25

0.751.001.251.501.75

Intensity


0 10 20 0 10 20

0

10

20

30

40

Intensity


0

100

200

300

400

Intensity


121Sb (DBG)Conc.=0.6613*1-0.0214R=0.99979BEC=0.022 µg/LLD=0.002 µg/L

ISTD: 115In

0 1 2 0 50 100

0.00.51.01.52.02.53.03.5

Intensity


5

0

10

15

20

Intensity


75As (DBG)Conc.=0.9257*1-0.0246R=0.99990BEC=0.025 µg/LLD=0.010 µg/L

ISTD: 69GA

111Cd (DBN)Conc.=1.6254*1-0.0077R=0.99982BEC=0.008 µg/LLD=0.002 µg/L

ISTD: 115In

65Cu (DBG)Conc.=0.3748*1-3.4172R=0.99969BEC=3.417 µg/LLD=0.111 µg/L

ISTD: 71GA

202Hg (DBN)Conc.=1.3078*1+0.0302R=0.99910BEC=0.064 µg/LLD=0.003 µg/L

ISTD: 115In

60Ni (DBG)Conc.=0.5155*1-0.0675R=0.99996BEC=0.067 µg/LLD=0.011 µg/L

ISTD: 71GA

208Pb (DBN)Conc.=0.05476*1-0.5894R=0.99936BEC=0.589 µg/LLD=0.010 µg/L

ISTD: 205Tl

66Zn (DBN)Conc.=5.6267*1-2.2068R=0.99968BEC=2.207 µg/LLD=0.021 µg/L

ISTD: 71Ga

RF generater powerPlasma gasAuxilliary gasCarrier gasNebulizer typeSampling depthSpray chamber temperatureColl. cell gas flow (He) DBG mode onlyQuantified isotopes

International standards (ISTD)

1.2 kW8 L/min1.1 L/min0.7 L/minMicroMist5 mm5 °C6 mL/min75As, 111Cd, 65Cu, 202Hg, 60Ni, 208Pb, 121Sb, 66Zn69Ga, 71Ga, 115In, 205Tl

Parameter Setting

75As111Cd65Cu60Ni

208Pb121Sb66Zn

1001

1132

993

841

951

842

923

971

1012

823

951

921

872

983

1091

922

923

851

991

942

973

SampleRecovery rate (%)

Beer 1 Beer 2 Beer 5

75As 111Cd 65Cu 60Ni

208Pb 121Sb 66Zn

2.050.07

29.102.25––0.395.28

3.490.05

28.705.62––0.19

23.90

2.390.07

40.501.53

> LQ2.155.04

1.460.08

38.202.58––0.452.83

0.390.15

22.404.47––0.55

29.20

Element Beer 1 Beer 2 Beer 3 Beer 4 Beer 5

Recovery (%) =Value after spike – Initial value

Initial value

x 100

APPLICATION

Moreover, ICPMS-2030 is able tosave all mass issued from samplemeasurement. The developmentassistant of LabSolutions ICP-MSsoftware can propose the opti-mum parameters for each elementin the sample. Method develop-ment has never been easier andfaster.

Experimental setup on ICPMS-2030

In the experimental work, fivecommercially available beers wereevaluated: St. Bernardus Abt 12from Belgium, and Becks Gold,König Pilsener, Erdinger andBitburger Pils, all originating fromGermany.

Thanks to the ICPMS-2030 sys-tem, analysis of beer could be performed without any samplepreparation. All analyzed sampleswere degassed using only ultra-sound. After this treatment, theywere aspirated directly to theICPMS-2030.

Eight different elements werequantified simultaneously: As,Cd, Cu, Hg, Ni, Pb, Sb and Zn.Analytical measurements condi-tions are summarized in table 1(page 23).

Conclusion

Beer is one of the favorite alco-holic beverages in European coun-tries with a statistical per capitaconsumption of around 68 L.

Quality is therefore expected tobe high and continuous qualitycontrol is essential. However, beermay contain a variety of heavymetals such as arsenic, lead andcadmium at low levels.

High-sensitivity analytical toolssuch as the ICP-MS are best suit-ed to detect these low level con-taminants to permanently ensurethe highest quality of beer.

the various elements present inbeer samples.

In order to determine the methodaccuracy, three of five beer sam-ples were spiked with each ele-ment (0.5 ppb, 5 ppb or 50 ppb).Results are shown in table 3 andcalculated according to:

For each element studied, calibra-tion curves include five points inthe concentration range from 0.1to 200 µg/L in a matrix-matchedsolution using 1 % nitric acid and5 % ethanol.

Beer samples were measured intriplicate, and three of them weremeasured as quality control sam-ples (Becks, König and St. Bernar -dus), spiked with 0.5 ppb, 5 ppbor 50 ppb resp., depending on theelement concentration.

An internal standard solution in 1% nitric acid (69Ga, 71Ga, 115In,205Tl) was mixed online with sam-ple, before being aspirated in thenebulizer.

As shown in figure 3 (page 23), allcorrelation coefficients r achieve a0.999 level. Moreover, low valuesof detection limits (LD), calculat-ed automatically by LabSolutionICP-MS software with 3� meth -od, indicate the high suitabilityand ability of ICPMS-2030 fortrace contaminant analysis. Foreach beer, results are summarizedin table 2.

The quantitation results in table 2demonstrate that ICPMS-2030 isable to simultaneously quantify


Table 3: Spike-Recovery rates in beer: 1 spike of 5 ppb. 2 spike of 0.5 ppb. 3 spike of

50 ppb.

Table 2: ICPMS-2030 results for each beer sample [µg/L]

Literature

[1] Pfenninger, H.: Brautechnische Analysen -

methoden (1996)

[2] J.S. Hough et al., Malting and Brewing

Science (Springer US, 1982).

[3] M. Coelhan et al., Am. Chem. Soc. “Widely

Used Filtering Material Adds Arsenic to

Beers” (2013),

https://www.acs.org/content/acs/en/

pressroom/newsreleases/2013/april/

widely-used-filtering-material-adds-

arsenic-to-beers.html

CrMnNiVNbMo

12.848.1567.651.3690.491.097

12.878.237.851.390.491.14

Element Quantitation valueConcentration, wt %

Certified value

The EDX-7000P and EDX-8000Pinstruments are BfS (safety stan-dards of the German Federal In -stitute for Safety) type approvalcertified.

Both spectrometers are equippedwith an automatic collimatorswitching system and a sampleobservation camera for localanalysis and small sample meas-urements. Advanced PCEDX


Figure 2: Sample display screen in PCEDX Navi

Table 1: Quantitative Value of GH2036 sample by FP Method

Figure 3: EDX spectrum of GH2036 shaving

PRODUCTS

Navi software is specially de -signed for less experienced users.

Standardless quantitative fastanalysis of small metal particles

Can the EDX-7000P/8000P spec-trometers be used successfully forstandardless quantitative fastanalysis of small metal particles?In an experiment, measurement of one stainless steel shaving byEDX-8000P was performed toestimate the capabilities of EDXspectrometers for standardlessquantitative elemental analysis ofmetal microparticles by Funda -mental Parameters (FP) method.Stainless steel is used in the pro-duction of valves for aircraft,automobile and tractor dieselengines and fastenings for engines.

One shaving of stainless steelGH2036 (China) in the nativeform was placed in the center of the sample compartment (fig-ure 2).

Safety of people inmodern transportOne metal shaving, and five minutes are enough

Figure 1: EDX-7000P/8000P

T imely diagnosis of enginewear is key to safety of peo-ple using aircraft, automo-

biles or railway trains. Analysis of engine oils is one of the maintypes of such applications.

Engine oils contain fine wearproducts as well as particles ofmetals and alloys in the form ofshavings. Elemental analysis ofsuch pieces permits determinationof the engine part wearing out,

and measurement of concentra-tions of main alloy/steel compo-nents in oil helps to estimate thedegree of wear of that part.

Testing laboratories of manymajor airlines use X-ray fluores-cence spectrometers for fast analy-sis of small metal shavings. Energydispersive X-ray fluorescencespectrometers such as Shimadzu’sEDX-7000P/8000P (figure 1) aresuitable tools for such analysis.

A collimator of 1 mm diameterwas selected for the analysis. A routine measurement procedureof unknown sample by FP meth -od was used, as included in thestandard spectrometer software.The spectrum of the sample isshown in figure 3.

Total analysis time including place -ment of the sample in the cell wasless than five minutes.

Conclusion

Results of the analysis are shownin table 1. The results show anexcellent match of quantitationand certified values.

The analysis results show that theEDX-7000P/8000P can be usedsuccessfully for standardless quan-titative fast analysis of small metalparticles without any samplepreparation.

LATEST NEWS


Shimadzu’s online TOC-4200analyzer has been grantedMCERTS accreditation based

on the performance standards andtest procedures set for continuouswater monitoring equipment.

MCERTS is the certification sys-tem of the Environmental Agencyof England and Wales (UK) formeasurement equipment. It pro-vides the framework conditionsand quality objectives for compa-nies to meet in order to complywith the authority requirementsfor environmental monitoring.

ties ensure that they are doingeverything possible to protecttheir environment. Requirementsfor obtaining this certificationinclude laboratory testing and a 3-month field test under real con-ditions.

TOC-4200

The TOC-4200 is a powerful ana-lyzer that is operated under cat-alytic combustion at 680 °C. Theanalyzer removes the inorganiccarbon content automaticallyfrom the sample and subsequentlyinjects an aliquot onto a 680 °Chot platinum catalyst where allorganic compounds are oxidizedto carbon dioxide.

The resulting CO2 is transferredby a carrier gas stream to a highlysensitive and CO2-selective NDIRdetector where it is measured. TheTOC concentration is calculatedusing an external calibration. Theintegrated dilution function allowsTOC analyses up to 20,000 mg/L.In addition, it allows automateddilution of the sample when themeasurement range is exceeded.

The automated dilution as well asthe self-calibration functions and

MCERTS is quickly becoming a required performance and relia-bility standard by organizationsaround the world. With accreditedequipment, companies and au thori -

On the safe side withMCERTS accreditationOnline TOC-4200 reveals its strengths during field tests

Ref. value (ppm)Measurement 1Measurement 2Measurement 3Measurement 4Measurement 5Measurement 6Mean value

Test point

54.895.014.94.954.944.954.94

1

2524.3324.7124.7524.6924.3524.2524.51

2

5049.6550.1549.5749.5750.0349.1649.69

3

7575.7775.1975.3474.8676.174.1375.23

4

10010199.57

100.7101.399.24

101.5100.55

5

Table 1: Results for the measurement range 0 - 100 mg/L

TOC-4200


LATEST NEWS

the optimized sampling allow avirtually independent operation ofthe measurement system.

Numerous alarm and status sig-nals simplify the detection ofexceeded limit values or the needfor maintenance. In addition tothe conventional options, Modbuscommunication is also available.An optional web browser enablesa “view” of the instrument fromany networked computer.

Laboratory tests

The TOC-4200 performance data,such as the mean measurementerror, linearity and reproducibilitywere determined in laboratorytests. For this purpose, the TOC-4200 was installed in thelaboratory and calibrated as afunction of the measurement rang -es. Subsequently, five measurementpoints were measured six timeseach: 10, 25, 50, 75 and 100 % ofthe respective measurement range.

Mean deviation

For the determination of the meanmeasurement deviation, the meandeviation from the reference valuewas calculated for each measure-ment point. The highest value islisted in the certification report.To pass the test, this value must beless than 10 %.

The mean deviation for the mea -surement range 0 -100 mg/L is1.99 %. The test for this range wastherefore passed. For the linearitydetermination, a linear plot wasdetermined from the mean valuesof the measurement points. Thedeviation of the measured datafrom the straight line was subse-quently calculated in %. The max-imum value may not exceed 5 %.

Linearity

For the measurement range 0 -100 mg/L, the linearity is -2.23 %,which meets the test requirementsfor this range. For the reproduc -ibility, the standard deviation and

Further information

on this article:

• Product Conformity

Certificate:

MC160311/00

Ref. value (ppm)Mean valueValue of the linearregression lineDeviationDeviation in %

Test point

54.94 5.012

-0.07-1.46

2524.51 25.06

-0.55 -2.23

21

5049.69 50.12

-0.43 -0.87

3

7575.23 75.18

0.05 0.07

4

100100.55 100.24

0.31 0.31

5

Test PointStandard deviationRelative STD

Reproducibility

10.043 0.87

20.226 0.92

30.357 0.72

40.694 0.92

50.935 0.93

Ref. value (ppm)Run 1Run 2Run 3Run 4Run 5Run 6Mean Error (%)

Test point

5-2.25 0.20 -2.04 -1.01 -1.21 -1.01 -1.22

1

25-2.75 -1.17 -1.01 -1.26 -2.67 -3.09 -1.99

2

50-0.70 0.30 -0.87 -0.87 0.06 -1.71 -0.63

3

751.02 0.25 0.45 -0.19 1.45 -1.17 0.30

4

1000.99 -0.43 0.70 1.28 -0.77 1.48 0.54

5

Table 2: Mean error in %

Table 3: Linearity

Table 4: Reproducibility

the relative standard deviationwere calculated from the measureddata of each measurement point.Again, the highest value may notexceed 5 %.

Reproducibility

The reproducibility for the 0-100 mg/L measurement range is0.93 %. The test for this range wastherefore passed. Measurementswere also carried out for the meas-urement ranges 0 - 500 mg/L, 0 -1.000 mg/L and 0 - 10,000 mg/L.All values obtained were belowthe specified limits. In addition,data were obtained to determinedrift, matrix influence and res -ponse time.

Field test

For the field test, data collectedover three months from a cus-tomer installation in a wastewaterapplication (measurement range 0 to 100 mg/L) was evaluated.Particular attention was paid tooperating time and downtime.Downtime includes time for cali-bration, maintenance, service andtroubleshooting. The resultingavailability should be higher than95 %. The TOC-4200 reached 100 %.

Conclusion – unique TOC on the market

The TOC-4200 achieved a 100 %availability in the field test, high-lighting its robustness and reliabil-ity. It is the only online TOC ana-lyzer utilizing catalytic combus-tion oxidation available on themarket with MCERTS accredita-tion. This technology offers aclear advantage for anyone in -volved in the analysis of water andwastewater with a high salt con-tent, solids or suspended matter aswell as complex organic com-pounds.

The certificate (MC160311/00)was issued for the TOC measure-ment ranges 0 -100, 0 -500, 0 -1.000 and 0 -10,000 mg/L.

Literature

www.csagroupuk.org/wp-content/uploads/

2017/02/MCERTSCertifiedProductsCWMSPar

t2.pdf

http://www.csagroupuk.org/wp-content/uploads/ 2017/02/MCERTSCertifiedProductsCWMSPart2.pdf



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Pisa, ItalyJune 11 - 16, 2017www.csi-conference.org

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Rotterdam, NetherlandsJune 13 - 15, 2017www.gasanalysisevent.com

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Shimadzu live NEWS – print and digital

New solutions for tomorrowLaunch of Shimadzu European Innovation Center

I n early March, Shimadzuopened its European Innova -tion Center. In presence of

Dr. Teruhisa Ueda, President andCEO of Shimadzu Corporation,Duisburg’s Mayor Sören Link,Yasunori Yamamoto, CEOShimadzu Europa, JapaneseConsul Ryuta Mizuuchi, andShuzo Maruyama, General Ma -nager Analytical & MeasuringInstruments Division, ShimadzuCorp., cut the tape.

In addition, a Daruma mask waspainted in a Japanese ceremony

to bring happiness and success.Numerous opinion leaders,thought leaders and experts frommarkets and science were invitedas guests.

Shimadzu’s European InnovationCenter innovations-oriented is aThink Tank combining scientificand technological know-how inorder to use Shimadzu’s expertiseto provide even more customer-focused service. It applies a de -centralized structure to be inclose local proximity to scientistsand related markets. This pro-

vides direct access to the users aswell as to projects and samples.

Clinical applications, imaging technology, food, and composites

With their leading-edge researchexpertise, highly-reputed scien-tists from well-known Europeanuniversities cover the academicpart of the Shimadzu EuropeanInnovation Center. For years,they have cooperated withShimadzu in various projects.Their scientific focus areasinclude clinical applications,imaging technology, food, andcomposites, with an emphasis onnew methods, tools, techniques,diagnostics, and solutions. Theirwork will, for example, furtherfacilitate will help to increaseanalytical and medical-diagnosticresearch with focus on patients’health as well as consumer andenvironmental protection.

Innovations-oriented exploration of four per-spectives

With regard to clinical, imaging,food, and composites, the

Shimadzu European InnovationCenter explores four focus areas:

• Trends & Demands: based onEuropean needs and demands

• Adaptation & Development,i.e. special accessories and jigs,adaptations, special software,new and special methods

• Compliance to European regu-lations, such as official regula-tions and standards, and localrules for limits of hazardoussubstances

• Strong cooperation: betweenShimadzu’s Innovation Centersand Shimadzu’s R&D team inJapan, developing global solu-tions based on global needs.

Analyzers involved in the Euro -pean scientists’ research projectsin particular include chromatog-raphy, mass spectrometry, andmaterial testing.

So far, other Shimadzu Innova -tion Centers are located in Mary -land, USA, Singapore and Bei -jing, China where they serve asdrivers of joint research and newproduct developments.

Figure 1: Dr. Teruhisa Ueda (r./CEO Shimadzu Corporation) and Dr. Hiroki Nakajima

(Chief of European Innovation Center) are painting the traditional „Daruma.“

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