shimadzu news 1 2011...sample pretreatment – online spe method »10 mercury in your eye – hg...

1/2011

NEWS

1/2011

NEWS

New TOC-L series:Ecofriendly andtimesaving

GC-2025: Economical,practical, effective

Mobile news enjoy-ment: Experience the Shimadzu News virtually anywhere

Eco-label: Small effort,large impact for thesake of the environment

Shimadzu NEWS, Customer Magazine of

Shimadzu Europa GmbH, Duisburg

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Editorial Team:

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Ralf Weber, Tobias Ohme

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German: 7,710 · English: 18,510

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Shimadzu Europa GmbH, Duisburg, Germany

May 2011

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IMPRINT

New Generation:

The TOC-L series

eco-label Shimadzu News 1/2011

2

Eco-label for excecofriendly syste

Living in harmony withnature and the environ-ment while preserving the

basis of life for mankind as wellas flora and fauna is more thanever a challenge for all societiesand cultures of this world. Envi-ronmental governance is a com-prehensive issue relating to indus-trial, emerging and developingcountries. It is also an importantissue in terms of the increasingworld population, which willexceed the seven billion mark in2011. The prognosis for worldpopulation by 2014 is 8 billionand by 2050 it will surpass 9 bil-lion. Issues concerning nourish-ment, food supply, resources andcommodities therefore need to beaddressed urgently.

Sustainability, environmental andclimate protection cannot be del-egated. These issues concern eachand every individual, families,groups, societies, as well as cor-porations being part of the eco-nomic cycle and industries whichare consuming and processingresources.

Different thinking, counteractingand adopting new attitudes andactions are feasible – this route

has already been pursued fre-quently and successfully. Rivershave been renaturated, catalyticconverters have been built intoautomobiles, lead-free fuels have

been introduced, the use ofCFC’s has been banned, and reg-ulations such as RoHS, WEEE as

Shimadzu eco-label

GCMS-QP2010 Ultra

LC-20AP

Eco-label for exceptionally ecofriendly systems »2

Allergenic mouse pad and leather wristlet – FTIR spectroscopy »4

Windows in the spotlight – UV-VIS spectroscopy »6

Exceptional: Co-Sense for Impurities – Drug safety »8

Tracing PAH analysis with automated sample pretreatment – Online SPE method »10

Mercury in your eye – Hg content in

contact lens solutions »12

Automatic quantification of doxylamine and diphenhydramine in human plasma »14

High-precision analysis of mineral waters »26

NEWS 2.0 – The Shimadzu News App »13

Economical, practical, effective – GC-2025 »17

A fresh breeze sweeps pyrolysis – The new

Multi-Shot EGA/PY-3030D pyrolyzer »18

Green – Yellow – Red – Safe hydrogen

handling »20

Sharper than an eagle’s eye – The new

Shimadzu Video extensometer TRViewX »21

Eco-friendly and timesaving – New TOC-L series »22

Flavor analysis in wine products »24

iPad® control expands HPLC network functionality »28

New: Shimadzu News Pharma Special »28

eco-label

APPLICATION

TELEGRAM

READ FOR YOU

SOFTWARE

INTERN

PRODUCTS

3

eco-labelShimadzu News 1/2011

eptionallyms

well as the German DrinkingWater Ordinance have beenimplemented. Of course, there isstill much that needs to be done.It is a road taken in small steps,

as it is not always easy to geteveryone on board.

General lines are drawn, forinstance, by the United NationsEnvironment Programme(»UNEP Environmental ‘BlueAngel’«) in the Montreal orKyoto Protocols. On nationallevels there are Ministries for theEnvironment, while the corporateworld employs environmentalprotection officers.

Since the mid 1990’s Shimadzuhas specified ‘environmental pro-tection and harmony with nature’in its ‘Cubic Heart’ symbol aspart of its corporate philosophy.Shimadzu’s analytical instrumentscontribute to the protection ofhuman health and the environ-ment. Many systems help to rec-ognize negative effects on theenvironment, for instance con-ventional gas chromatographs areapplied for the analysis of pesti-cides in the environment and infoods.

Combatting global warming isone of the most urgent tasks ofthe future. Shimadzu has there-fore issued an energy-saving pro-gram. Through energy-friendlymanufacturing processes, CO2emissions have been reduced in

GC-2025

TOC-L

its production facilities – forinstance by use of solar energy.The rate of consumption of com-posite materials has also beenreduced. The percentage of greenoffice supplies and productionmaterials could be increased to 90 % respectively 66 %. Techni-cal improvements of air condi-tioning systems as well as waste-

water treatment also contributeto environmental protection at Shimadzu.

Shimadzu has created its owneco-label under which new prod-ucts have been developed whichgenerate less CO2 emissions dur-ing operation. These new prod-ucts use at least 25 % less energycompared to their predecessormodels, thereby reducing runningcosts.

In addition to lower materialsand lower energy consumption,one of the current instruments –the GCMS-QP2010 Ultra – alsofeatures an eco-mode for stand-by operation. Furthermore, envi-ronmentally friendly materials inaccordance with RoHS guidelineswere used in the manufacture.Further savings in the operationof these instruments, for instancevia the reduction of consumablesand applied gases or an extensionof maintenance interval, also havean effect on the supply chain.This reduces the need for on-siteservice and contributes to energysaving at customer service depart-ments.

The eco-label is already featuredon Shimadzu’s GCMS-QP2010

Ultra and SE and the LC-20APsystems, as well as the brand-newGC-2025 and the TOC-L series.

In Japan where Shimadzu, inaddition to instrumental analysissystems, also offers other productsegments (for instance semicon-ductors), many instrumentsalready carry the new eco-label.In Europe four eco-label instru-ments have now been introducedto the market and others will follow. The most recent ones(GC-2025 and TOC-L series) are presented on pages 17 and 22of this issue.

APPLICATION Shimadzu News 1/2011

4

Tracing an allergy with single reflection

Contact allergies are well-known phenomena of thehuman skin surface. Very

often, the source of the allergy isunclear. Most allergy tests in useare for the exclusion of pollens,animal fibres or colors. Colorsare mainly used for daily textiles,e.g. leathers. Tests are also neces-sary on special metals in theworld of jewellery, such as Nick-el with known allergy connec-tions.

What is a contact allergy?

The allergy symptom startsthrough first contact of the aller-gen with the skin or mucous

Allergenic mouse pad anFTIR spectroscopy

membrane. This first contact does not cause any skin irritation,but it causes a sensitivity in thebody. With the next contact tothe material the skin activates itsimmune system an allergic reac-tion can soon be observed. As aninflammation it fights the aller-gen, but only in the area wherethe allergen contacted the skin.

In this application a contact aller-gy is described which was causedby two objects. Standard allergytests had not been helpful. Thetwo materials of interest were amouse pad and a leather wrist-band. What do both have in com-mon causing the skin reaction?

For the analysis, an instrumentdedicated to surface analysis isneeded, e.g. a single reflection

diamond based ATR (AttenuatedTotal Reflectance) unit integratedinto a FTIR sample compartment.

The test person showed differentreactions when applying twoleather wristbands. In one case,the skin appeared normal but inthe other case, an eczema wassoon apparent (Figure 1).

Single reflection ATR enabled theanalysis of the surface of differentleather-based materials as well as the mouse pad. Both of theleather samples were in contactwith the skin – one was a colored,smooth leather, and the second anundyed leather with the usualrough surface. The ATR measure-ment technique with a KRS-5crystal allows beam penetrationof approx. 2 μm into the samplesurface.

The analysis was done with FTIR spectroscopy and an ATRaccessory enabling a non-destruc-tive sample analysis. The sampleis placed on a measurement window and does not need anychemical pretreatment. Figure 2shows both spectra.

The main difference in figure 2 isthe signal at 1,727 cm-1. The sig-nal is a –C = O signal belongingto the acid based –COOH groupand may be present from differ-ent sources of molecular structureor substances of this class.

The spectrum was compared to a skin spectrum to prove thathuman skin traces at the surfacedid not influence the analysis ofthe leather band.

The skin spectrum shows no sig-nal peak at around 1,727 cm-1.The same infrared analysis wasdone with the surface of themouse pad that caused the skintrouble.

Figure 1: View of a contact allergy seen on an arm – a smooth skin reaction caused by a brown coloured leather wristband.

The zoom shows details of a typical eczema resulting from a contact allergy.

5

APPLICATIONShimadzu News 1/2011

d leather wristlet

A search of the infrared spectrafrom the mouse pad within an IRlibrary resulted in positive identi-fication as Polymethylmethacry-late (PMMA). It has a good over-lapping for the signal at 1,727 cm-1.Acrylate is known as a materialwhich can cause contact allergy.

Conclusion

It can be helpful to do a surfaceanalysis of the materials suspect-ed of being the source of the con-

tact allergy. The FTIR techniquecombined with ATR, particularlythe single reflection methodenables control of surface layersfrom thicknesses between 0.6 to 2 μm. These measurements helpto point the direction of the nextsearch for the allergy. Whether itis the polymer or a polymer com-ponent needs to be researched inmore depth with additional spe-cific allergy tests.

Instrumentation• IRAffinity-1

• DuraSamplIR, diamond based

single reflection unit

• IRsolution and libraries

We will gladly send you further infor-

mation. Please note the appropriate

number on your reply

card or order via the

News App resp. News

WebApp. Info 391

Figure 2: FTIR leather spectra. Blue is untreated leather while red is the treated

leather surface

Figure 3: FTIR spectrum from the skin of a finger with single reflection accessory

Figure 4: FTIR single reflectance spectrum from the surface of a mouse pad Figure 5: Comparison of Library spectrum (blue line) and the mouse pad surface

(black line)

0.010.020.030.040.050.060.070.080.09

0.10.110.120.130.140.150.160.170.180.19

0.20.210.220.230.240.250.260.270.280.29

0.30.310.320.330.340.350.360.370.380.39

4600 4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400

1/cm

Abs

0.010

0.020.030.040.050.060.070.080.09

0.10.110.120.130.140.150.160.170.180.19

0.20.210.220.230.240.250.260.270.280.29

0.30.310.320.330.340.350.360.370.380.39

0.40.410.42

4600 4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400

1/cm

Abs

0.010

0.020.030.040.050.060.070.080.09

0.10.110.120.130.140.150.160.170.180.19

0.20.210.220.230.240.250.260.270.280.29

0.30.310.320.330.34

4600 4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400

1/cm

Abs

-0.05-0.025

00.025

0.050.075

0.10.125

0.150.175

0.20.225

0.250.275

0.30.325

0.350.375

0.40.425

0.450.475

0.50.525

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

1.0

1.05

0.575

0.625

0.675

0.725

0.775

0.825

0.875

0.925

0.975

1.025

4600 4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400

1/cm

Abs


6

Windows in the spotlight

In the Hitchcock movie ‘RearWindow’, the window open-ing onto the courtyard was

open most of the time. In thisway, James Stewart could toleratethe summer heat of 1954 and alsosee the murder happening in hisneighbor’s house. But how, inthese times of global warming,can a comfortable indoor climatebe provided during the hot sum-mer months? Climate changeplaces increasingly higherdemands not only on environ-mental behavior, but also on ourway of life.

In addition to the use of air con-ditioning systems, efficient use ofbuilding materials is also helpful,and windows play a significantrole. Use of selected flat glasshelps to prevent as much heat aspossible from entering the room,while still allowing enough lightto pass.

Light transmittance in flat glass

The quality of flat glass in thebuilding industry is testedaccording to DIN EN 410: ‘Glassin building – determination ofluminous and solar characteristicsof glazing.’ In Japan JIS R 3106 isapplied: ‘Testing method onTransmittance, Reflectance andEmittance of Float Glasses andEvaluation of Solar Gain Coeffi-cient.’ Testing includes lighttransmittance and reflectance inthe visible spectral range of 380to 780 nm, solar transmittanceand reflectance between 300 and2,500 nm as well as normal emit-tance in the 2,000 - 400 cm-1

range (5,000 - 25,000 nm as IRmeasurement).

In the examples shown here,measurements were carried outaccording to the Japanese indus-trial standard JIS R 3106. Formeasurements in the visible

Determination of the transmittance and reflectance of

Figure 1: Display of the ‘Daylight’ software with calculation of results

Table 1: Instrument measurement parameters according to JIS R3106

Close to parallel

beam of light

incident from the

normal direction

The air layer is

used as the

standard sample,

and its spectral

transmittance is

taken to be 1

300 - 2,500 nm

< 300 nm, 5 nm max. 380 - 780 nm, 10 nm

max. 780 nm and higher, < = 50 nm max.

380 - 780 nm

10 nm max.

Close to parallel

beam of light

incident from the

radiation slit at

an angle not

exceeding 15

degrees

Specular reflector

of reflectance

specified by the

absolute reflec-

tance measurement

method (sample 1),

or specular reflec-

tor of reflectance

specified by

comparison with

sample 1

Close to parallel

beam of light inci-

dent from the radia-

tion slit at an angle

not exceeding 15

degrees.

Close to parallel

bundle of rays

incident from nor-

mal direction

Specular reflector

of reflectance

specified by the

absolute reflec-

tance measurement

method (sample 1),

or specular reflec-

tor of reflectance

specified by

comparison with

sample 1

IRAffinity-1 FTIR

spectrophotometer

and SRM-8000, an

accessory for spec-

ular reflection

5 - 25 μm

4 cm-1

Light radiation

at an angle not

exceeding 15

degree

Aluminum-coated

mirror with

certified absolute

reflectance (float

flat glass with

vacuumdeposited

aluminum film)

Visible range Solar range

Transmittance Reflectance Transmittance Reflectance

NormalEmittance

UV-3600 UV-VIS-NIR spectrophotometer ISR-3100 Integration sphere

(Ulbricht sphere) with three detectors

Analytical

instrument

Measurement

wavelength

range

Resolution

Incident light

conditions

Standard sample

for comparison

Close to parallel

beam of light

incident from the

normal direction

The air layer is

used as the stan-

dard sample and

its spectral trans-

mittance is taken

to be 1

7


– UV-VIS spectroscopy

as well as in the solar range, Shimadzu’s UV-3600 with theISR-3100 integration sphere wasused. The company’s IRAffinity-1with a directed SRM-8000 reflec-tance unit was applied for thedetermination of the normalemittance. Both instruments canbe used in the infrared range(thermal radiation). The UV-VIS-NIR UV-3600 system covers thenear infrared (NIR) range, andthe FTIR system covers the mid-infrared range (MIR).

According to JIS R 3106, themeasurement parameters can belisted as shown in table 1.

Evaluation of results is carriedout in accordance with JIS R3106. A spreadsheet program oroptimized software can be usedfor calculation. Parameters forthe visible (te) and solar (tv)transmittance as well as re-flectance determined as pe andpv, can be listed using Shimadzu’s‘Daylight’ software.

The following standard valuescan be determined optionally (see table 3).

As an example, the visible andsolar transmittance and the chro-maticity values for five types ofglass were calculated according to

flat glass in the building industry according to DIN EN 410/JIS R 3106

Table 3: Tristimulus values which can be determined using the

‘Daylight’ software

Figure 2: UV-VIS-NIR spectra of glasses in transmittance: black corresponds to

Glass-0, red to Glass-1, blue to Glass-2, green to Glass-3 and violet to Glass-4

Table 2: Visible and solar transmittance for five flat glass samples with Standard Illuminant D65 calculated under an observation

angle of 2°

JIS R 3106. The values are listedin table 2 and the UV-VIS-NIRspectra are shown in figure 2. TheStandard Illuminant D65 wasselected for the calculation as thisrepresents daylight according tothe CIE (International Commis-sion on Illumination). An angleof observation of 2° was selected.The results presented show just asmall extract of the determinationrange. [1][2]

[1] Shimadzu Application News No.

A396, ‘Daylight Transmittance

Application Data of Glass Plate’

[2] Shimadzu Application News No.

A404, ‘Glass Plate Analysis in

Accordance with JIS R 3106’

1/nm

T%

-9,112

0

50,000

100,123

300 500 1,000 1,500 2,000 2,100

x

1

2

3

4

5

86.756

36.167

31.559

9.164

8.108

90.672

29.913

27.223

1.527

1.389

85.830

28.586

25.912

9.124

8.267

90.672

29.912

27.223

1.525

1.387

98.478

60.079

54.484

48.573

44.027

GLASS-0

GLASS-1

GLASS-2

GLASS-3

GLASS-4

Sample number te tv y z File name

te, pe

dte, tpe

tv, pv

dtv, dpv

User

X, Y, Z

dX, dY, dX

x, y

dx, dy

dWL

Daylight transmittance, reflectance (JIS R 3106)

Difference of daylight transmittances, reflectances

(JIS R 3106)

Visible light transmittance, reflectance

(JIS R 3106, JIS Z 8722)

Difference of visible light transmittances, reflectances

(JIS R 3106, JIS Z 8722)

Calculated by user defined weighted factor file

Tristimulus Value X, Y, Z (JIS Z 8722)

Difference of X, Y, Z

Chromaticity Coordinates x, y (JIS Z 8722)

Difference of x, y

Dominant Wavelength dWL (JIS Z 8701)

We will gladly send you further information. Please note

the appropriate number on your reply card or order via the

News App resp. News WebApp. Info 392


8

Exceptional: Co-Sense fo

Nowadays, regulatoryauthorities of the phar-maceutical industry

emphasize risk assessment. Thisis why the term ‘risk basedapproach’ is used. Depending onthe permissible daily dosages ofdrugs, the guidelines specify cor-responding threshold values forimpurities. In compliance withrisk assessment, dangerous impu-rities must be removed as far aspossible.

ICH (International Conferenceon Harmonization) guidelinesQ3B(R2) Q3A(R2) and Q3C(R4)deal with contaminations in newdrugs and active substances. Thesame also applies to the guide-lines for generic drug approval(ANDA’s – Abbreviated NewDrug Applications) of the Ameri-can Food and Drug Administra-tion.

The following impurities canoccur during synthesis as well asduring production:

systems, the Co-Sense for Impu-rities features suitable controlsoftware for straightforward andvisual system control.

The blue flow line depicted infigure 2 shows the separation ofthe binary gradient system in thefirst dimension, before and afterenrichment on the trap column(at switching valve R). The purpleflow line shows the situationbefore and after separation by thebinary gradient system in the sec-ond dimension.

Figure 3 shows that upon switch-ing valve L to the new position,the trap column at valve R is nowloaded in the first dimension,while the LC-20AP preparativepump ensures a sufficient make-up flow (yellow flow line) with aweak eluent to prevent prematureelution of the components fromthe trap column.

After a suitable enrichment time,the valve L is switched back tothe original position and valve Ris switched in order to separateand detect the components thatare collected on the trap columnin the second dimension.

User interface

The graphical user interfaceenables straightforward and intu-itive system control. The ani-mated graphics show the systemstatus. Two separate chromato-gram windows show the chroma-

need to be identified and quanti-fied – depending on the maxi-mum daily dosage permissible.

One-dimensional HPLC systemsdo not usually offer the requiredsensitivity or corresponding sepa-ration efficiency for analysis. In these cases two-dimensionalsystems with sensitive detectors(LCMS) are recommended.

Co-Sense for Impurities

The two-dimensional Co-SenseHPLC system for Impurities(Figure 1) is suitable for high-sensitivity measurement of impu-rities with straightforward detec-tion (first dimension: UV; seconddimension: UV or light scatter-ing). In comparison with LCMS,UV or light scattering detectionis more straightforward and cost-effective for high-sensitivityquantitative determination ofimpurities.

Functional principle

Co-Sense fractionates and con-centrates the impurities that havebeen separated in the first dimen-sion onto an trap column. In thesubsequent separation step of thesecond dimension, an improvedseparation is obtained as well as a 10 to 20-fold increase in sensi-tivity, which results from down-scaling the column diameter. Asthe control of two-dimensionalHPLC systems is quite complexcompared to one-dimensional

• organic impurities• impurities in raw materials• by-products, intermediate and

degradation products• reagents, ligands and catalysts• solvent residues, heavy metals,

inorganic salts• other materials such as filters,

activated carbon

All these impurities, in corre-sponding concentrations, consti-tute risks for the patient. Theserisks need to be eliminated. Theguidelines specify the concentra-tion levels at which impurities

Figure 1: Co-Sense for Impurities

Figure 2: Co-Sense for Impurities in

stand-by position before or after enrich-

ment respectively

Figure 3: Co-Sense for Impurities during

enrichment

Figure 4: Co-Sense for Impurities during

separation in the second dimension

9


r Impurities Drug safety

Figure 5: User interface of the Co-Sense for Impurities

Figure 6: High sensitivity and improved precision

Figure 7: Improvement of the separation efficiency

tograms in the first and seconddimensions, as well as the timewindow for the fractionation andadditional status plots for pumppressures and temperatures. Gra-dient programming is also dis-played in two separate windows.

The system monitor shows thecurrent flows, pressures and elu-ent compositions. System param-eters can be entered directly andindependently of the methodused. A sample table allows batchprocessing of multiple samplesaccording to different methods.

Features

Co-Sense for Impurities isequipped with two separatedetectors allowing data acquisi-tion in both dimensions. Thehigh-pressure tolerance of theUV detector cell in the firstdimension also enables highmake-up flows to prevent lossescaused by premature elution fromthe trap column. The pump forthe make-up flow is a preparativecompact high-performance pumpdelivering the desired outputwithin the shortest time possible.The pump can be switched offduring the stand-by mode, saving

eluent and reducing energy con-sumption.

A separate window for enteringthe flow volumes ensures time-accurate switching of the valvesand start-up of the make-uppump, allowing reliable fractiona-tion. The system package alsoincludes preconfigured capil-laries, already provided by thesoftware in the default setting.

Application examples

Figure 6 shows the peak of a0.00001 % spiked impurity of anactive substance. The chromato-gram in the first dimension (Fig-ure 6/left) shows that the peak is

very close to the detection limit.A 10-fold repeat measurementyields a relative standard devia-tion of the peak areas of 18.6 %RSD, whereas in the seconddimension the impurity peak lieswell above the limit of quantifica-tion. A 10-fold repeat measure-ment in the second dimensionresults in a peak area precision of1.2 % RSD.

Figure 7 shows the improvementof the separation efficiency in thesecond dimension. In the first

dimension (Figure 7/left) the0.0008 % impurity of the mainactive substance cannot be identi-fied below the purple fractiona-tion mark. The second dimensionin the right image shows an over-lay of the active substance withthe impurity, the pure active sub-stance, the pure impurity and theblank injection. It can easily beseen how well the impurity is

separated from the main compo-nents.

Summary

Based on the requirements of the pharmaceutical industry andthe regulatory authorities, theCo-Sense for Impurities systemoffers high-sensitivity analyses ofimpurities at the trace level. Thespecial software enables reliableand straightforward operation.Via the two-dimensional chroma-tography setup, sensitivity and

separation efficiency are im-proved immensely. Furthermore,this setup enables combination ofvarious chromatographic tech-niques to improve separation effi-ciency. At present, Co-Sense forImpurities is truly exceptional.


10

Tracing PAH analysis witsample pretreatment Onlin

Nowadays, there is anincreasing demand toautomate sample pre-

treatment in order to reducelabour costs and increase produc-tivity. In environmental laborato-ries trace enrichment is one of themost laborious tasks, as thisinvolves activities such as liquid-liquid extraction (LLE), clean-upand re-concentration by solventevaporation. In many cases, solidphase extraction (SPE) has suc-cessfully replaced LLE.

The use of online SPE requiresless solvents and brings an addi-tional benefit: there is no need toevaporate the extraction solvent,which is beneficial for overallrecoveries of the target com-pounds. Moreover, all of thedesired compounds will be de-tected. In case of off-line pre-treatment an aliquot of theobtained extract is always in-jected into the analysis system.

Another development in sampleanalysis is increasing throughput.In many cases, speed of analysisis the key factor. In environmen-tal analysis however, samples arequite complex. Even where com-pounds are detected using more

selective detection methods (e.g.fluorescence detection), enoughseparation power is still necessaryto fully resolve all detected com-pounds. Otherwise false positiveresults may occur.

In some cases, the possibility offalse positives can be ruled out or at least diminished by the useof a second detector. Sometimes,a fast analysis method is used forscreening. When a positive resultemerges it needs to be confirmedby a second technique. As statedabove in environmental analysis,samples are very complex so onlymethods with very selectivedetection techniques (e.g. LCMS/MS or GCMS) can be used forscreening.

online SPE method for thedetermination of PAHs

Shimadzu Benelux together withVitens, the largest drinking waterproducer in the Netherlands, hasdeveloped an online SPE (solidphase extraction) method for thedetermination of polycyclic aro-matic hydrocarbons (PAH) indrinking water, ground water andsurface water. The company sup-plies about 350 million m3 of

Minutes

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

9,000

10,000

11,000

mV Max. Inten.: 8,605.922

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0

Figure 1: Chromatogram of PAH standard 1 μg/L

drinking water annually to onethird of the Netherlands and isinternationally active in helpinglocal drinking water companies inAfrica, South America and Asiato improve their water supplyand sanitation.

The analysis of polycyclic hydro-carbons is primarily carried outusing HPLC with UV or fluo-rescence detection or GCMSalthough the latter two are gener-ally more accepted. The objectivein this case was to combine SPEwith an HPLC method with fluorescence detection.

As a starting point an HPLCmethod for the complete separa-tion of 16 EPA priority PAHswas taken. The method incorpo-rates a C18 reversed-phase col-umn onto which a water-acetoni-trile binary high pressure gradi-ent was executed. Separation wasfurther improved by lowering thecolumn temperature to 20 °C andadjusting the steepness of the gra-dient from 25 to 100 % acetoni-trile in 30 minutes. The minimumresolution between the criticalpair (acenaphtylene and fluorene)was around 3.4. The low temper-ature of the column gives maxi-

mum resolution for the PAHcompounds which enables easyswitching of excitation and emission wavelengths of the RF-20Axs fluorescence detector.

When method robustness wasestablished, the HPLC systemwas further extended with onlineSPE capability. For this, an SPEcartridge, a pump with four sol-vent selection valves for cleaning,conditioning and flushing of theC8 SPE material and two 6-port2-position valves were added. Inthis stage, more degassing capaci-ty was added and the autosamplerwas replaced by a preparativeSIL-10AP which is most suitedfor large volume injections.

Before sample loading, the SPEcartridge was first cleaned withacetonitrile, conditioned withmethanol and flushed with water.4 mL of sample was injected andtransported to the SPE cartridgewith a flow of 1 mL/min of anacetonitrile-water mixture. PAHcompounds tend to stick any-where in the HPLC system so asolution of 33 % acetonitrile isneeded to overcome this problem.After sample loading, the car-tridge was again flushed with

water before the compoundswere desorbed with 100 %acetonitrile. The flow com-ing from the SPE cartridgewas downstream mixed withwater to form the water-ace-tonitrile gradient for elution

Figure 3: HPLC system

11


of the PAH from the analyticalcolumn.

Analytical conditions

Column: Pursuit PAH3 4.6 mmi.d. x 100 mm L, 3 μmPre-column: ChromSep Guard,Pursuit PAH 3 x 10 mm LMobile phase: A: water / B: acetonitrile

Gradient: B: 25 % –> 100 % (30 min)Flow rate: 1.0 mL/minTemperature: 20 °CDetection: fluorescence (seetable)Injection volume: 4 mLSPE column: HySpere Resin SH25, 2 x 10 mm LLoading flow: 1 mL/min water-acetonitrile 7/3 (v/v)

The limit of quantification(LOQ) lies between 0.0007 and0.0059 μg/L depending on thematrix, except for naphthalene(0.0087 - 0.021 μg/L). The LOQis calculated as three times thestandard deviation of an additionof 0.01 μg/L which was deter-mined on eight separate days.The repeatability is between 0.39and 6.4 % (n = 8), the repro-ducibility ranges from 1.3 to 9.9 % (n = 8).

Using the RF-20Axs, which is themost sensitive HPLC fluores-cence detector in the world, satis-fies the needs particularly forhigh-sensitivity environmentalanalysis.

[1] All 16 EPA PAHs can be

detected with a UV detector.

With fluorescence detection

only 15 out of 16 EPA PAHs

could be detected, as acenaph-

thylene does not exhibit native

fluorescence.

[2] Sample was mixed with acetoni-

trile in the sample vial prior to

injection

Figure 2: Schematic representation of SPE system

Table 1: Table with wavelength settings

0.0

30.0

32.1

33.7

35.0

35.9

37.2

42.9

50.3

224

276

250

256

287

252

268

290

305

330

320

370

390

440

402

398

430

480

Naphthalene

Acenaphthene, fluorene

Phenanthrene

Anthracene

Fluoranthene

Pyrene

Benzo[a]anthracene, Chrysene

Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo-

[a]pyrene, Dibenz[ah]anthracene, Benzo[ghi]perylene

Indeno[123cd]pyrene

Time Ex Em Compound(s)

h automatede SPE method


12

Mercury in your eyeX-ray fluorescence analysis – Hg content in

contact lens solutions

Mercury has been knownfor ages, and can befound in ancient Greek

history. In the middle ages it wasused for medical treatments, andvery often it was over-dosed.Today, the element is also part ofeveryday products such as sterilesolutions for cleaning contactlenses. One of the components of

the lens solution may be Thiom-ersal (commonly known as Thi-merosal in the US).

Thiomersal is a mercury-basedpreservative used since the 1930sin the manufacture of vaccinesand other pharmaceutical prod-ucts such as antiseptics, and alsofor cosmetics and contact lenssolutions. It is used to preventbacterial and fungal growth. Dur-ing vaccine production it has alsobeen used both to inactivate cer-tain organisms and toxins and tomaintain a sterile production line.

Mercury and mercury compounds

Mercury is a naturally occurringelement found in the earth’scrust, soil, water and the air. It isreleased into the environment byvolcanic eruptions, weathering of

rocks and the burning of coal.Through the food chain mercurycan find its way into the humanbody.

A sugar cube in a bathtub

How much mercury is in a con-tact lens solution? It varies fromcountry to country – in Germanyup to 0.007 % of thiomersal isallowed in cosmetic products (eye make-up and eye make-upremover [Directive 76/768/EE]).In a tested contact lens solutionthe concentration of Thiomersalwas 0.001 %. This is equal to 10 ppm or a sugar cube solved ina big bathtub (270 L).

How much mercury can be found in fish?

Predatory fish such as sharks andtuna contain rather high concen-

[keV]

0.00

0.50

1.00

1.50

10.0 20.0

[cps

/uA

]

Figure 1: FP Measurement of contact lens solution measuring method: FP (fundamental parameter), measuring time: 300 s,

measured Hg concentration: 41 ppm

“The medium is the message“ – possibly Canadian communications theoristMarshall McLuhan’s most famous phrase. He viewed the media as ‘exten-sions’ to our human senses, our body and our mind. In the past decade espe-cially, these so-called ‘extensions’ have become exceedingly versatile andconvenient – starting with web 1.0 to the social networks of today which keepusers ‘online’ at virtually every location on earth.

As a modern customer magazine, Shimadzu News is now also breaking newground. The magazine, long accessible via the website, is now also availableas Shimadzu News App for the iPhone® or Android smartphones from theApp Store. In addition to the current publication, previous issues are avail-able in the archive. Additional functions and overviews as well as an exten-sive search function complete the offer.

In ‘MyShimadzu’, users can fill out the digital order form to request informa-tion on articles, Shimadzu’s general catalogue, or register for the Shimadzu e-Newsletter. Those who already have a Shimadzu ID for the exclusive sec-tion of the website will soon also be able to access the application databasein order to learn more of possible applications.

Easy Shimadzu News App installation:

• Search the App Store for Shimadzu – or scan the QR code

• The App is shown• Tap on the icon to start installation

By the way: the Shimadzu News App also runs on the iPad®. Simply installand adjust to the desired size.

Also available for Android, Blackberry® and iOS systems – The Shimadzu News WebApp*

Simply type www.shimadzu-webapp.eu or scan the following QR code.

The exact installation steps for iOS and Android can also be obtained in PDF format from the Shimadzu website.

*The WebApp/Shimadzu News App requires a web-enabled

smartphone (iPhone or Android). The Blackberry smartphone

is also suitable – separate instructions are not available.

NEWS 2.0 – The Shimadzu News App

13

TELEGRAMShimadzu News 1/2011

trations of mercury. A concentra-tion of 0.5 ppm for Tuna and upto 1 ppm for sharks is quite com-mon. Whether eating a tuna steak(200 g) for dinner or applying adrop of lens solution (0,05 mL)to your eye every morning over aperiod of three months – in bothcases almost the same amount ofmercury compound is providedto the body. Of course it’s not thesame compound, and is applieddifferently.

X-ray fluorescence analysis measures Hg content in contact lens solutions

For analyzing lens care solutionsFP-measurements (fundamentalparameters) were carried outusing Shimadzu’s EDX-720 X-ray fluorescence spectrometer. In order to obtain a better signalto noise ratio the sample solutionwas concentrated by evaporationof water to 1/10 of the initialquantity. Since nearly half of theweight of Thiomersal is due to

Mercury is toxic independent of its forms

The effects of exposure to mercury on health depend on its chemicalform (elemental, inorganic or organic), the route of exposure (inhalation,ingestion or skin contact) and the level of exposure. Depending on thetype and amount, exposures to mercury can damage the nervous system,kidneys, liver and immune system.

The two organic forms of mercury, methylmercury (found in fish) andethylmercury (in thiomersal), are closely related but have important dif-ferences. Methylmercury is more potent. Accumulation in the body ismore likely since the time needed for the body to eliminate it (known asthe half life) is about 50 days. Ethylmercury does not accumulate in thebody to this extent since its half life is only about 7 - 10 days.

Ethylmercury is rapidly converted in the body to inorganic mercury andexcreted. Mercury becomes harmful when it reaches a certain level inthe body. The toxicity depends on the amount of mercury consumed inrelation to body weight. Infants are at greater risk than adults due totheir lower weight. Mercury is accumulated over time.

It’s advisable to reduce total exposure to mercury in babies and youngchildren in a world where other environmental sources (particularly infood such as fish) may be more difficult to eliminate.

Mercury, the expected concen-tration of the original samplesolution is 5 ppm, and 50 ppmafter evaporation of the water.

Results of the analysis met theseexpectations. A mercury concen-tration of 41 ppm (expected 50ppm) was measured. X-ray fluo-rescence analysis is therefore asuitable method for determina-tion of the concentration of mer-cury in fluids. It is easy-to-use,precise and reliable.


14

Automatic quantificationdiphenhydramine in hum

Dipl.-Chem. L. Mut,

Dr. rer. nat. T. Grobosch,

Dr. med. T. Binscheck

BBGes (Berlin Institute for

Central Health Tasks),

Institute for Toxicology – Clinical

Toxicology and Poison Control

Centre Berlin, Oranienburger

Str. 285, D-13437 Berlin,

Germany

Acute poisoning is anemergency situation call-ing for immediate,

unequivocal and reliable detec-tion and determination of theconcentration of foreign sub-stances in blood in order toestablish the correct treatment forthe patient. Continuous availabil-ity of analytical instrumentationfor toxicological analysis is there-fore essential. In addition, thecompetitive advantage of a labo-ratory is dependent on a highanalytical-technological capa-bility.

In general, analysis is carried outon serum or plasma samples, asthese are easily withdrawn froman unconscious person. More-over, the concentration of activesubstances in blood is more easilycorrelated with the clinical pre-sentation of the patient than withthe concentration in urine. Foractive compounds at low concen-trations or with a short half-lifein blood, urine analysis can alsoprovide valuable information onthe condition of the patient (1), (2).

Urine is the sample material ofchoice for drug analysis, as theconcentration of foreign sub-stances remains detectable in highconcentrations for days (3). Inthe TOX.I.S., toxicological iden-tification system, (1) an addition-al method for quantitative deter-mination in plasma has now beenintegrated. The method wasdeveloped at the Institute forToxicology in Berlin, Germany(BBGes) in the working group ofDr. Grobosch in collaborationwith Shimadzu. This articledescribes the applied methodolo-

and didesmethyl-diphenhy-dramine, subsequently oxidizedto diphenylmethoxy acetic acidand further conjugated to glu-tamine and glycine (Figure 1).DPH is eliminated mainly via thekidneys (approximately 60 %within 96 hours in the form of itsmetabolites) – a maximum of 1 %of the active compound appearsunchanged in the urine (18), (19).The specified average eliminationhalf-life is four (2.4 to 9.3) hours(16).

DOX metabolism occurs prima-rily in the liver. N-desmethyl-

critical concentration in plasmafor DOX is specified as 3 mg/Land for DPH as 5 mg/L (14).

Symptoms for DOX and/or DPHpoisonings are skin redness (ery-thema), dry mucous membranes,coordination disorders, restless-ness, anxiety, states of agitation,hallucinations – in severe casesseizures, cardiac arrhythmias,ataxia and motoric unrest. Lethalpoisonings are characterized bycoma, heart / acute respiratorydistress syndrome and majorseizures (15).

DPH is strongly bound to plasmaproteins (85 to 99 %). The distri-bution volume is 3 to 4 L/kg (16).Metabolism is mainly carried outin the liver (CYP2D6, CYP1A2,CYP2C9 and CYP2C19 [17]).DPH is first dealkylated to mono

gy and presents examples of twopoisoning cases.

Introduction

Doxylamine (DOX) and diphen-hydramine (DPH) are first gener-ation competitive histamine H1-receptor antagonists with anti-cholinergic, hypnotic, sedative,local anesthetic and antitussiveproperties (4), (5). They are avail-able without prescription, areimmensely popular in the drugscene and rank among the mostcommon causes of acute poison-ing. DOX and DPH are pre-scribed for sleep disorders andare often purposely taken in sui-cide attempts (6), (7). The effec-tive daily dosage for DPH isbetween 30 and 100 mg (8) andfor DOX between 25 and 50 mg(9). The lethal dose for DPH andDOX is 40 mg/kg (10) and 25 -250 mg/kg (11) respectively. Acombined intake with alcohol,cocaine, morphine, barbiturates,benzodiazepines or DPH leads tosynergy effects (12), (13). The

TOX.I.S. supports automated and quantitative deter

Figure 1: DPH metabolism in humans

: b�Sample =AreaSample

AreaInt.Standard

b = slope of calibration curve

15


of doxylamine andan plasmamination of drugs in plasma

doxylamine, N,N-di-desmethyl-doxylamine and their N-acetyl-conjugates were detected (Figure2) (20), (21). The eliminationhalf-life is approximately tenhours (21).

Case 1

A 28-year old male (185 cm, 85 kg)was admitted to hospital withclinical symptoms of alcoholintoxication. His face and handswere reddened. Poisoning bydrug intake was not ruled out.

Case 2

A 41-year old woman (170 cm, 65 kg) was admitted to hospitalin a confused mental state withinvoluntary movements. Thewoman was suffering fromdepression. A rapid urine testcarried out in the hospital waspositive for tricyclic antidepres-sants.

Materials and methods,chemicals and standards

Methanol LC-MS grade wasobtained from Sigma Aldrich(Steinheim, Germany). All stan-dards, reagents and mobile phasescan in future be obtained fromRECIPE Chemicals + Instru-ments GmbH (Germany).

Instrumental configuration

The toxicological identificationsystem TOX.I.S. is configured asfollows:

Degasser: (2 x DGU-20A5),Pumps: (LC-20AT and LC-20 AB), High-pressure valve: (FCV-20H2), Column switching valves: (2 xFCV-14AH and 2 x FCV-12AH),Autosampler: (SIL-20AC), Column oven: (CTO-20AC),photodiode array detector

(SPD-M20A) as well as systemcontroller (CBM-20AC), all from Shimadzu (Duisburg,Germany).

Online extraction

An SPE type (RECIPE) columnwas used for solid-phase extrac-tion. SPE buffer, mobile phase A,mobile phase B and SPE rinsingsolution can be obtained fromRECIPE.

Sample preparation

300 μL of the internal standard inmethanol was added to 200 μL ofa plasma sample. The mixturewas subsequently shaken for fiveminutes at 2,000 r/min and cen-trifuged for four minutes atapproximately 14,500 x g. Thesupernatant (300 μL) was trans-ferred to a new 1.5 mL-Eppen-dorf cup and diluted with 1.0 mLSPE buffer.

Chromatographic conditions

Chromatographic separation wascarried out on an analytical col-umn with a precolumn of thesame type, both from RECIPE.Gradient elution was carried outby variation of the mobile phaseflow rate (0.6 and 2.0 mL/min).The column temperature was 40 °C, the UV detection wave-lengths were 230 and 205 nm, andthe injection volume was 1.0 mL.Analysis (including extraction)took place within 45 min.

Identification and quantification

A drug substance is considered tobe reliably identified when itsrelative retention time is at least95 % and spectral comparison hasbeen shown to be at least 99 % inagreement with the library. Tocalculate the concentration, thefollowing equation was used:

Calibration and controls

For the 6-point calibration, ana-lyte-free human donor plasmawas spiked with DOX/DPH (0.25, 0.5, 0.75, 1.0, 2.5 and 5.0 mg/L). Each point on the cal-ibration curve was calculated byaveraging from n = 10 measure-ments of the respective calibra-tion solution. Two controls (0.6and 1.2 mg/L) were preparedanalogous to the calibration solu-tion.

Results and discussion

The first experiments based onomitting the methanolic precipi-tation step, led to a comparative-ly low lifetime of the extractioncolumn (< 25 injections). Onlyby using methanol to precipitateplasma proteins could the lifetimebe increased to 500 injections perextraction column. At the sametime, the quality of the chroma-tograms was markedly improved,as fewer matrix peaks appeared.For the identification of �

Figure 2: DOX metabolism in humans

Table 1: Therapeutic and critical concentrations, operating ranges and limits of determination for DOX and DPH

Doxylamine (DOX)

Diphenhydramine (DPH)

0.1 - 0.6

0.2 - 1.0

3

5

0.25 - 5.0

0.15 - 5.0

0.25

0.15

Substance Therapeutic range (mg/L)

Critical concentration(mg/L)

Practical operating range (mg/L)

Limit of determination(mg/L)


16

unknown substances, an in-houselibrary, currently containingapproximately 500 UV spectrawith RT and RRT, as well as acommercial UV spectral library(UVTOX of Prof. F. Pragst con-taining > 3,000 entries) was avail-able.

The calibration curves for DOX(y = 67.25x) and DPH (y =25.18x) exhibit good linearitywith correlation coefficients >0.999. The upper and lower limitsof determination for DOX andDPH are suitable for the quanti-tative determination of both sub-stances within the scope of toxi-cological analysis (Table 1).

The controls (1 = 0.6 and 2 = 1.2mg/L) were selected to includethe lower and upper therapeuticrange. The repeatability for con-trol sample 1 (n = 8) was 6.2 %(DOX) and 6.0 % (DPH) respec-tively, for control sample 2 (n = 8) 10 % (DOX) and 8.5 %(DPH) respectively. The time-different intermediate precisionfor control sample 1 (n = 8) was8.7 % (DOX) and 9.3 % (DPH)respectively, for control sample 2(n = 8) 7.5 % (DOX) and 8.6 %(DPH) respectively.

In case 1, analysis of plasma sam-ples via HS-GC could not estab-lish alcohol poisoning (c < 0.03

mg/L in the higher therapeuticconcentration range (0.07 and0.17 mg/L). In addition, hydro-cortisone was detected (Figure 4,peak 9).

Summary

The new TOX.I.S. method forthe determination of drugs inplasma, developed by the Insti-tute for Toxicology Berlin, Ger-many in collaboration with Shimadzu, has been described bydiscussing two poisoning cases.The advantage of this method isthe straightforward but efficientsample preparation as well as theautomated identification andquantification of foreign sub-stances in plasma. For the identi-fication of foreign substances, aUV spectral library containingapproximately 500 entries (RT,RRT) as well as the UVTOXcommercial UV spectral library(> 3,000 entries) of Prof. F. Pragstis currently available. The sub-stances stored in the UV spectrallibrary contain the most com-monly used drugs (for instancetricyclic antidepressants, benzo-diazepines, etc.) with weaklyacidic, neutral and basic proper-ties as well as some of theirmetabolites.

Sources

1. L. Schönberg, T. Grobosch,

D. Lampe and Ch. Kloft. New

screening method for basic com-

pounds in urine by on-line extrac-

tion-high-performance liquid chro-

matography with photodiode-

array detection. J of Chromato-

graphy A.1134, 2006, 177 -185.

2. Björnstad, K, Beck, O and

Helander, A. A multi-component

LC-MS/MS method for detection

of ten plant-derived psychoactiv

substances in urine. J of Chro-

matography B. 877, 2009,

1162 -1168.

3. Jane, I, McKINNON, A and

Flanagan, RJ. High-Performance

Liquid Chromatographic Analysis

of Basic Columns Using Non-

Aqueous Ionic Eluents. J of

Chromatogrphy. 17, 1985, 486,

191-225.

The whole list of references is available

at www.shimadzu.eu/info/news

of dinordiphenhydramine,nordiphenhydramine and DPHcan occur in the chromatogram(8). In addition to the substancesmentioned, diphenhydramine-N-oxide (Figure 3, peak 4) wasfound in the plasma sample.Slikker et al. found that themetabolite profiles of DOX inplasma and urine are similar (22).Diphenylmethoxyaceticacid can-not be extracted from plasma dueto the selected extraction condi-tions.

In the second case, DOX as wellas nordoxylamine and DPH wereidentified in the plasma sample(Figure 4). Concentrations were <0.25 mg/L (DOX) and 0.29 mg/L(DPH) and were therefore in thelower therapeutic range. In addi-tion, amitriptyline, nortriptylineand five unknown amitriptylinemetabolites more polar than theirparent compound amitriptyline,could be identified.

For the quantification of amitrip-tyline and nortriptylene, calibra-tion solutions in the range up to 1 mg/L were prepared. Each cali-bration solution was measuredthree times (n = 3). The functionof the calibration curve foramitriptyline is: y = 17.17x (R2 =0.999) and y = 9.40x (R2 = 0.999,nortriptyline). Based on thesefunctions, the amitriptyline andnortriptyline concentration in thepatient was calculated: amitripty-line was with 0.084 mg/ L in thelower therapeutic range (0.05 -0.2 mg/L); nortriptyline with 0.16

g/L), contrary to initial suspi-cions. Using TOX.I.S., caffeineand hydrocortisone, as well as3.24 mg/L DPH could be detect-ed (Figure 3). The patients’symptoms such as facial redden-ing as well as dysphasia and coor-dination disorders, in combina-tion with a DPH concentration inthe upper therapeutic range,could be attributed to takingDPH. In addition to DPH, itsmain metabolites dinordiphenhy-dramine and nordiphenhy-dramine could be detected quali-tatively (Figure 3).

Aderjan et al. point out that insevere and deadly intoxications, a ‘three-peak pattern’ consisting

Figure 3: UV chromatogram of the plasma sample in case 1: 1 = dinordiphenhydra-

mine, 2 = nordiphenhydramine, 3 = diphenhydramine (DPH), 4 = diphenhydramine-N-

oxide, 5 = hydrocortisone and 6 = IS (N-ethyloxazepam)

Figure 4: UV chromatogram of the plasma sample in case 2: 1 = nordoxylamine,

2 = doxylamine (DOX), 3 - 7 = amitriptyline-metabolites 8 = diphenhydramine (DPH),

9 = hydrocortisone, 10 = nortriptyline, 11 = amitriptyline and 12 = IS (N-ethyloxazepam)

17

PRODUCTSShimadzu News 1/2011

reduce the split gas flow duringanalysis. The GC re-establishesthe required split ratio in time forthe next injection. At split ratiosof 1:100 or higher, more than 80 % of expensive carrier gasescan be conserved per analysis. As the production of the techni-cal gases used for GC is alsoenergy intensive, not only theoperating cost but ultimately alsothe emission of greenhouse gasesis reduced.

The GC-2025 is the beginning ofan era of novel analytical instru-ments uniting performance andeco-friendliness. The use of ecol-ogically selected materials allowsfor improved recycling of asmany components as possible.Energy-saving and environ-mentally sound manufacturingmethods are already appliedduring production. The realpotential of the GC-2025, how-ever, lies in its energy and gassavings during several years ofuse and, hence, its contributionto the reduction of CO2 emis-sions.

According to Asian wisdom,“each journey begins with thefirst step.”

Economical, practical,effective – GC-2025

In accordance with Shimadzu’snew eco-label (see page 2 ofthis issue) new products are

not only designed to be energy-optimized, but are also manufac-tured in an ecologically efficientway in order to already start con-serving energy during productionand, consequently, to reduce carbon dioxide emission. A cur-rent example is the GC-2025(Figure 1).

30 - 50 % energy savings

Due to the improved oven designand insulating materials, the GC-2025 reduces electricalpower consumption by approxi-mately 30 % during normal operation, compared with the GC-2010 Plus. Gas chromato-graphs used in routine analysis or process monitoring must beready-to-measure at all times, although they are not continu-ously measuring samples. Here inparticular, the GC-2025 featuresvarious gas saver and shutdownas well as autostart functions that

can be implemented, dependingon how quickly the GC must beready-to-measure once a newsample is pending.

Consistent use of the automaticshutdown function reduces thepower use by approximately half,leading to a reduction of almost237 kg CO2 emissions within oneyear.

Small and compact, the GC-2025also meets the increasing demandfor more effective use of expen-sive laboratory space. Comparedto the GC-2010 Plus, the ovencompartment is reduced butoffers enough space to accommo-date analytical flow line compo-nents consisting of an injector,possibly a pre-column and sepa-ration column, as well as a detec-tor. The oven offers adequate spa-ce for the installation of all custo-mary capillary columns. Customsetups are not necessary.

Detector gases controlledelectronically

The detector gases of the flameionization detector are controlledvia electrical pneumatics. Thegases are program-controlled andcan at all times be reduced or,when needed, increased and ignited. The sensitivity of theFID-2025 with a specified MDQof 2 pgC/s (MDQ = MinimumDetectable Quantity) is onlyslightly less than the current mostsensitive flame ionization detec-tor featured in the high-endmodel GC-2010 Plus (MQD 1.5pgC/s).

Efficient carrier gas savings

For applications with high splitratios, the electronic carrier gassupply of the split/splitless injec-tor offers several possibilities to

Figure 1: GC-2025 AF

with AOC-20i autosampler

Figure 2: Shimadzu’s eco-label

tion to its improved thermal sta-bility, the temperature range ofthe pyrolyzer furnace has beenextended. The new furnace nowcovers a temperature range of 40 °C up to 1,050 °C.

This enables the analysis of tem-perature-sensitive compoundsand also the cracking of highlytemperature-stable polymersusing high-temperature pyrolysis.

Highest productivity

Sample throughput is often limited by the cycle time of thefurnace. A reduction in timebetween individual sample mea-surements can significantly in-crease sample throughput. Due tothe low thermal mass of the newceramic furnace, it has been pos-sible to substantially reduce heat-ing and cooling times. While thepredecessor model PY-2020iDneeded approximately 14 minutesto heat the pyrolysis furnace

PRODUCTS Shimadzu News 1/2011

18

A fresh breeze sweeps p

For many years, Shimadzuand Frontier Laboratorieshave teamed up in pyroly-

sis GCMS. In 2011, Frontier Laboratories will introduce itsnew Multi-Shot EGA/PY-3030D.In combination with Shimadzu’sGCMS-QP2010 SE, the Multi-Shot EGA/PY-3030D provides aninnovative system for the com-prehensive analysis of numerouspolymers.

Just like its successful predeces-sor, the PY-2020iD, this newpyrolyzer is based on the provenvertical micro furnace pyrolysistechnology. The new design ofthe pyrolysis/GC interface con-tributes to the increased heatingand cooling rates and improvedthermal stability, leading to higher productivity and im-proved reproducibility.

The wide range of new acces-sories opens up new potentialsfor the analysis of polymers. Inaddition, these sample introduc-tion systems offer increasedapplication possibilities including

the analysis of weathering prod-ucts.

New ceramic furnace

The PY-3030D is equipped with alow thermal mass ceramic heaterthat guarantees a temperatureaccuracy of +/- 0.1 °C. In addi-

The new Multi-Shot EGA/PY-3030D pyrolyzer

from 50 °C to 600 °C, the newpyrolyzer needs just four min-utes.

Cooling is also fast, decreasingtime to next sample measurement

Figure 1: The entire pyrolysis-GCMS system with PY-3030D pyrolyzer and GCMS-QP2010 Ultra mass spectrometer

19


yrolysis

by a factor of three, correspon-ding to a saving in time of 66 per-cent. This vastly improved pro-ductivity particularly benefitsusers carrying out routine mea-surements using the EGA(evolved gas analysis) method.

For the EGA method a short col-umn (2.5 m x 1.5 mm ID, no sta-tionary phase) is installed intothe GC. The sample is heated inthe pyrolysis furnace using atemperature program over a widetemperature range, e.g. from 50 °C up to 600 °C. The tempera-ture of the GC oven is kept at300 °C for the complete run, sono chromatographic separationtakes place. In fact, the result is a curve displaying the intensity of a signal as a function of thepyrolysis temperature. For thispurpose, the pyrolysis furnaceneeds to switch repeatedly be-tween temperatures, wherebycooling from the maximum tem-perature down to the initial tem-perature (e.g. 600 °C down to 50 °C) can take up to 30 minutes.With its new high-performancecooling fan, the ceramic furnaceof the PY-3030D now needs anastonishing eight minutes. In thisway, significantly more samplescan be measured in the workingday. Productivity can be in-creased even further using theAS-1020E autosampler with itssample carousel accommodatingup to 48 sample cups.

Optimized repro-ducibility

The reproducibility of a pyroly-sis measurement depends signi-ficantly on the temperature stability of the pyrolysis furnaceas well as on the other compo-nents of the pyrolysis system. In the PY-3030D pyrolyzer, bothtemperature accuracy of the

pyrolysis furnace and interfaceheating between pyrolyzer andGC injector have been improvedto +/- 0.1 °C. When comparedwith the PY-3030D’s predecessor,this positive effect is evidentespecially in better reproducibili-ty at temperatures above 600 °C.

The temperature stability of the‘stand-by position’ should not beignored. The sample is locatedhere between desorption andpyrolysis in the double-shottechnique. Up to 600 °C, the PY-3030D maintains tempera-tures at less than 50 °C for thestand-by position which increaseminimally, even at higher pyroly-sis temperatures (800 °C - 1,000°C). In addition, optimized rins-ing of the sampler with carriergas after a new sample has beenintroduced ensures higher repro-ducibility. Water and air areremoved quickly and effectivelyfrom the system.

The design of the interface be-tween pyrolyzer and gas chro-matograph has also been revisedand the maintenance procedurehas been simplified, in particularthe exchange of pyrolyzer liners.

New applications

Frontier Laboratories has devel-oped a range of new samplersoffering novel possibilities forversatile analysis of polymers.Switching between sample intro-duction methods such as double-shot pyrolysis, liquid injection,reactive pyrolysis or sample irra-diation with UV light is possiblesimply by exchanging samplers.

• Micro-UV irradiator (photothermic, oxidativedegradation)The sample is irradiated with axenon lamp in the pyrolysis

furnace at any desired tempera-ture. The emitted UV-light isapproximately 2,000 times moreintense than light from a deu-terium lamp. In this way, it ispossible to simulate weather-dependent degradation process-es of synthetic materials andother polymers, while processesthat often take weeks can nowbe reduced to a few hours. Thisconfiguration is complementedby an additional gas or air sup-ply, so that the degradationprocesses can take place underoxidative conditions. The irra-diated sample is subsequentlyanalyzed for modifications viapyrolysis. Using a CryoTrap,highly volatile degradationproducts formed during irradia-tion can be trapped and addi-tional information on thedegradation processes can beobtained.

• Online micro-reaction samplerUsing ‘reactive pyrolysis’, polardegradation products such asfatty acids, small organic acidsor alcohols leading to small,broad and severely overlappingpeaks on a non-polar standardpyrolysis column, can be esteri-fied in the sample cup. The re-action products formed are sep-arated on the GC column whichcan be detected in a mass spec-trometer. Sample and reagentare placed in a glass vessel; theglass capsule is melted shut andplaced in the appropriate sam-pler. By means of the samplerthe sealed vessel is transferredinto the pyrolysis furnace andthe reaction takes place at apredefined temperature. Afterthe preselected reaction time,the sampler opens the sealedglass capsule and the carrier gaspurges the reaction productsonto the GC column.

The new accessories and the newmaximum temperature of the PY-3030D pyrolyzer offer com-pletely new application possibili-ties, such as irradiation of a sam-ple with UV-light or high-tem-perature pyrolysis. Optimizedtemperature control ensures in-creased reproducibility of pyro-lysis data, especially at highertemperatures. In addition, theoutstanding performance of theGCMS-QP2010 SE contributesto the excellent reproducibility ofthe data. While Pyrolysis GCMSis a versatile method for the anal-ysis of polymers, it is often rathertime-consuming. Analysis timeand hence productivity of thesystem can be drastically im-proved by the increased heatingand cooling rates.


20

Green – Yellow – Red

When hydrogen was dis-covered, it was called‘inflammable air’.

Today it is used in industry andtechnology for many applica-tions. Approximately 30 milliontons per year are used as energysource, reducing agent and hard-ening agent for fats and coolingagent.

Hydrogen is the optimal carriergas for obtaining the best gaschromatographic separationswithin the shortest possible time.High flow rates at markedly lower pressures make hydrogensuperior to all other carrier gaseswhen fast chromatographic sepa-rations with high resolution arerequired. There is however oneproblem: hydrogen is flammableand hydrogen/air mixtures abovethe lower explosion level ofapproximately 4 % are highlyexplosive. This is why helium isthe GC carrier gas of choice, inspite of its considerably higherprice.

green-yellow-red, continuouslyprovide information on thehydrogen concentration withinthe oven. ‘Green’ indicates thatno hydrogen is detected. Whenthe LED display remains in theyellow range for longer time, it isrecommended to test whether thesystem is gas-tight. ‘Red’ LED,accompanied by an acousticwarning signal indicates a signifi-cant gas leak.

When the hydrogen concentra-tion in the oven reaches the 1 %level, the device interrupts thehydrogen gas flow and switchesto an inert gas (Figure 2). Theremaining hydrogen is purgedout of the system. Even at highhydrogen flows, safety is assured,as explosive mixtures are onlyformed at concentrations fourtimes higher. When the gas leakhas been repaired, the sensor isreactivated via ‘Reset’ and thehydrogen flow is activated.

With productive helium sourcesrapidly dwindling, helium isbecoming a valuable commodity.The price difference from hydro-gen will increase and, consideringthe economical benefits, switch-ing to hydrogen may become aninteresting alternative.

A ‘total flow’ of this magnitude is achieved when using high splitratios. When the gas saver func-tion of modern GC systems is used, these high flows onlyoccur during sample injection –although a certain residual riskstill remains.

Increased danger also exists whenusing a so-called ‘methanizer’ incombination with a flame ioniza-tion detector (FID). The hydro-gen gas used for the FID flame isalso used for catalytic reduction,thereby enabling sensitive detec-tion of carbon monoxide and car-bon dioxide by FID detector dueto conversion to methane. Whenthe catalyst is mounted to theFID, additional leaks can occurwhich are not covered by theusual system check of the GCsystem.

Green – yellow – red

To exclude these risks, indepen-dent control through continuousmeasurement of the oven gasesusing a hydrogen sensor (Figure 1)is recommended, for instance an external device like the oneshown here from ScientificInstruments Manufacturer GmbH(SIM) in Oberhausen, Germany.

This external hydrogen sensorcan be mounted onto any GCsystem. The control unit is con-nected to a sensor within the GCoven. LEDs with the colors

Although state-of-the-art GCsystems feature diagnostic func-tions recognizing gas leaks at anearly stage, a certain residual riskremains. When the carrier gasflow in the GC system is veryhigh, the reaction time becomesvery short and an explosion with-in the GC oven can no longer beruled out.

Excluding residual risks

Gas chromatographs usuallywork with initial gas flows (alsocalled ‘total flow’) of 10 to 1,200mL/min. The volume of the ovenis approximately 14 liters, but canalso be smaller. At a volume flowof 50 mL hydrogen per minute,more than 11 minutes are neededto reach the point that an explo-sive mixture may form. At 500mL/min this time decreases toless than two minutes, wherebythe formation of an explosivemixture – a mixing ratio larger orequal to 4 % hydrogen in air –becomes possible.

Safe hydrogen handling

Figure 3: Back view of the hydrogen sensor control unit with gas connections

Figure 2: LED display warning at a hydrogen concentration of approximately 1 %Figure 1: Front view of the hydrogen sensor control unit with LED display

21


Sharper than aneagle’s eyeThe new Shimadzu Video extensometer

TRViewX in the accuracy class 0.5

An eagle’s eyes are amongthe sharpest in the animalkingdom. Even from a

distance of over 600 meters, anAmerican Bald Eagle can spot achunk of meat as small as 3 cm.

Shimadzu’s new TRViewX videoextensometer exceeds by far thisamazing performance: from adistance of more than 0.5 m, theTRViewX is able to detect linearelongations with an absoluteerror of only 1.5 μm and couldspot the same chunk of meatfrom an altitude of 9,000 meters.

Also for highly elastic materials

With a relative error of 0.5 %, the TRViewX is one of the fewvideo extensometers in the worldmeeting the demands of ISO 9513class 0.5. And this, when re-quired, over a measuring range ofup to 240 mm and at an ultrafast

measuring rate of 1,000 mm/min.The measuring range can, more-over, be increased to a phenome-nal 800 mm. In this way, evenelongations and yield strengths of highly elastic materials can bedetermined conveniently andaccurately.

Longitudinal and verticalelongation gauge

Eagles can see forwards and side-ways simultaneously. Similarly,longitudinal and vertical elonga-tion gauges are virtually integrat-ed in the TRViewX. With a mea-surement accuracy class of 0.5,sample widths of up to 300 mmcan be measured.

The video extensometer can befully integrated within Shimadzu’sTrapezium-X software. In addi-tion to the conventional stress-strain curve, Poisson’s ratio andthe Lankfort value can be deter-

mined using just one measuringdevice.

In combination with theTRViewX, the Trapezium-X soft-ware offers even more functional-ity. The assistant function sup-ports users in the accurate align-ment of the test specimen, there-by reducing the error source ofpossible lateral forces. A marking

aid helps in the correct applica-tion of markers on the test speci-men at the initial gauge length.

Individual photos and image sequences

During measurement, the videosignal can be recorded as syn-chronized with the force values.In this way it is possible to recal-culate and to unequivocally

Figure 1: Shimadzu TRViewX video extensometer with dual camera for wide

measuring ranges

Figure 2: Stress-strain curve with integrated video recording

assign the video image to a speci-fic measuring point. In manyways, the TRViewX can be con-sidered to be a real ‘shootingstar’. As it is, individual photosor even image sequences from thevideo (snapshots) are possible atall times, which can be integratedeasily in the data report – manu-ally as well as fully automatically.

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22

Eco-friendly and timesa

Since 45 years, TOC analyz-ers have been a part of Shimadzu’s product range,

including laboratory and onlineTOC systems as well as TNbsystems. With its TOC-V series,Shimadzu is the worldwide leaderin TOC analysis.

The new TOC-L laboratoryseries includes four newly de-signed models all equipped withShimadzu’s well-known 680 °Ccombustion tube and down-stream NDIR detector. In addi-tion, the TOC-VWP (PC con-trolled) and TOC-VWS (stand-alone) analyzers are available forwet-chemical oxidation applica-tions.

All applications from ultrapure water to sewage

The TOC-L systems, with theirextended measuring range of upto 30,000 mg/L TC (detectionlimit 4 μg/L) support all applica-tions from ultrapure water,drinking water, surface water andindustrial effluents up to highlycontaminated sewage. Measure-ment of liquid, solid and gaseoussamples is possible as well. Theproven ISP module enables fullyautomatic acidification and sparg-ing of individual samples without

contact with the environment(NPOC method) – also withoutuse of an autosampler. The fullyautomatic dilution functiondilutes highly contaminated sam-ples, thereby minimizing mainte-nance need of the catalyst and thecombustion tube. The dilutionfunction is particularly user-friendly for the creation of multi-point calibration curves. All thatis needed is preparation of a stocksolution and subsequently speci-fying, in the software, which cali-bration points are to be createdfrom this solution. The instru-ment carries out the rest automat-ically (refer to figure 5). Thissaves valuable laboratory time.

New features and options

Important advancements, includ-ing electronic carrier gas flowcontrol, distinguish the newTOC-L family. Small sample vol-ume measurements can now becarried out using a special kit. A bright display light indicatinginstrument status (‘Ready’, ‘Mea-surement’, etc.) can be seen froma distance.

For measurement of samples con-taining high salt concentrations

and low TOC concentrations,another option is available. In thiscase it is often not possible todilute the sample sufficiently. The high-salt sample combustiontube kit was originally developedfor the online TOC-4110. Basedon excellent experience, the saltkit was also developed for thelaboratory. The modified com-bustion tube and catalyst allowsignificantly more measurementsto be carried out before mainte-nance is needed. Just how manymore measurements are possibledepends specifically on the saltlevel and the TOC measuringrange. Using the salt kit for sea-water applications, approximately2,500 injections (40 μL injectionvolume) are possible.

An additional halogen scrubbercan be installed for samples con-taining high chloride concentra-tions, for instance due to hydro-chloric acid.

Simultaneous TNb

(total nitrogen) and TOC determination

The newly designed TNM-Loption enables simultaneous TNb(total nitrogen) and TOC deter-mination without the need for

New TOC-L series – from ultrapure water to highly c

Figure 1: TOC-L with ASI-L

Figure 2: : TOC-L with TNM-L modul

23


additional bench space. For thisapplication, the measuring rangehas also been extended to 10,000mg/L with a detection limit of 5 μg/L (TOC-LCSH/CPH). Detec-tion is carried out using chemolu-minescence.

Laboratories with high samplethroughput need a flexible andeasily operated autosampler suchas the ASI-L, which was devel-oped specifically for the TOC-Lseries. Depending on the type ofapplication, three different rack

types (9 mL, 24 mL and 40 mL)can be selected. When new sam-ples arrive at the laboratory whilethe instrument is already in theprocess of measuring, these cansimply be added to the autosam-pler (in the edit mode).

Standalone model

The standalone model is equipped with a new, easy-to-read TFT Color LCD screen. The efficiently arranged keypadand easy menu navigation enable

straightforward operation of theTOC analyzer. Measurement datacan be conveniently stored on aUSB stick, printed or, optionallyoutput from LAN. The operatingsoftware is now also available inGerman.

TOC-Control L software

The TOC-Control L software isa consistent advancement of theuser-friendly TOC-Control V 2.00 software. The newly con-figured sample window is evenmore intuitive and simplifiesaccess to sample-relevant infor-mation. Entering data in the sam-ple table is possible via a simple‘drag & drop’ function. On theleft-hand side is a list of the cre-ated calibration curves, measure-ment methods, control samplesand measurement sequences.These can now be sorted accord-ing to system and measurementparameters. A preconfigured vali-dation sample table simplifies theimplementation of instrumentspecifications such as sensitivity,linearity, reproducibility anddetermination limit.

Shorter wizards speed up the cre-ation of calibration curves andmeasurement methods. It is nowalso possible to use fractional fac-tors in the dilution function,allowing the creation of a calibra-tion curve with equidistant pointsfrom a calibration solution (Fig-ure 5). A preconfigured valida-tion sample table simplifies test-ing of instrument specifications.

Improved templates for sampletables can now be created forroutine analysis. The standbyoption can also be viewed andmodified during measurement.

Proven functions such as insert-ing new samples, control samplesand calibration standards duringoperation, control cards, export

functions and 21 CFR Part 11 aremaintained.

First eco-friendly TOC instrument

The TOC-L conforms to Shimadzu’s eco-label documentingan active contribution to ecologicalpreservation. Compared to theirpredecessors, instruments carryingthe eco-label are energy-saving andrequire much less space. TheTOC-L is 20 % narrower and itsenergy consumption has beenreduced by 43 %. In addition, theeco-label complies with the Euro-pean RoHS requirements.

vingontaminated sewage

Figure 3: TOC-L CSH

Figure 4: TOC-Control L software

Figure 5: 10-point calibration curve with

dilution function

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24

Flavor analysis i

The study of the volatilefraction in wine productshas become more impor-

tant, as these compounds make amajor contribution to the con-sumer’s overall perception of thequality of particular food anddrink products.

To improve the gustatory andolfactory properties of grapewines or give them certain char-acteristics, wine aromatization isoften carried out illegally byadding different flavored sub-stances of both plant and syn-thetic origin. The usage of anytype of flavored elements, includ-ing those of synthetic origin, fornatural wine production is pro-hibited by EU and RM legislation(INVV in the Republic of Mol-dova, 2008).

was applied, providing theextraction of volatile and semi-volatile compounds in a concen-tration range from tenths of ppbup to tens of ppm. For the identi-fication, the general library ofNIST mass spectra and the FFNSC 1.3 were used; the latterwas particularly developed forflavors and fragrances (availablefrom Shimadzu Europa GmbH).

Results and discussions

Comparison of raw white winewith the “Muscat” wine:The presence of a range ofmonoterpenes (C10H16) was iden-tified: beta-myrcene (2,6,7-octa-triene), p-cymene, D-limonene,beta (Z, E)-ocimene and terpine-ol. All of these monoterpeneswere identified in grapes of fla-vored varieties (Sanchez-Palomo,2005), although these are formedin insignificant amounts and arenot of interest in the olfactoryfield. At the same time, they arepart of the composition of essen-tial oils extracted from exotic andflavored plants:

• limonene: from lemons andoranges

• terpinol: from coriander• myrcenelum: from Myrcia

acris plant

The objective of this research was to compare the efficiency ofvarious analytical injection tech-niques used to detect the addi-tives with flavoring potential inwine.

Materials and methods

Research materials:For the analysis, raw materialwhite and red wine were used, towhich were added aroma of“Muscat” to the raw white wineand “Isabella” to the raw redwine from industry in the recom-mended ratio (1 :10,000). Com-parative analysis of the composi-tion of raw material wine and ofthe “variety” wine was subse-quently carried out using head-space (HS) and headspace solidphase microextraction (HS-SPME) GC/MS.

The Laboratory apparatus:All tests were carried out usingShimadzu’s GCMS systemequipped with the three-dimen-sional automated system for sample injection (AOC-5000)(Figure 1).

Applied method:20 mL vials were used, into which10 mL of sample and 4 g of NaClwere administered. For the SPMEa 100 μm Carboxen-PDMS fibre

Figure 2: Comparison of HS-GCMS analysis of white wine (black) and Muscat (purple)

Figure 1: Shimadzu GCMS system equipped with AOC-5000

0.20.1

0.30.40.50.6

0.8

1.0

1.3

1.51.4

1.21.1

0.9

0.7

1.6

3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5

(x 10,000,000)

25

READ FOR YOUShimadzu News 1/2011

recorded – two chemicals of synthetic origin with pineappleflavor (enantilic ether) and fruitcaramel (butyrate < 3-metylbutyl-,2-methyl->). The hexylic ester ofthe butanoic acid, present inextremely low quantity (pineap-ple flavor) can be of syntheticorigin, but it is also detected inthe composition of natural wines(Form No. 203-821-270 3/08,2008).

The presence of the p-Cresol,2,6-di-tert-butyl compound, anantioxidant agent of syntheticorigin, restricted to food prod-ucts, demonstrates the syntheticorigin of the aroma concerned.This compound, which manifestsallergic effect and is suspected tobe carcinogenic, is not part of theflavoring compounds, but isincluded in the composition ofthe synthetic aroma due to itsantioxidant effect. 3-phenyl-2-cyclohexene-1-one also repre-sents a synthetic compound thatcould be used as a solvent for p-Cresol, 2,6-di-tert-butyl.

Conclusions

1. It is relatively easy to detectthe origin of the aroma. In the

Original Article: Chemistry Journal

of Moldova, Volume 4, No.2, 2009

»COMPARISON OF ANALYTICAL

METHODS SENSITIVITY FOR

SAMPLES INJECTION IN THE

DETECTION OF COMPOUNDS

WITH FLAVORING POTENTIAL

OF WINES«

Authors: RODICA STURZA,

CONSTANTIN SÎRGHI,

MARIANA VRÎNCEAN,

Technical University of Moldova

case of the naturally identical,the presence of a greater num-ber of traces characteristic ofsubstances with flavoringpotential, was detected. Thenumber of components bearingflavoring potential was lowerfor synthetic aroma (only fivecomponents bearing flavoringpotential were found), whileother two chemical havingnothing in common with fla-voring substances but fulfillingvarious functions were alsorecorded.

2. The research demonstrated thatthe use of GC/MS with sampleinjection by HS method andwith the HS-SPME can be suc-cessfully applied to identify thearomatic profile of wines, inorder to detect wine counter-feiting (using nature identicaland synthetic aromas).

3. The GC/MS method with sam-ple injection by the HS-SPMEprovided a higher sensibilitythan the method of samplesinjection by application of HStechnique.

• ocimenum: from basil leaves• p-cymene: from camphor tree

wood.

As the purpose of this researchwas to compare the sensitivity ofthe analytical methods, the rawmaterial wine as well as the“Muscat” wine were analyzedusing HS-SPME (Figure 3). Inaddition to the compoundsdetected by the HS (headspace)GCMS, some monohydroxy ter-penic alcohols were reported asterpineol, and 1-terpinen-4-ol.The presence of these compoundswith flavoring potential, althoughin insignificant quantities, de-monstrates the natural origin ofthe used aroma (essential oils) forthe “Muscat” white wine.

Comparison of raw red winewith the “Isabella” wine:The presence of methylanthrani-late (a component of the primaryflavors of American hybridgrapes) is confirmed. The abun-dance of this trace is prevalentamong registered flavoring com-ponents.

Two significant traces of enan-thylic ether and butyrate < 3-methylbutyl, 2-methyl-> were

Figure 3: Comparison of HS (black) and HS-SPME-GCMS (purple) analysis of

Muscat wine

Figure 4: Comparison of HS-SPME-GCMS analysis of red wine (black)

and Isabella (purple)

n wine products

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

2.50

2.75

3.00

3.25

3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0

(x 10,000,000)

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0

(x 100,000,000)


26

High-precision analysis

Consumption of bottledwater has been increasingsteadily in the last years.

The average consumption of min-eral water was approximately 140liters per person in Germany in2010. The trend is still increasing,since bottled water is a healthyand inexpensive drink in compar-ison to other soft drinks.

Mineral waters contain mineralsand other dissolved substanceswhich influence the taste or addtherapeutic value. Mineral watersare generally obtained from natu-rally occurring mineral springs orsources. The dissolved substancesin either sparkling or still waterconsist of various salts, carbonateand sulfur compounds.

waters. In 2010, they have evalu-ated more than 100 mineralwaters and found some importantcontaminations with heavy

The German test organizations“Öko-Test” and “Stiftung Wa-rentest” monitor the quality ofGerman and European mineral

Atomic absorption spectroscopy – Microsampling me

Figure 1:

AA-7000

Source: Werner Krug / www.gourmetreise.at

27


of mineral waters

metals such as arsenic, boron andmanganese.

Furthermore, the concentrationof alkaline and alkaline earth ele-ments did not match the certifiedvalues on the labels. For example,mineral water which is declaredas calcium-rich must have a mini-mum concentration of 150 mg/Lcalcium. On the other hand, alow-sodium water must not ex-ceed a concentration of 20 mg/L,as this type of water is often usedfor therapeutic purposes.

The concentration levels of theessential and toxic elements haveto be controlled so that a con-stant water quality can be main-tained. Quantitative measure-ments of elements at the traceand ultra-trace concentration lev-els are carried out using atomicabsorption spectrophotometerssuch as the Shimadzu AA-7000 inflame and graphite furnace atom-ization (Figure 1).

Flame micro samplingmethod vs. flame con-tinuous method

Furthermore, the AA-7000 incombination with the ASC-7000sample preparation station allowsthe automated flame micro sam-pling method (Figure 2). In thismethod, the flame atomic absorp-tion analysis is conducted withsmall sample volumes (2 - 90 μL),while in the conventional flamemethod (hereafter “flame contin-uous method”), the sample iscontinuously aspirated with aflowrate of approximately 8 mL/min and larger sample volumesare needed for aspiration.

The flame micro samplingmethod has several advantagesover the flame continuous

thod analyzing Na, K, Ca and Mg

method: analysis is possible witha small amount of sample, andwhen the autosampler is used,automatic dilution of the sampleand automatic addition of buffersolutions are possible in order tocompensate for interferences.

Moreover, since only a smallamount of sample is introduced,the flame micro sampling methodis effective for analysis of highmatrix samples which may causeclogging of the burner in theflame continuous method. So themethod is the right choice fordetermination of alkaline andalkaline earth elements in mineralwater.

Sodium, Potassium, Calcium andMagnesium belong to the essen-tial mineral substances in thehuman organism. These elementsinfluence the generation of en-zymes and hormones, control theosmotic pressure in tissues andbody fluids and are important forthe exchange procedures in thecell membranes. The recommend-ed daily amounts (Na: 550, K:2,000, Ca: 800 - 1,000, Mg: 350mg/L) can be partly covered byconsumption of mineral waters.But the composition of mineralwaters according to the essentialelements has a wide variety, anddepending on the origin the com-position might be quite different.

DIN/EN regulations controlNa, K, Ca and Mg contents

Control of Na, K, Ca and Mg ina variety of mineral waters hasbeen performed according to cur-rent DIN/EN regulations withthe Shimadzu AA-7000 atomicabsorption spectrophotometer ina fully automatic multi-elementsequence. The blank, standardsand the water samples are all

placed in the autosampler andthen mixed automatically withthe corresponding reagents whichhave to be added according to theDIN/EN method. In the case ofSodium and Potassium, 40 μL ofCsCl solution (12.65 g CsCl + 50 mL HCl (d = 1.16) filled up to500 mL volume with H2O) willbe added for a 400 μL mixingvolume of standard and sample

Figure 2: Microsampling method

solution which is homogenizedbefore injection to the flame. Inthe case of Calcium and Magne-sium, a La2O3 solution (5.875 gLa2O3 + 50 mL HCl (d = 1.12)filled up to 250 mL volume withH2O ) has been used.

All instrumental parameters andmeasuring conditions are loadedautomatically from the softwareand combined in a multi-elementsequence. These conditions areset automatically for each ele-ment including optimized burnerheight and gas flow rates.

Under these conditions, a seriesof more than 20 drinking waterand mineral water samples hasbeen analyzed. A reference mate-

rial (NIST SRM 1640) was alsomeasured as a laboratory controlsample, showing an excellentrecovery rate of 99 %.

AA-7000 in combination with themicrosampling kit is a “state ofthe art” atomic absorption spec-trophotometer for high precisionmeasurements of element concen-trations in mineral waters.

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INTERN

28

iPad® control expands HPLC network functionality

New: Shimadzu News Pharma Special

The network functionality ofthe Nexera and prominenceHPLC systems have been

expanded and can now be moni-tored and controlled from an iPadwireless device. This new technol-ogy builds on the existing webinterface used in current ShimadzuHPLC systems and provides addi-tional management options.

When the iPad is used togetherwith workstation PCs, simultane-ous monitoring and control ofoperating and usage conditions ofmultiple HPLC systems within asingle network is possible.

Shimadzu has launched a Spe-cial Edition of the ShimadzuNews specifically for the

needs of the pharmaceutical indus-try. 40 pages introduce solutionsand applications for a multitude of topics such as drug research,development and testing as well asmethod development, manufactur-ing and quality control.

The applications cover many dis-ciplines of analytical instrumenta-tion, e.g. chromatography, TOCand spectroscopy. Indepth articlesdescribe new as well as established

methods. In a highly regulatedenvironment, the pharmaceuticalindustry depends on increasinglysensitive measurements, and thesame time efficiency, cost-effec-tiveness and ecology.

Some selected highlights: TOCanalysis of ultra pure water, detec-tion of heavy metals by EDX,impurity analysis by two dimen-sional LC and LCMS-IT-TOF,and extrusion testing of blisterpackaging. The new Crude2Puresystem, jointly developed by Shimadzu Corporation and Glaxo-

SmithKline UK, demonstrates Shimadzu’s innovation and abilityto provide tailor-made technolo-gies.

Shimadzu Pharma News will soon be available as download atwww. shimadzu.eu or via App foriPhone® and Android (ShimadzuNews WebApp / Shimadzu NewsApp).

A printed version can also beordered directly from Shimadzu.Shimadzu News Pharma Special ispublished in English.

Many tasks which previouslyrequired a trip to the lab can nowbe performed wirelessly via theiPad.

The mobility and document brows-ing features of the iPad provideadditional gains in laboratory efficiency through quick and easy access to vital information.Shimadzu’s upgradable modularHPLC design allows these newfunctions to be used by existingNexera and prominence seriesequipment as well.

The new functionality enables:• Improved efficiency through

equipment status monitoring,such as batch monitoring ofanalysis conditions and operat-ing status including error re-porting

• Improved efficiency in equip-ment maintenance tasks

• HPLC system and analyticalcolumn cleaning. Sample pre-treatment, processing of analysis

data and other tasks can now beperformed while working awayfrom the HPLC equipment.

With increasing demand for regu-lation and validation in the phar-maceuticals, food and beverage,and nutritional supplements indus-tries, there is a need for more effi-cient maintenance managementwhich allows for multiple instru-ment inspection from a single plat-form.

In the HPLC laboratory, manytasks need to be done at once. By enabling access via wireless

networking from the iPad, a vari-ety of tasks can be performed withthe flexibility to move easilybetween different lab stations orlocations.

Trademarks

iPad is a registered trademark

of Apple Inc. in the United States

and/or other countries.

Figure 1: Analysis screen Figure 2: Group monitor Figure 3: Maintenance screen

shimadzu news 1 2011...sample pretreatment – online spe method »10 mercury in your eye – hg...

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