3D-D

arst

ellu

ng,N

ASA

/JPL

-Cal

tech

Laboratory opening ceremony withhammer stroke

Experience »Excellence in Science«live on more than 1,500 sqm in theShimadzu Laboratory World.

World premiere: HPV-X

The new high-speed video cameraHyper Vision HPV-X – 10 millionframes per second!

The gardener did it ...

An evidence-based trial with theLCMS-8040 Triple Quadrupol

The ravages of time – IR spectros-copy investigates aging of a polymerbag 2

The gardener did it ...A legal trial using the LCMS-8040 triple quadrupole 6

Talking about meats – TOC deter-mination in phosphoric acid in thefood industry 7

How to keep a clear view – Qualityassurance applying spectroscopy forEye-Cleaning solutions 12

Redefining spectrometric niches –High absorbance readings in UV analysis of Tertiary-Butyl-Catechol(TBC) 16

Trace analysis with plasma tech-nology – World premiere – The newdetector concept: barrier ionizationdischarge detector 4

Top athlete – IRTracer-100 for highsensitivity, high resolution and highspeed applications 5

Crucial steps ahead – World premiere – The new HPLC SPD-M30Aphotodiode array detector 8

Long winter period pollutes airportwastewaters – Efficient monitoring by online-TOC 10

New tool for healthcare and cosmetic products – SPFCalculatorsoftware for Shimadzu UV-VIS instrumentation 17

Shock waves – World premiere – The new high speed video cameraHyper Vision HPV-X 18

From soft to hard – The new HMV-Gmicrohardness tester 19

Moldy off-odors in fruits and vegeta-bles? – Determination of trichloro-anisole and tribromoanisole 14

Laboratory opening ceremony with hammer stroke – »Excellence in Science« on 1,500 m2: World and European premieres 20

APPLICATION

PRODUCTS

LATEST NEWS

SHIMADZU NEWS 2/2013

CONTENT

The ravages of time

F or 15 years, it modestlywrapped objects in thehousehold. It had a place in

the sun near a window with aview. But then, all of a sudden, theplastic bag disintegrated into dust.At first into small parts, whichupon further touching fell apartinto even smaller bits. The baghad acquired a ‘fractal’ life.

What has happened?

Solar radiation triggered oxidationof the polymer, as has been de-

scribed frequently in the litera-ture. To verify this assertion, frag-ments of the aged plastic bag wereinvestigated non-destructivelyusing infrared spectroscopy (IR)and the ATR measuring technique(Figure 1). In the present case, adiamond ATR unit was selected.As oxidation is a surface phenom-enon, the ATR method is highlysuitable. Depending on wavenum-ber, optical element and window,the penetration depth is about 2 μm (at 1,000 cm-1) into the sur-face.

IR spectroscopy investigates aging of a polymer bag

Figure 1: The pressure rod of the DuraSamplIR pushes a disintegrated piece of the plastic

bag against the diamond prism

3SHIMADZU NEWS 2/2013

APPLICATION

Measurements

To generate a reference spectrum,a commercial polyethylene (PE)white plastic bag without printwas measured. This bag serves as‘fresh’ polyethylene at the definedtime ‘zero.’ The spectrum is freefrom CO vibrations originatingfrom the group of carboxylicacids.

Inner as well as outer surfaces ofaged plastic bag samples wereexamined (Figure 2). The samplesoriginate from the white parts ofthe bag which have been exposedto the sun. In this way, it was pos-sible to compare the aged foil tothe fresh foil without any distor-tion of the results due to coloredprints and polymer layers contain-ing other substances.

Figure 2 shows the infrared spec-tra for comparison between freshand aged foil. In the fingerprintregion (1,000 - 1,400 cm-1) the foilsdiffer fundamentally from oneanother according to different ad-mixtures or fillers. The infraredvibrations of polycarbonate andacrylate do not correspond to thetriplet structure in the range of1,200 - 1,050 cm-1.

Detailed clarification of which ofthe vibrations in the fingerprintregion are due to the aging pro-cess would be necessary. The car-

Theory

During polyethylene oxidation,hydroxyl, carbonyl and vinylgroups are formed from the long-chain -[-CH2-CH2-]n- The poly-mer chain shortens and becomesmore brittle, leading to disintegra-tion of the material after sufficientconversion or progressing of oxi-dation.

Polyethylene inherently evokes aninfrared spectrum that has veryfew bands. Three significant vibra-tional ranges leave room for IRwindows, one of which is locatedin the so-called ‘fingerprint’ re-gion. This is why polyethylene isalso used as carrier material forother highly viscous substances(e.g. oils) in order to measuretheir infrared spectra.

As already mentioned, polyethyl-ene exhibits a simple IR spectrum.The polyethylene spectrum be-comes more ‘interesting’ whenaggregants are intended to influ-ence its target characteristics. Inthis case, vibrational bands en-hance the absorptions in the IRwindow. During oxidation ofpolyethylene, carboxylic acidderivatives are formed, with COvibrations which are stronglyinfrared active. Small amountsalready generate strong absorp-tions in the infrared spectrum at1,700 - 1,750 cm-1.

boxylic acid vibrations represent asimple range to detect aging. Inaddition, the aged foil – inner andouter surface – can now be com-pared. The signal at 1,710 cm-1 isclearly recognizable, arising fromthe carboxylic acid group. Thepresence of this vibration pointsto the aging process.

Abs

.

1/cm1,900 1,800 1,700 1,600 1,500 1,400 1,300 1,200 1,100 1,000 900 800 700 600 500

Figure 2: Infrared spectra of various polyethylene samples. The green line represents the

‘fresh’ polyethylene and the grey (inner surface) and blue (outer surface) lines represent

the aged material

Figure 3: Representation of eight infrared spectra from four samples. The dark blue to

bright red spectra represent the inner surface and the green to blue spectra represent the

outer surface.

Figure 4: CH2-vibrations in the range of 1,400 - 1,500 cm-1. Green represents the ‘fresh’

foil while blue represents the aged (outer surface) foil.

%T

1/cm1,850 1,800 1,750 1,700 1,650 1,600 1,550 1,500

90

92.5

95

97.5

100

102.5

105

1/cm1,550 1,500 1,450 1,400 1,350

Abs

.

PRODUCTS

4 SHIMADZU NEWS 2/2013

T he need for a robust, easy tooperate but sensitive univer-sal detector in gas chromato-

graphy has existed for a long timealready. The flame ionization de-tector (FID) is popular due to itsoutstanding combination of long-term stability and sensitivity. Un-fortunately, its detection spectrumlacks permanent gases such asnitrogen, carbon dioxide etc. Thethermal conductivity detector(TCD) is a universal, robust de-tector and can detect all compo-nents. It is not, however, sensitiveenough for today's detectionrequirements. The family of heli-um ionization detectors (HID)offers a solution. These detectorsare highly sensitive, although they

Trace analysis with plasma World premiere – The new detector concept: barrier ionizatio

(see Figure 3) bring helium to theexcited state and create a coolhelium plasma.

A thin tube made of quartz glass serves as

Figure 1: Barrier Ionization Discharge Detector (BID)

Figure 3: Cross-sectional drawing of a BID detector.

Introduction of the discharge gas and helium plasma generation takes

place in the upper half of the detector, while detection of the components

eluting from the capillary column takes place in the lower half.

Figure 2: Plasma technology of the BID

require a certain finesse in han-dling and some compromises alsohad to be made with regard totheir long-term stability.

The new BID detector concept

With the barrier ionization dis-charge (BID) detector, Shimadzulaunches a new concept in heliumionization technology (Figure 1).As with most HID detectors, ahelium plasma is generated byelectrical excitation of heliumatoms (Figure 2). The dischargegas (ultrapure helium) used forthis purpose is introduced at thehead of the detector. The elec-trodes arranged in the upper half

dielectric barrier between the elec-trodes and the helium plasma. Inthis way, the electrodes are not indirect contact with the heliumplasma and are therefore not con-taminated or affected by the plas-ma itself. This is one reason forthe long-term stability of the bar-rier ionization discharge detector.Tests have shown that the relativesensitivity hardly changes, evenover more than 3,000 hours ofoperation. Only during the firstweeks of operation does thedetector sensitivity increase some-what (see Figure 4).

In principle, the BID can be divi-ded into two zones (Figure 3).The plasma is generated in theupper zone, ionization and detec-tion of the chromatographicallyseparated components takes placein the lower zone. Ionization ofthe components does not takeplace through collision with excit-ed helium atoms, but rather vialight emitted from the heliumplasma. The ionization energy ofthe light is 17.7 eV, whereby theBID is able to detect all organicand inorganic compounds at lowerionization energy. Only heliumitself and neon cannot be detected.

5SHIMADZU NEWS 2/2013

PRODUCTS

technologyn discharge detector

Rela

tive

pea

k re

spon

se

Operation time (hours)

0.2

0

0.4

0.6

0.8

1.0

1.2

96 2,688 3,240

1.00 1.06 1.06

Figure 4: Long-term stability of the

relative BID sensitivity

T he new IRTracer-100 is amiddle-range FTIR systemoffering high core perfor-

mance, including the highest sensi-tivity levels in its class (S/N ratioof 60,000 : 1), high resolution (0.25 cm-1), and high measurementspeed (20 spectra per second inRapid Scan mode). High core per-formance stands for sophisticatedFTIR analysis, such as highly sen-sitive measurement of micro con-taminants, tracking measurementsof rapid chemical reactions, or pre-cise measuring of semiconductoror other materials.

To guarantee high performancewith maximum stability, it alsofeatures an interferometer withadvanced dynamic alignment andbuilt-in dehumidifier and an in-strument monitoring function.

IRTracer-100, makes it simple tofully utilize the high performancecapabilities and enter sophisticatedapplication areas.

The LabSolutions IR softwareincorporates data processing func-tions such as advanced ATR cor-rection and Kubelka-Munk con-version, quantitation functionssuch as the multi-point calibrationcurve method and the CLS meth-od, as well as the spectral searchingfunction as standard features. Op-tional add-on software is alsoavailable to further increase theapplication range with time course,PLS-quantitation, mapping, highlevel macro programming andmuch more. For accurate identifi-cation of unknown samples, theLabSolutions IR software includesa library of 12,000 spectra.

sample compartment allows aneasy setup of accessories includingauto recognition.

Specifications are top-level forboth hardware and software.Using the IRTracer-100 in combi-nation with the new LabSolutionsIR software family which was developed jointly with the

Customized system configuration

The IRTracer-100 system is ex-tremely flexible with a wide rangeof accessories and easy-to-use soft-ware options meeting the needs ofeach specific application. Measure-ments are possible from the nearto the far infrared range. The large

Top athlete IRTracer-100 for high sensitivity, high resolution and high speed applications

Figure 1: IRTRacer-100 Fourier Transform Infrared Spectrophotometer

Improved detection limits

Special ‘sapphire cobalt alloy’electrodes have been developedfor compound detection. The BIDreaches detection limits that areabout 50 - 100 times better thanthe TCD and, depending on thecompound 1.5 – five times betterthan the FID. With five orders of magnitude, the dynamic rangeof the BID is equal to that of theTCD and only slightly smallerthan the dynamic range of theFID.

Despite its high sensitivity, theBID appears to be highly tolerantto high concentrations. In thisregard the BID, just like the TCD,

can be used for the analysis of liq-uid samples. The signal arisingfrom the solvent used for the sam-ple does not have to be faded outvia ‘heart-cut’ techniques. Al-though the detector is overloadedby the solvent, it does not needmuch more time than a FID toreturn to baseline level. This isanother strong feature of the newplasma technology.

BID bridges an application gap

By combining long-term stabilitywith high sensitivity, the BIDbridges a gap between the robustbut less sensitive TCD and thehighly sensitive, but in terms of

operation, quite challengingpulsed discharge helium ioniza-tion detector (PDHID).

High sensitivity combined withgood tolerance for detector over-load brings the BID into play as apossible substitute for a FID de-tector. Especially for organic com-pounds containing heteroatoms(e.g. short-chain alcohols, aldehy-des and ketones), the much moresensitive BID scores well in com-parison with the FID. As a result,the barrier ionization dischargedetector not only bridges a gap,but also offers new perspectivesfor many applications currentlyrequiring multiple detectors (e.g.greenhouse gas analyzers).

Minutes

0100,000200,000300,000400,000500,000600,000700,000800,000900,000

1,000,0001,100,0001,200,0001,300,0001,400,0001,500,0001,600,0001,700,000

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

0.00

0.25

0.50

0.75

1.00Inten. (x 10.000)

100 200 300 400 500 600 700 800 900

m/z

APPLICATION

M any valuable Mediterra-nean plants hibernateduring the cold season in

greenhouses, where they are wa-tered and fertilized regularly inorder to reveal their full splendoragain in the following summer.But a greenhouse in St. Gallen,Switzerland led to the plantsdeadly fate. They had been poi-soned with an unknown sub-stance. The Canton’s police forcewas called in.

A suspect was quickly found. Buthow could it be proven that theplants had really been poisoned?This became the responsibility ofthe forensic science services of theSt. Gallen Cantonal Police.

Wherever possible, two independ-ent methods of analysis are usedto provide physical evidence. Thestaff of the forensic science servicenow had to figure out whichmethods would stand up to legalscrutiny in court.

LCMS/MS provides clues

One option was Shimadzu’s newlyinstalled LCMS-8040 triple quad-rupole mass spectrometer. The useof liquid chromatography coupledto tandem mass spectrometry

water and subsequently filtered.In addition, an uncontaminatedsoil sample was extracted to use asa blank control. Would this fastand straightforward methodalready suffice to convict the per-petrator? Yes!

In all five potting soil samplesinvestigated, the plant poison

chromatographic conditions waslargely omitted due to time pres-sure. The exciting moment ofdetection of a plant poison in thepotting soil had soon arrived.

The approach

25 g of the contaminated soil wasslurried with 50 mL of ultrapure

(LCMS/MS) offered an excellentpossibility. This technique is supe-rior to other methods in terms ofselectivity, due to the underlying‘multi-reaction monitoring’ (MRM).The desired parent compound isselected via the first quadrupole(Q1) and fragmented in the colli-sion cell (Q2), while one or morespecific fragments are selected bymeans of the third quadrupole(Q3). It is possible to determine awide range of analytes with onlyone analytical method, even with-out complex sample preparation.Figure 1 shows a schematic repre-sentation of the LCMS-8040 triplequadrupole.

Development of the detectionmethod was promptly incorporat-ed into the current user trainingfor the LCMS-8040 triple quadru-pole MS and the accompanyingLabSolution software.

The fully automated MRM opti-mization was performed with adilution of the substance recov-ered from the suspect pesticidecontainer.

An HPLC method was quicklyadded, but optimization of the

6 SHIMADZU NEWS 2/2013

The gardener did it ...A legal trial using the LCMS-8040 triple quadrupole

Figure 2: Chromatogram and spectrum of an extracted potting soil sample in which the poison could unequivocally be detected

Figure 1: Schematic representation of the Triple Quadrupole LCMS-8040

7SHIMADZU NEWS 2/2013

APPLICATION

could be detected unequivocally(Figure 2 – chromatogram andspectrum of an extracted pottingsoil). 1 μL of the filtered solutionwas injected into the LCMS-8040which was coupled to the Nexera X2 UHPLC system. Inaddition to optimized mass transi-tions (MRMs), the method includ-ed a full scan of a defined massrange in the positive as well as inthe negative ionization mode. Thisis possible without loss of sensi-tivity due to the excellent speedparameters of the LCMS-8040.With a polarity switching time ofonly 15 ms, this is one of the fas-test systems on the market andoffers a scan rate of 15,000 u/s anddwell times of 1 msec.

The second detection method

The DART-TOF-MS (DirectAnalysis in Real Time – Time ofFlight) of a different supplier wasselected as the second detectionmethod. DART is an ion sourcethat instantaneously ionizes gases,liquids and solids under ambientpressure. DART does not requireany sample preparation, meaningthat solids and liquids can be ana-lyzed by mass spectrometry intheir native state. Ionization takesplace directly on the sample sur-face. The process involves aninteraction between the analytemolecule and electronically excit-ed atoms or vibronically excitedmolecules.

A DART ionization source can be connected to Shimadzu’s singlequad LCMS-2020 mass spectro-meter as well as to its triple quadLCMS-8030 and LCMS-8040mass spectrometers.

Science proved ... it was the gar-dener who killed the plants.

Talking about meatsTOC determination in phosphoric acid in the food industry

P hosphoric acid is one of themost frequently used inor-ganic acids in industrial ap-

plications. It is applied as startingmaterial for the manufacture ofphosphate-containing fertilizers as well as for the production ofwater-softening agents such asdetergent additives.

Phosphoric acid is also used in thefood industry – as acidificationagent and preservative in bever-ages or as antioxidant in meatsand meat products. Particularlyfor these types of applications, itis important to apply acids thatare pure and free from foreignsubstances. Manufacturers andprocessors of phosphoric acids areincreasingly using the TOC (TotalOrganic Carbon) sum parameterfor quality control. This parame-ter is a measure of the contamina-tion of phosphoric acids by organ-ic components.

Wet-chemical UV oxidation at 80 °C

The determination of the TOCcontent in phosphoric acid is carried out via wet-chemical UVoxidation using Shimadzu’s TOC-VWP. Its core technology is thepowerful oxidation applying acombination of sodium persulfateand UV oxidation at 80 °C. Thisensures that all dissolved carboncompounds are converted to CO2.

In the presence of persulfate ionsand UV illumination, OH-radicalsare formed which have a strongoxidative effect and convert organ-ic compounds to carbon dioxide.A carrier gas transports the car-bon dioxide formed to the NDIRdetector where they are detected.Automated reagent preparationeliminates any contamination ofthe reagent solutions and mini-mizes the blank value of the in-strument.

Calibration of the system was car-ried out in two different ranges.

Are

a

Concentration [mg/L]

0

60

120

180

247.17

0 0.5 1.0 1.1

Figure 1: Calibration of the system in the range of 0.1 to 1 mg/L

Calibration is shown here for therange of 0.1 to 1 mg/L. TOC de-termination in phosphoric acidwas carried out using the NPOC(Non-Purgeable Organic Carbon)method. Prior to TOC determina-tion, neutral or alkaline samplesare acidified in order to decom-pose all inorganic carbonates andbicarbonates. This step could beomitted for phosphoric acid.

Concentration of the phosphoricacid does not play a significantrole in the determination; it isonly necessary to ensure that theacid is not too viscous. The 85 %phosphoric acid solution wastherefore diluted 1 : 5 with water.The resulting 17 % acid solutionwas transferred into the instru-ment using an OCT-1 autosam-pler. For each analysis, a 3,000 μLaliquot of the acid was injected.The 17 % phosphoric acid solu-tion measured in this way resul-ted in a TOC concentration of0.61 mg/L. The relative standarddeviation over three injections was1.8 %.

Figure 2: Injections of the 17 % phosphoric acid solution

Sign

al [m

V]

Time [min]

-4

50

100

150

0 2 4 6 8 10

Figure 1: The 80’s reloaded: First generation SPD-M1A HPLC photodiode-array detector Figure 2: The new SPD-M30A

SPD-M30A – B/A= 2.90

0

230 240 250 260 270 280

A

B

0

5,000

uV

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

Minutes

Figure 4: The new SPD-M30A obtains a stable baseline 20 minutes after switching on the

instrument, whereas a competitor instrument still exhibits a noticeable baseline drift even

after one hour

Figure 3: Benzene spectrum obtained

with the SPD-M30A. Looking at the ratio

between maximum B and minimum A,

it can be concluded that the spectral reso-

lution of the detector is excellent.

Flow rate : 0,5 mLl/min

MP : Methanol

Oven : Ambient

PRODUCTS

W ith the introduction ofthe SPD-M30A detector,the Nexera UHPLC

series adds a new member to thefamily. Just like Shimadzu’s pho-todiode detectors of the past (Fig-ure 1), the new detector (Figure 2)is also one step ahead of the ever-increasing demands of modern

the-art electronics and the flowcell are crucial components as well.

Optical path length and cell volume

To meet today’s demands inUHPLC, the detector cells musthave the smallest possible cell vol-ume in combination with thelongest possible optical pathlength (typically 1 cm for standardHPLC cells). The flow line and

provide very fast data acquisitionrates. At the same time, ultrafastseparations should not suffer fromloss of sensitivity.

In order to obtain informative data,the instruments must provide highspectral resolution. Combinedwith high sensitivity, high spectralresolution represents the optimum,and it is one of the strengths ofthe new SPD-M30A. The sophis-ticated optical unit, the state-of-

high-performance liquid chroma-tography.

In the era of UHPLC where peakwidths of less than one second arequite common, detectors must

8 SHIMADZU NEWS 2/2013

Crucial steps aheadWorld premiere – The new HPLC SPD-M30A photodiode array

9SHIMADZU NEWS 2/2013

PRODUCTS

Minutes

-35,000

-30,000

-25,000

-20,000

-15,000

-10,000

-5,000

0

5,000

0 50 100 150 200 250 300 350 400 450

uV

60 min

30 °C

25 °C

60 min120 min

Flow rate : 0,5 mL/min

MP : Methanol

Wavelength : 254 nm

Figure 5: An increase in ambient temperature of + 5 °C (- 5 °C) does not influence the

baseline of the SPD-M30A. The baseline of a competitor instrument is clearly influenced by

ambient temperature fluctuations.

detector

the shape of the cell must supportthe fastest possible fluid exchangein order to minimize dispersion.The combination of optical unitand flow cell should be designedin such a way that refractive indexeffects become negligible.

The benefits of performance

The optical unit was optimizedfor the use of capillary flow cells.This involves the use of a 1,024-element CMOS photodiode-array.This combination allows highspectral resolution of 1 nm (Fig-ure 3). In addition, the entire opti-cal unit is thermostatted. In thisway, the instrument is ready foroperation faster and is significant-ly less sensitive to ambient tem-perature fluctuations (see figures 4and 5).

To reduce noise even further, aspecial high-performance Deuter-ium lamp is used.

The key role of the capillary flow cell

The new capillary flow cell (Fig-ure 6) has an optical path lengthof 1 cm, which is standard formost analytical cells. Exceptionalhowever, is the cell volume ofonly 1 μL. Stray light and refrac-tive index effects are reduced to a

clear difference between the signalintensities due to the differentoptical path lengths. It is obviousas well, that higher plate numbersand improved resolution can beachieved through the low disper-sion and the smaller cell volume inthe SPD-M30A.

For highly sensitive measure-ments, the optional HS cell with apath length of 85 mm and a vol-ume of only 8.5 μL is available.Figure 8 shows a comparison be-

tween the standard cell of the newSPD-M30A and the optional HScell.

To meet the requirements in a reg-ulated environment (for instanceGLP and GMP), the cells of theSPD-M30A feature an ID func-tion which ensures traceability tothe cell employed based on thedata files.

Future-proof design

It is known that high data acquisi-tion rates are required for ultra-fast separations. In theory, 20 data

Figure 6: Standard capillary cell of the

SPD-M30A

uV

Minutes

0

25,000

50,000

75,000

100,000

125,000

150,000

175,000

200,000

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4

Figure 7: Comparison between the SPD-M20A containing the UFLC cell (red) and the SPD-M30A equipped with the standard capillary cell

(black) under equal chromatographic conditions

minimum due to the extremelywell reflecting capillary and theuse of advanced fiber optics tech-nology.

A cell with this geometry is theoptimal solution for use in thesemi-micro range in UHPLC aswell as in conventional HPLC.Figure 7 shows a chromatogramoverlay of the predecessor model,SPD-M20A with the 2.5 μLUFLC cell and the SPD-M30Awith the standard cell. There is a

points are needed per peak forproper peak recording. Accord-ingly, the data acquisition rateshould be higher than 20 Hz forpeak widths of one second.

In accordance with requirements,the new SPD-M30A allows selec-tion of various data acquisitionrates of up to 200 Hz, whichyields a distinct peak profile withpeak widths of 0.1 sec. �

T he long frosty period duringlast winter had an impact onairports. In extreme cases,

heavy snowfall resulted in ground-ing of all air traffic when plowingservices were not able to clear therunways. The frigid temperatures,however, left further ‘traces.’

Ice and snow on the wings of air-planes increase their total weightand have a negative impact ontheir aerodynamics. For reasons ofsafety, airplanes need to be de-icedjust before they are ready for take-off. The de-icing agent that is mostfrequently used is a mixture ofwater, glycol and additives. Theexact composition depends, amongother things, on the outside tem-perature.

TOC monitors the organic load of wastewater

After spraying the airplanes, thede-icing agent enters the sewagesystem where it leads to a signifi-cant increase of the organic load.

Even when the agent used is bio-degradable, the effluents must besubjected to a controlled treatment

Long winter periowastewaters

Figure 1: TOC-4200

Efficient

PRODUCTS

10 SHIMADZU NEWS 2/2013

uV

Minutes

0

25,000

50,000

75,000

100,000

125,000

0.525 0.530 0.535 0.540 0.545 0.550 0.555 0.560 0.565 0.570 0.575 0.580 0.585 0.590 0.595

0.0 2.5 5.0 7.5

Minutes

1

2

3

4

5

67

Standard Cell

High-SensitivityCell

Column : Shim-pack XR-ODSII(75 mm L. x 2.0 mm I.D., 2.2 μm)

Mobile Phase : 50 % AcetonitrileFlow rate : 1.5 mL/minSample : AlkylphenolsWavelength : 254 nm

Mobile PhaseFlow rateSampleWavelength

Column

50 % acetonitrile 1.0 mL/minAlkyl phenones 245 nm

Shim-pack XR-ODSII (75 mm L x 2.0 mm I.D., 2.2 m)

Figure 9: Chromatogram overlay at various data acquisition rates

Figure 8: Comparison between the

SPD-M30A standard capillary cell and

the optional HS cell

Figure 9 shows a peak which hasbeen recorded with a base widthof approx. two seconds at differentdata acquisition rates. It can clear-ly be seen that a data acquisitionrate even of 100 Hz, in compari-son with 40 Hz, allows a moreaccurate peak representation.

It is also evident that at a peakwidth at baseline of approx. twoseconds, the 200 Hz data acquisi-tion rate does not offer any signifi-cant improvement.

Software extends field of use

Additional features in the newLabSolution software extend the

field of use in photodiode-arraydetection:

• With the ‘intelligent Peak De-convolution Analysis’ function(i-PDeA), it is possible to easilyquantify overlapping peaks orpeaks containing impurities anddifferent spectra, using the firstderivative of the spectrum

•The ‘intelligent Dynamic Rangeextension Calculator’ (i-DReC)function enables quantification ofhighly concentrated sampleswhose signals exceed the lineardetection range by many times.For quantification without ex-trapolation, the standard calibra-tion curve created within the lin-ear range of the detector is used.In practice, the linear range of thedetector is extended over severalorders of magnitude withoutadditional hardware.

Both functions are highly user-friendly and, in addition to allow-ing manual parameter setting,automatic parameter selection isalso possible.

Conclusion

The new SPD-M30A records high-resolution data with the highestquality. In terms of sensitivity andspeed the new i-PDeA and i-DReC software features signifi-cantly extend the field of use.

Table 1: Analytical conditions of figure 9

to carbon dioxide. The resultingCO2 is transported by a carrier gasstream to a highly sensitive andCO2 selective NDIR detector,where it is measured. The TOCconcentration is calculated usingan external calibration.

The integrated dilution functionenables TOC analyses up to 20,000mg/L as well as automatic sampledilution when the measuring rangeis exceeded.

The measured value is transmitteddirectly to a control room that ini-tiates suitable measures when athreshold value is exceeded. Theanalyzer can also take direct ac-tion. For example, a slider can beclosed automatically to prevent thedischarge of contaminated waterinto watercourses or stagnantwater bodies.

Multiple sample streams in one instrument

An airport may have several sepa-rate wastewater collection systems.In this case, multiple samplestreams must be measured usingone instrument, requiring the useof a multi-stream sampler (see figure 2). The sample is passedthrough a strainer and reaches thesample chamber where it is homo-genized using a rotating knife be-fore being transferred to the in-strument for further analysis. Inthis way, even samples containinglarge amounts of particulate mattercan be measured without any prob-lems. After sampling, the chamberand strainer are cleaned with rins-ing water. The rinsing water pre-vents carry-over effects whenswitching sample streams. Themeasuring parameter can be select-ed individually for each samplestream. In addition, the user canfreely select the sequence by whichthe sample streams are to be meas-ured.

The automatic dilution function,the self-calibration check and the

optimized sampling process allowvirtually independent operation of the instrument at the airport.Numerous alarm and status signalssimplify detection of exceededthreshold values or indicate main-tenance requirements. In additionto the conventional possibilities,Modbus communication is avail-able. An optional web browserenables access to the instrumentfrom any networked computer.This makes the TOC-4200 theideal instrument for continuousTOC determination of wastewaterstreams at airports, especially dur-ing the winter period.

d pollutes airport

process. For the airport operator,it is therefore important to knowthe organic load of the airport’swastewater. The TOC sum param-eter has been well established as anassessment parameter for waste-water analysis.

TOC (Total Organic Carbon) is a measure of the concentration of organically bound carbon andtherefore reflects the pollutionlevel of organic substances inwastewater. Depending on the useof the de-icing agent, the TOCvalues can fluctuate significantly.

Continuous online NPOC monitoring

Of course, one rarely finds an air-port that includes a laboratorystaffed with laboratory technicians,so an analysis system is neededthat can monitor the organic car-bon pollution level continuouslywhile operating under mainte-nance-free and relatively autono-mous conditions.

Important for TOC determinationis the differentiation between or-ganic and inorganic carbon. Car-bonates and hydrogen carbonatesare, after all, present in all naturalwaters. The most widely usedmethod for TOC determination isthe so-called NPOC method. Inthis method, the sample is acidifiedto convert the carbonates and hy-drogen carbonates present in thesample to CO2. The resulting car-bon dioxide is subsequently purgedusing a gas stream passed throughthe sample.

Tried and tested and powerful –the TOC-4200

The TOC-4200 process analyzer ispredestined for this application.The TOC-4200 is a powerful ana-lyzer that uses catalytic combus-tion at 680 °C. After the analyzerhas automatically removed theinorganic carbon, a sub-quantity isinjected onto a hot (680 °C) plat-inum catalyst. Here, all organiccomponents present are oxidized

Figure 2: Multi-stream sampler

monitoring by online-TOC prevents environmental damage

11SHIMADZU NEWS 2/2013

PRODUCTS

Diagram 1: Element ratios in Eye-Cleaning

solutions

A 100-times dilution was selectedfor working with the Eye-Clean-ing solution. In this way, it is pos-sible to determine magnesium(now 0.36 ppm), calcium andpotassium with flame atomicabsorption technique using theAA-7000F. For determination ofsodium, the observed absorptionwavelength has to be changed tothe less-sensitive 330.3 nm-line,which is of factor 200 less sensi-tive in comparison to the most

common 589.0 nm-line.

Micro Sampling

To have more scope inmethod development and

individualization in thefinal steps of themethod optimizationprocess, Shimadzu’s

Micro Sampling is per-fectly suited to measure

the Eye-Cleaning solu-tion. For example, when

applying ionisation buffersas prescribed for determina-

tion of sodium in drinkingwater (in accordance with

German Drinking WaterDirective).

The AA-7000F in combinationwith the ASC-7000 sample prepa-ration station allows the automat-ed flame Micro Sampling method(Figure 3). In this method, flame

T he eyes are one of the mostimportant sensory organs.But they are very sensitive

to accidents, necessitating precau-tions in case of emergency. Anexample of an eye accident couldbe ingress of particles or chemicals(particularly in laboratories). In this case, the eyes need to berinsed with a special Eye-Cleaningsolution.

The quality assurance of such asolution is very important to en-sure that the rinsing helps ratherthan causing even more problems,e.g. through introduction ofmicroorganisms which can causeserious infection of the eyes. Toprevent the solution from contain-ing microorganisms, the filling hasto be aseptic. It is an efficient wayto fill a plastic bottle directly after

Analytical Task

The analytical challenge of thissample is the highly varying levelsof the elements Na, K, Mg andCa. For example, sodium is pres-ent in a high ppm range whereasthe concentration of magnesium is100 times lower (Diagram 1).Based on the fact that sample pre-paration nowadays has to be high-ly automated with the lowestamount of work, one dilutiononly of the sample should besufficient to determine all ele-ments, instead of several dilu-tions to match each analyticalworking range.

trol the stability and real concen-tration of the elements in the finalsolution, an additional controlstep is indispensable for increasedsafety. Therefore, it is necessary todetermine the element concentra-tions of sodium (Na), potassium(K), magnesium (Mg) and calcium(Ca) in a fast and reliable way.

AAS or ICP-OES?

For the analysis of Na, K, Mg andCa it is desirable to use both tech-niques, Inductively Coupled Plas-ma Optical Emission Spectros-copy (ICP-OES) and AtomicAbsorption Spectroscopy (AAS).With the ICPE-9000 system andthe AA-7000 dual atomizer in-strument, Shimadzu meets thedemands of quality assuranceaspects.

The AA-7000 is the system ofchoice for economic analysis of up to 4 - 5 elements. When six ormore elements should be deter-mined quickly, the ICPE-9000system is more applicable (com-pare figure 2). Additional criteri-ons for decisions can be present,e.g. the different detection limitsof the analytical systems. But incase of the Eye-Cleaning solutionthis is not a point because all fouranalytes are high concentrated toimitate the human tear fluid toavoid eye-irritations.

extruding and moulding it into thecommon bottle shape. Filling thebottle at this time with the tem-perature-stable solution results infast cooling of the bottle material.The productivity of this manufac-turing process known as blow fillseal (bfs) is much higher thanwhen working with air as coolingmedium or flushing the bottlewith rinse solution, quite apartfrom the possibility of higher con-tamination risks. These are someof the reasons that Holopack®

(near Stuttgart, Germany) offersthis technique (The ready bottledsample is shown in figure 1).

A different aspect in quality as-surance is the screening of thecontents. Normally, the amountsof salts included in an Eye-Clean-ing solution are well known bythe manufacturers. But in order toexclude weighing errors or to con-

How to keep a clear viewQuality assurance applying spectroscopy for Eye-Cleaning solutions

APPLICATION

12 SHIMADZU NEWS 2/2013

Na K Ca Mg

Figure 1: Analyzed product: Sterile Eye-

Cleaning solution bottled by bfs-technique

13SHIMADZU NEWS 2/2013

APPLICATION

atomic absorption analysis is con-ducted with small sample volumes(50 - 90 μL), whereas in the con-ventional flame method (hereafter“flame continuous method”), thesample is continuously aspiratedwith a flowrate of approximately8 mL/min, and larger sample vol-umes are needed for aspiration.

In the first step (Figure 3) thesample can be diluted and water,ionization buffers and/or standardsolutions (standard addition meth-od) can be added. The total mix-ing volume is 600 μL. The result-ing solution is injected in steptwo.

The flame Micro Sampling meth-od has several advantages com-pared to the flame continuousmethod. Analysis is possible witha small amount of sample, andwhen the autosampler is used,automatic further dilution of thesample and automatic addition ofbuffer solutions are possible inorder to compensate for interfer-

ences. Moreover, since only asmall amount of sample is intro-duced, the flame Micro Samplingmethod is effective for analysis ofhigh matrix samples which maycause clogging of the burner in theflame continuous method, such asthe Eye-Cleaning solution.

Final method and results

Method parameters providing thebest measured results are summa-rized in table 1. Using these para-meters, it was possible to measureover hours with no clogging ofthe burner head, as can happen

Figure 2: The flow chart indicates the suitable element analysing technique

1. Sample preparation (Autosampler)

2. Sample injection 2 - 600 μL mixing port, 50 - 90 μL injection

Discontinousabsorption signal

Time

Abs.

Rinse water

Figure 4: Absorption signals and calibration pattern for magnesium

Figure 3: Flame Micro Sampling method

Measurement elementWavelengthSlit widthFlame typeGas flow rateSampling time Interference bufferWorking range [mg/L]

Na330.3 nm

0.2 nmAir-C2H2

1.8 L/min20 sec

CsCl-solution10.0 - 40.0

K766.5 nm

0.7 nmAir-C2H2

2.0 L/min20 sec

––1.25 - 5.00

Ca422.7 nm

0.7 nmAir-C2H2

2.0 L/min20 sec

La2O3-solution0.50 - 2.00

Mg285.2 nm

0.7 nmAir-C2H2

1.8 L/min20 sec

––0.25 - 1.00

Instrument AA 7000 with autosampler ASC 7000 incl. Micro Sampling Kit

Table 1: Final method parameters for quality assurance of highly concentrated elements in Eye-Cleaning solutions

Abs. Abs. = 0.012 Conc. + 0.0018 R2 = 0.9999

0.000

0.050

0.100

0.150

0.200

0.250

0.300

0.350

0.400

0.450

0.500

0.0 20.00.000 0.250 0.500 0.750 1.000

10.0

Conc. (ppm)Time (sec.)

when measuring high matrix sam-ples with common continuousflame method.

To illustrate measurement results,the calibration plus the absorptionsignal of magnesium are shown inFigure 4. The recovery was in a

good range for all elements in-cluded in this research (Table 2).The AA-7000 in combination withMicro Sampling is a “state of theart” atomic absorption spectro-photometer for high precisionmeasurements of element concen-trations in Eye-Cleaning solutionsas well as in mineral waters (seeShimadzu News 01/2011). In gen-eral, this method is an interestingtool for clinical or pharmaceuticalapplications as it complies withFDA CFR 21 Part 11, and thepossibility to optimize all parame-ters including individual sampledilution even in a multi-elementalmeasurement sequence emphasisesthe Micro Sampling technique.

NaK

CaMg

Analyte Expected(weighted)

Result(measured)

Recovery

158 mmol/L10.0 mmol/L3.24 mmol/L1.48 mmol/L

157 mmol/L9.81 mmol/L3.28 mmol/L1.48 mmol/L

99.4 %98.1 %

101.2 %100.0 %

Table 2: Measurement results for the Eye-Cleaning solution

We will gladly send you additional informa-

tion. Please enter the corresponding number

on the reply card or order via Shimadzu’s

News App or News WebApp. Info 410

LATEST NEWS

Erich LeitnerInstitute for Analytical Chemistry and Food Chemistry,Technical University of Graz,Austria

T he compound 2,4,6,-trichlo-roanisole (TCA) is oftenmentioned in the literature,

particularly since H.R. Buser’spublication identified TCA as akey component of the “cork taste”in wine.1 A number of other re-ports have been published on thesensoric effects on food by TCAand also 2,4,6-tribromoanisole(TBA). In 1990, J.C. Spadonefound that 20 % of raw coffeefrom Brazil was contaminatedwith TCA.2 Most recently, TBAwas in the news regarding productrecalls from the pharmaceuticalcompanies Pfizer and Johnson &Johnson who had to withdrawproducts from the market as aresult of contaminated packaging.A robust and sensitive method todetermine TBA and TCA in arange of fruits and vegetablesexhibiting unwanted moldy off-odours has been developed.

Sensoric Properties and Sources of TBA and TCA

TCA and TBA have an unpleasantmoldy off-odour which is regis-tered by humans – even at verylow concentrations. These com-pounds can be perceived at differ-ent levels by humans in differentfood matrices.3 Figure 1 shows the chemical structures of the twocompounds.

It should be noted that none ofthese substances were added tothe food products intentionally,but both substances are formed

chromatography (comprehensiveGCxGC) with negative chemicalionization (NCI) was used. Incomprehensive GCxGC twocolumns of different polarities arecoupled in series. The first columnin this set-up usually has conven-tional dimensions, while the sec-ond column is substantially short-er (0.5 - 3 m).

All compounds eluting from thefirst column are cryo-focused atthe 2nd column head by a jet ofcold nitrogen gas and subsequent-ly heated up in a constant intervaltime (modulation frequency, usu-ally 2 - 8 s) by a jet of hot nitrogengas to be injected into the secondcolumn. In this way, peaks fromthe first dimension are fractionat-ed and additional separation onthe second column takes place.

For a better overview of separa-tion, the resulting data are usuallyshown in so-called contour plotsrather than in chromatograms. Ina contour plot the retention timeon the first column is plottedagainst the retention time on the

pounds. Initial measurements ondifferent fruits and vegetableswith a low resolution quadrupoleMS in selected ion monitoring(SIM) mode showed, however,that such a method is not useful inthe analysis of real world samplesbecause of massive spectral inter-ferences (see figure 2).

To solve this problem, a com-bination of multidimensional

from halophenols which are usedas bactericides (PCP) during theanti-poisoning process of micro-organisms. The formation mecha-nism could be identified in theproduction of wine stoppers madeof natural cork. A number ofmicroorganisms could be detectedboth in – and on – the naturalcork as a result of the productionprocess. Formation occurs eitherby direct methylation of trichlo-rophenol and/or tribromophenolor a methylation reaction after adechlorination of halide phenolswith more than three chlorine orbromine atoms. Of the large num-ber of halide anisoles, TCA andTBA have by far the lowest odourreception level.

Analytical Methods

Due to the high volatility of thesubstances, high-resolution gaschromatography (GC) is the meth-od of choice for analysis. An elec-tron capture detector (ECD) or amass spectrometer is recommend-ed for use in selective and sensi-tive detection of halide com-

14 SHIMADZU NEWS 2/2013

Moldy off-odors in fruits andvegetables?Determination of trichloroanisole and tribromoanisole using SPME coupled to Comprehensive GCxGC and mass selective detection (HS-SPME-GCxGC-qMS-NCI)

Figure 1: Trichloroanisole and tribromoanisole

2,4,6-trichloroanisole

Water: 0,03 ng/L

Beer: 0,09 ng/L

Water: 0,02 ng/L

(Whitfield)

2,4,6-tribromoanisole

Figure 2: Extracted ions (m/z 212) by GC-qMS-EI

[min]

10.00 11.00

15SHIMADZU NEWS 2/2013

LATEST NEWS

second column, with the maxi-mum length of the y-axis beingthe modulation frequency. Com-pounds that are shown parallel tothe y-axis are not separated in aone-dimensional chromatographicsystem. In addition, the modula-tion of the peaks leads to a bettersensitivity as the peak width ofnormally five to six seconds isreduced in a comprehensive sys-tem to 200 - 400 ms.

Using Negative ChemicalIonization

The signal-to-noise ratio (S/N) for10 ng/kg TCA was increased from18 : 1 (electron ionization (EI) inSIM mode) to 72 : 1 (NCI in SIMmode). If NCI is used in combi-nation with comprehensiveGCxGC, a further increase of the S/N to 300 : 1 is observed,resulting in a quantitation limit of 0.1 ng/kg. The only drawbackof this method is the formation offragments corresponding to thehalide atoms (m/z = 35 and 37 forchloroanisoles and m/z = 79 and81 for bromoanisoles), making theuse of deuterated standards impos-sible. The figure below shows thecontour plot of a standard samplewith a concentration of 10 ng/kgof each of different haloanisols.Figure 3 shows the contour plotsof halide anisols in a real worldsample of mango. Sample prepara-tion was performed by automatedheadspace solid-phase microex-traction (HS-SPME) using a 2 cm50/30 μm divinylbenzene/carbox-ene/ polydimethylsiloxane fibre at 80 °C for 60 min. Sample amountwas 1 g of homogenized material.Calibration range was 1-100 ng/kg.

Conclusion

Comprehensive two-dimensionalgas chromatography coupled toautomated SPME using NCI wasshown to be a selective and sensi-tive method for the determinationof the odour active compounds2,4,6-trichloroanisole and 2,4,6-tribromoanisole. The method isalso robust and simple. Determi-nation of the target compoundswithout any interference from thematrix is possible with this com-bined method. First results fromreal world samples (mango, garlicand different types of mush-rooms) obtained from a grocery

Erich Leitner

studied technical chemistry at the Technical

University of Graz, Austria, focusing specifical-

ly on analytical chemistry. He graduated in

1992 and received a PhD in 2005 in food

chemistry.

He has over 25 years of experience in organic

trace analysis using gas chromatography-

based methods. He focuses specifically on the

identification of odour active substances using

analytical and human sensory methods.

store showed alarmingly highcontamination levels. A thoroughinvestigation of different fruitsand vegetables is planned.

References1. H.R. Buser, J. Agric Food Chem. 30, 359-362

(1982).

2. J.C. Spadone, J. Agric. Food Chem. 38(1),

226-233 (1990).

3. Anonymous:

www.knowabouthealth.com/third-tylenol-

recall-by-jjs-mcneil/4075/

Figure 3: (a) Mango 1 / (b) Mango 2

0.000

0.400

0.800

1.200

1.600

2.000

2.400

2.800

3.200

3.600

16.000 16.667 17.333 18.000 18.667 19.333 20.000 20.667 21.333 22.000 22.667 23.333 24.000 24.667 25.333 26.000 26.667 27.333 28.000 28.667 29.333

0.000

0,400

0.800

1.200

1.600

2.000

2.400

2.800

3.200

3.600

16.000 16.667 17.333 18.000 18.667 19.333 20.000 20.667 21.333 22.000 22.667 23.333 24.000 24.667 25.333 26.000 26.667 27.333 28.000 28.667 29.333

Standard 10/ng/kg each, haloanisoles

We will gladly send you additional informa-

tion. Please enter the corresponding number

on the reply card or order via Shimadzu’s

News App or News WebApp. Info 411

tional InGaAs detector (IndiumGallium Arsenide).

This new development gives spec-troscopists a new choice. It is nolonger necessary to invest in avery high specification doublegrating, double monochromatorsystem to cover this absorbancerange. The UV-2700 is much morecompact, just a third of the size ofconventional reference instru-ments and with a fraction of thecosts.

Application example

The following example showshow to reduce costs not onlyfrom the instrument but also fromthe application side. A chemicalcompany has been using a methodfor determination of TBC, an in-hibitor of polymerization reac-tions applied to increase the han-dling time for bonding agents,which involves a reaction withNaOH to produce a red color.The color has been used for quan-titation as it exhibits lower absor-bance reducing the need for dilu-tion. Direct measurement of TBC

APPLICATION

U V-VIS spectroscopy hasbeen a fundamental tool formost laboratories since it

was first used routinely nearly 70years ago. The technique is widelyapplied in research, quality con-trol and assurance laboratories inthe chemical and pharmaceuticalindustries.

this range to 4.5 - 5 abs throughthe use of pre-monochromators tofurther reduce stray light. Beyondthis is a further niche of ‘Refer-ence’ grade instruments usingdouble monochromators and ad-vanced wavelength drives to reachas high as 7 - 8 abs.

Smaller, lighter and more powerful

With the launch of the new Lo-Ray-Ligh™ grating, Shimadzuhas completely redefined the con-ventional spectrophotometer nich-es. This new grating offers dramat-ic reduction of stray light enablinga single monochromator (as in theUV-2600) to deliver > 5 abs per-formance, and a double mono-chromator system (UV-2700) toreach > 8 abs – in an instrumentwhich is physically smaller andlighter than most conventionaldouble-beam systems. The gratingalso offers a wider wavelengthrange than any earlier generationgrating, permitting the UV-2600to read up to 1,400 nm with theISR-2600 Plus integrating sphereoption which contains an addi-

The UV-VIS market has been di-vided into sections created by thelimitations of the componentquality of diffraction gratings,detectors and source lamps. The‘normal’ banding consists of in-struments which are able to readin the order of 2 - 4 absorbance(abs). ‘Research’ machines extend

16 SHIMADZU NEWS 2/2013

Redefining spectrometricnichesHigh absorbance readings in UV analysis of Tertiary-Butyl-Catechol (TBC) without colorimetric derivatization

0.000

2.000

4.000

6.000

7.280

238.6 250.0 300.0 350.0355.1

Abs

.

nm

Abs

.

Standard calibration curve

Concentration (mM)

-0.834

0.000

2.000

4.000

6.000

7.570

0.000 10.000 20.000 30.000 40.000 50.000

Figure 3: High absorbance spectra from TBC Figure 4: Calibration curve from TBC method, high absorbance against concentration

in mM

Figure 2: Chemical structure of TBC

(Tertiary-Butyl-Catechol)

Figure 1: The Shimadzu UV-2700 UV-Vis-NIR spectrophotometer

Anew UV-VIS instrumenta-tion software for the health-care and cosmetic segments

outperforms the new regulationsto be applied from July 2013.These adjustments will be fixed bythe European Community, relat-ing to the production and market-ing of cosmetics [1]. Other regula-tions are the Colipa [2], FDA [3],Boots Star Rating [4] and JCIA(Joint Commission InternationalAccreditation - Health Organisa-tion). All of them are part of theSPFCalculator Software whicheven helps to calculate some phys-ical properties. This product hasbeen designed in cooperation withthe Aqualis software house inMilano, Italy.

The SPFCalculator presents 17parameters requested for the qual-ification of a sun protection prod-uct. The program includes moreinformation on the sun screenproduct than is required by theguidelines. The calculator is easyto handle and just needs a simpletraining for users. The software

(OTC) sunscreen products marketed inthe U.S.’, updated 6/23/2011

[4] Measurement of UVA: UVB RatioAccording to the Boots Star RatingSystem (2008 Revision), Boots,Nottingham, UK, 2008

can be updated based on changesin the regulations. The seventeenparameters which can be calculat-ed are shown in table 1.

Users can easily test the sun pro-tection product and change itsformulation where necessary,before carrying out the very ex-pensive in vivo measurements.

Shimadzu can provide a completeeasy to handle solution: a packagecontaining the UV-2600 instru-ment, the ISR-2600 integratingsphere in combination withUVProbe and the SPFCalculator.It is a total solution in accordancewith European CosmeticsAssociations requirements. Thestrength of the package is thatother parameters such as color,appearance, quality of packagingetc. can be determined using thesame combination.

References

[1] Regulation (EC) No 1223/2009 of theEuropean Parliament and of theCouncil of 30 November 2009 on cos-metic products

[2] Colipa, (European Cosmetics TradeAssociation) ‘In Vitro Sun ProtectionMethods’ group

[3] Sunburn Protection Factor (SPF). Foodand Drug Administration (UnitedStates). 2009-04-30; ‘Questions andAnswers: FDA announces newrequirements for over-the-counter

New tool for healthcareand cosmetic productsSPFCalculator software for Shimadzu UV-VIS instrumentation

Table 1: Parameter selection for the SPF report

Ratio(UVAPF/SPFlabel)Exposure time

Critical lambda FDA

Critical lambda boots

UVA dose

Critical lambda (pre-irradiation)Star rating FDA

Boots star rating

UVAPF

Conversion factor

UVA-I/UV FDA

UVA/UVB after-irradiation Boots

UVAPF0

Exposure energy

Critical-lambda(after-irradiation)UVA/UVB pre-irradiation BootsJapan PA rating

17SHIMADZU NEWS 2/2013

PRODUCTS

at 275 nm has not been possibleusing conventional 0 - 4 abs UV-VIS instruments as the high-est concentrations of TBC at 50mM have an absorbance of nearlyseven Abs.

Using the UV-2700, it is possibleto directly measure the absor-bance peak of TBC at 275 nm.The following figure shows theabsorbance traces of 10, 20 and 50 mM TBC (axis scale 0 - 8 abs).

The figure shows that it is possi-ble to scan a sample which has amaximum absorbance of 6.87 at275 nm. The ability to quantitatethis product directly is demon-strated by a plot of the concentra-tion vs. absorbance from the stan-dard quantitation software inShimadzu UVProbe.

The relationship of absorbance toconcentration remains linearthrough to very high absorbance.In order to read at very high ab-sorbances, the Shimadzu UV-2700offers a ‘High Absorbance’ scanmode which can be used in con-junction with rear-beam attenua-tion to allow measurement of lightintensities less than one ten mil-lionth of normal open beam ener-gy.

Summary

The Shimadzu UV-2700 is an af-fordable and compact instrumentwhich dramatically increases theconcentration range of highly ab-sorbing species which can be di-rectly observed in UV spectros-copy. It offers a performance pre-viously available only in referencegrade, double monochromatorinstruments which were too largeand too expensive for most labo-ratories.

InstrumentationUV-2700, UVProbe software,Attenuator, standard 1 cm square cellholder, 1 cm square quartz cell

IMPRINT

Shimadzu NEWS, Customer Magazine ofShimadzu Europa GmbH, Duisburg

PublisherShimadzu Europa GmbHAlbert-Hahn-Str. 6 -10 · D-47269 DuisburgPhone: +49 - 203 - 76 87-0 Fax: + 49 - 203 - 76 66 25shimadzu@shimadzu.euwww.shimadzu.eu

Editorial TeamUta SteegerPhone: + 49 - 203 - 76 87-410 Ralf Weber, Tobias Ohme

Design and Productionm/e brand communication GmbH GWADüsseldorf

Circulation German: 4,730 · English: 16,400

CopyrightShimadzu Europa GmbH, Duisburg,Germany – September 2013.

Windows is a trademark of Microsoft Corporation. ©2013

Apple Inc. All rights reserved. Apple, theApple logo, Mac, Mac OS and Macintoshare trademarks of Apple Inc.

the pixels are sub-sampled to fur-ther increase the speed. This re-sults in an extremely poor resolu-tion in the high speed region.With the high speed CMOS sen-sor, the photo diode and memoryare connected 1 to 1, and with thesignal from each frame, all pixelsare written to memory simultane-ously. Since no sequential readoutoccurs there is no output amplifierlimitation, so high-resolution re-cording even at ultra-high speedsis enabled.

High resolution even at high speeds

The new HPV-X is able to record128 frames, 20 % more than theHPV-2. In the HP-mode (50,000pixels), a double-memory functionenables recordings of 256 consec-utive frames for recording evenlonger periods. This offers theusers the choice of prioritizingeither resolution or recordingtime.

Other high speed camera systemsneed to lower the resolution asrecording speed increases, but theHPV-X maintains the same highresolution even if recording speedis increased. That means thatultra-high-speed phenomena canbe analyzed in far more detail

PRODUCTS

U ltra-high speed recordingswith video cameras such asthe Shimadzu Hyper Vision

HPV-1 or HPV-2 become a stan-dard tool for characterizing andquantifying high speed events inorder to make invisible phenome-na visible to the human eye.

Shimadzu’s HPV-1 and HPV-2enable recordings at up to onemillion frames per second (fps)while maintaining excellent spatialresolution at any recording speed.

The need to capture high-speedphenomena is demanded by aca-demic institutions and researchinstitutes and also various manu-facturing industries. Applicationsinclude fuel injection in combus-tion engines, dispersion of inkdrops by inkjet printers, studieson hydrodynamics, destructionprocesses, shock wave develop-ment, visualization of machiningprocesses as well as fast chemicalreactions.

Unique features

The latest development in thisapplication field is the new HyperVision HPV-X High-Speed VideoCamera equipped with a propri-etary high-speed CMOS imagesensor, enabling ultra-high-speed

In a conventional high speed vi-deo camera, the photo diode isscanned pixel by pixel and the sig-nal is read out and written to anexternal memory. Due to limita-tions of the output amplifierspeed, the effective recordingspeed will be in the tens of thou-sands of frames per second, but

continuous recordings at 10 mil-lion frames per second whileensuring no blooming effects.This is a unique feature and a keydifferentiator in comparison toother high speed camera systems.

18 SHIMADZU NEWS 2/2013

Shock wavesWorld premiere – The new high speed video camera Hyper Vision HPV-X

Figure 1: HPV-X system configuration consisting of camera head and power supply unit

than when using a regular highspeed video camera. This propri-etary feature is included in allShimadzu Hyper Vision highspeed video cameras, but is notavailable from any other manufac-turer. The HPV-X is able to re-cord five million 100,000 pixelimages per second or ten million50,000 pixel images per second.

Easy handling

In contrast to any other highspeed camera systems, the HPV-Xis very compact and easy to use.Just like the previous models ofthe Hyper Vision series, the sim-ple system configuration, consist-ing of the HPV-X camera headconnected by cable to a laptopcomputer, offers a compact andhighly portable design that makeson-site setup especially easy. Italso retains the same HPV soft-ware that has been so popularwith current users all over theworld, featuring intuitive andeasy-to-understand setting screensmaking it easy to capture ultra-high-speed videos.

HPX-X at a glance

Sensor: CMOS (FTCMOS)

Recording speed:10 mio frames per second (Mfps)

Number of frames: 256

Resolution: 400 x 250 px

Constantly high resolution of up to 10 Mfps

Synchronization of several cameras

19SHIMADZU NEWS 2/2013

PRODUCTS

W hen thinking of micro-hardness testing, thedetermination of struc-

tural constituents of hard metallicor ceramic samples usually comesto mind. Studies on crystal segre-gation, hardness distribution ofnitrited layers and welded joints aswell as systematic hardness testingof new materials form the majorityof areas of application. However,the number of measurementsrequiring

urement. In this way, it is possibleto examine very hard materials aswell as thin layers such as metalfoils used in the manufacture ofsolar cells.

Twelve load ranges

Up to twelve load ranges fromHV0.001 to HV2 are supported.Thanks to the force-compensateddesign, up to four additional load

ranges can be freely de-fined, which can be

very useful in themeasurement ofborderline cases.In addition, a

motor-driven tur-ret enables easy switch-

ing to another objectivelens without the need torepeat testing if a too

high or too low loadrange was selected.

Overall, empha-sis has been pla-

ced on flexibleand conven-

ient

particularly small test forces in-creases rapidly with fast advancesin lightweight construction.

The completely redesigned HMV-series hardness tester uniting allrequired features in one instru-ment takes this development intoaccount.

The HMV-G models feature a vasttest force range from the conven-tional microhardness range of0.098 N up to 1.96 N down to thesmall load hardness range to 19.61N. In addition, the HMV-G canpush forward into the ultra-micro-hardness range and can applyforces of merely 9.81 milli-Newtonto 49.04 milli-Newton for meas-

From soft to hardThe new HMV-G microhardness tester

operation during the developmentof the new HMG-V. The G-shapedframe increases the sample com-partment considerably, enablingstraightforward measurement oflarge-volume samples or compo-nents. The measurement turret isavailable in two versions, with thepossibility to mount up to twoindenters as well as four objectivelenses simultaneously.

Three series for various applications

Three series are available depend-ing on the application need:• the manual version, suitable for

training purposes as well as forhigh-precision measurement for small measurement tasks inresearch

• the camera and PC-controlledversion for more complex andintensive measurement activitiesmeasuring indentation automati-cally

• the fully automated version forlarge measurement series andregular hardness distribution,with autofocus feature and anautomated stage.

Figure 3: Big alphanumeric LCD touch panel

Figure 2: Multi turret function with up to two indenters and four abjective lenses

The fully automated HMV-G-FAhardness tester with its multitudeof functions offers maximum con-venience and performance withminimal work complexity.

Dedicated support functions

Using the integrated ‘stage viewer’function, the entire stage is avail-able for sample observation. An‘edge detector’ recognizes samplegeometries and generates simpli-fied representations on the moni-tor. With the optimal imaging,even real samples with scratches orlight or dark backgrounds can bedetermined automatically withoutthe need for complex sample pre-paration such as polishing. Themeasurement series are then car-ried out by simply clicking thestart and end points or by selectingindividual points.

These support functions togetherwith the excellent measuring andprecision properties of the newHMV-G series also enable lessexperienced users to obtain fastmeasurement results. True to themotto ‘Everybody can become anexpert’.

Figure 1: Micro Vickers hardness tester HMV-G

LATEST NEWS

20 SHIMADZU NEWS 2/2013

I t could not have been plannedbetter: 150 guests from allover Europe were greeted by

bright sunshine and luminouscherry blossoms at the openingof Shimadzu’s new LaboratoryWorld. According to Japaneseculture, flowering cherries sym-bolize an awakening – the themefor this day that included an open-ing ceremony with representa-tives from business and politics, a Japanese Kagamiwari ceremony,a guided tour through the labora-tories as well as world and Euro-pean premieres of new products.

After short speeches from AkiraNakamoto, CEO of ShimadzuCorporation, the Japanese Con-sul General Kiyoshi Koinuma,Duisburg’s Mayor Sören Link aswell as Yasuo Miura, President ofShimadzu Europa, they cut theribbon together and officiallyopened the new LaboratoryWorld. Subsequent guided toursthrough the laboratory and semi-nar facilities were accompaniedby live demonstrations of select-ed applications and technologies

routine analyses and applica-tions in highly regulated envi-ronments (see article on page 8)

• the highly sensitive Tracera gaschromatograph, which can de-tect virtually all traces of organ-ic and inorganic compoundsdue to novel plasma technology– about 100 times more sensi-tive than the universal TCDand twice as sensitive as theFID (see article on page 4).

TOC analyzers, mass spectrome-ters and balances up to materialtesting machines. Mass spectrom-etry is presented in its own area.Shimadzu has significantly ad-vanced this technology in recentyears. In addition, laboratoryareas for customer applicationsand seminar facilities have beenexpanded. Shimadzu has investeda total of 3,2 million Euros in theexpansion of its laboratory andtraining facilities.

“During the entire week, we havewelcomed more than 200 cus-tomers”, explained Jürgen Kwass,Managing Director of ShimadzuEuropa. “The facilities at ourLaboratory World are designedin such a way that there are dedi-cated areas for discussion andexchange of ideas in addition tothe spacious product and labora-tory stations. Shimadzu antici-pates that due to the extendedconsumer and product safety reg-ulations, the testing and analysisneeds – and consequently theneed for training – will continueto increase in the future.

One world and three european premieres

In addition to the new ‘Labora-tory World’, Shimadzu has intro-duced four new products:

• the high-speed Hyper VisionHPV-X camera. Thanks to theworld's fastest sensor with 10 million frames/sec (Mfps),the camera records phenomenaduring shock waves or inmachining processes (see articleon page 18).

• the HS-20 headspace samplerfor gas chromatography foraccurate analysis of volatile andsemi-volatile compounds in awide boiling point range

• the Nexera X2 UHPLC systemwith the world’s most sensitivephotodiode-array detector for

at seven different stations. Fourproduct premieres also receivedcenter stage.

Kagamiwari ceremony withhammer stroke and rice wine

The inauguration of the Labora-tory World was concluded with aJapanese Kagamiwari ceremony.The lid of a keg of Sake wassmashed with wooden hammers,resulting in a delightful spray ofthe rice wine. A mutual ‘Kanpai’(toast) in wooden sake bowlswith all guests completed the cer-emony. Newspaper and televisionjournalists were present and havereported on this event.

In the following days, from 15 -19 April, customers of Shimadzu’sEuropean branches were intro-duced to the ‘Laboratory World’featuring individual product seg-ments.

On over 1,500 m2, testing facili-ties were created for Shimadzu’sentire product range – from chro-matographs, spectrophotometers,

Laboratory opening ceremony with hammer stroke“Excellence in Science” on 1,500 m2: World and European premieres

Traditional Kagamiwari ceremony with the Managing Director of the Analytical Division,

Teruhisa Ueda, Shimadzu's CEO Akira Nakamoto, Consul General Kiyoshi Koinuma as well

as the European Managing Directors Yasuo Miura and Jürgen Kwass (left to right).