Become an Expertwith ACTIVA MThe Master in True Multi-line Analysis

Multi-line concept

Interactive assistance

The art of CCD-based ICP-OES

A platform of support

ACTIVA M

Total Multi-line ConceptA revolutionary approach :from single-line to multi-line analysis

Specifications

Database

Complete spectra

Multi-line selection

Calibration statistics

Outlier detection

Dedicated hardware

High analytical performance

ACTIV

A M

Assistance tools

S3-base

IMAGE

MASTER

CALSTAT

SOS

ACTIVA M

ACTIVA M

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The classical way of conducting the determinationof an element in ICP-OES is to select a single linewith adequate sensitivity and free from spectralinterferences. If the nature and the concentrationof the matrix elements are not constant, there is arisk of unexpected spectral interferences, whichcan become significant, and the concentrationdeduced from the use of a single line may then bewrong, with no means of detecting the bias. When the analyte peak is interfered, a positive biaswill be generated, while the bias may be negativewhen the matrix influences the background correc-tion.

The ideal approach is to conduct multi-line analy-sis, a far more efficient way of taking benefit fromall the available information of the plasma. With theuse of multi-channel detection such as CCDdetectors, the amount of spectral information hassignificantly increased and it is then possible tohave acquisition of the full UV-visible spectrum foreach element, and to use multiple lines perelement. Multi-line analysis makes the detection of outlierspossible, thereby coping with unexpected spectralinterferences and, consequently, improving thereliability of the results.

Because method development and its validation may be a complex task, performing multi-line analysisimplies :

Bring ICP expertiseto your lab with an

easy-to-useinstrument!

Be confident in thequality

of your results!

Example of single-element spectrum (Ca 1 g/l)

1.4 x 107

1.6 x 107

1.2 x 107

1.0 x 107

8.0 x 106

6.0 x 106

4.0 x 106

2.0 x 106

0.0

Inte

nsity

(a.

u.)

Wavelength (nm)

800700600500400300200

Innovative Interactive Assistance

Unique and proprietary S3-baseS3-base (Single-element Spectra, Spectroscopicdata) is essential to take full benefit of multi-lineanalysis. Such a base responds to the need of re-liability in terms of wavelength compilation and lineintensity, because currently available wavelengthtables are not based upon ICP experiments, but onalternative radiation sources such as arc or spark. As a consequence, ICP users must perform te-dious experiments for line selection by overlappingspectra of the different elements expected in thesample, to find a sensitive line free from spectralinterferences. When the multi-line concept is used,method development becomes even more com-plex.

Thanks to the specific instrumental configurationof ACTIVA M, single-element, entire spectrum ac-quisitions were performed under standard ICPoperating conditions. This allowed the assignment of ICP lines and thecalculation of spectroscopic data, which led to thecreation of a base with double access: a collectionof single-element spectra and a data base contai-ning wavelengths, ionisation state, excitationenergy, sensitivity (S), background level, limit ofdetection (LOD), maximum concentration belowdetector saturation (Cmax) and line width (FWHM).

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List of sensitive lines

Lines that can be used overa given concentration range

Potential spectralinterferences

LOD

Cmax

S

FWHM

More than 50 000 lines have been, then, assigned,with the corresponding spectroscopic data varyingfor example from 60 lines for Pb, 183 for Ca, ~3000for Cr to ~5200 lines for Th.

S3-base provides appropriate spectroscopic data information for multi-line selection with MASTER.

MASTER

4

MASTER (Multi-line Analysis, Selection Tool forEnhanced Reliability) ensures the multi-line selec-tion for each application. Thanks to S3-base, theline selection is facilitated through the automaticFiltering and the Display procedures.

Basically, the analysts just have to specify the listof elements and their concentration range. Basedon the S3-base spectroscopic data, MASTERsuggests lines for each analyte that are adequatefor the defined concentration range and that are notinterfered by the concomitant elements when pre-sent at their highest expected concentration, to beunder the most pessimistic case. The number of

lines to be suggested, as well as sensitivity and in-terference filtering criteria, are user-defined. As anexample, for a concentration range 0.05 – 50 mg/Lof Cr as the analyte, in the presence of Mn in therange 10 – 500 mg/L, the filtering procedure sug-gests at least 8 appropriate Cr lines.

Then, MASTER displays the analyte spec-trum along with those of concomitant ele-ments and the blank spectrum. Thishelps in the ultimate validation orrejection of a line, and to determinethe correct background correctionpositions.

Lines and backgroundsof all elements are then

exported, for anautomatic set-up of

the analytical methodfor analysis. Thanks to

the proprietaryS3-base, tedious line

profiling optimisation isno longer needed.

IMAGE provides afingerprint of the

samples and ensurestraceability

with possiblere-processing

IMAGEBefore developing the method, it might be neces-sary to identify the elements and estimate theirconcentration range. Semi-quantitative analysis isperformed with IMAGE by using multiple lines,based on the acquisition of the complete spectrum(120 to 800 nm).

Spectra are stored for recalculation at any time forany element or line. All peaks can be visualised forconfirmation. Real sample spectra can then betransported to MASTER, providing full interactivitybetween IMAGE and MASTER.

Matrix elements:

Hide Highlight Edit

mg/l

Hide Highlight Edit

Cr 0.05 50

Mn 100 1000 mg/l

-50e5

25e6

50e6

70e6

265 265.1 265.2 265.3Wavelength

Logarithmic

Inte

nsit

y

N°5 Cr 286.257

-50e5

25e6

50e6

70e6

357.7 357.8 358.9Wavelength

Logarithmic

Inte

nsit

y

N°6 Cr 357.868

-50e5

25e6

50e6

70e6

286.6 286.7 286.8Wavelength

Logarithmic

Inte

nsit

y

N°7 Cr 286.674

-50e5

25e6

50e6

70e6

313.1 313.2 313.3Wavelength

Logarithmic

Inte

nsit

y

N°8 Cr 313.211

50e5

288.45 288.5 286.55Wavelength

Logarithmic

Inte

nsit

y

N°4 Cr 286.511

20e4

60e4

80e4

206.4 206.5 206.6Wavelength

Logarithmic

Inte

nsit

y

N°3 Cr 206.562

-50e5

25e6

50e6

70e6

265 265.1 265.2Wavelength

Logarithmic

Inte

nsit

y

N°1 Cr 205.57

-50e5

25e6

50e6

70e6

265 265.1 265.2Wavelength

Logarithmic

Inte

nsit

y

N°2 Cr 206.164

40e5

30e5

20e5

10e5

286.6

40e4

206.7

358

Wavelength LOD Type Cmax (µg/L) (g/L)

Cr 205.570 0.26 2 6.4Cr 206.164 0.37 2 8.6Cr 206.561 0.53 2 13.0Cr 286.511 1.12 2 2.5Cr 286.257 126 2 2.9

Cr 313.211 1.52 2 3.4Cr 286.674 1.41 2 3.2Cr 357.868 1.36 1 3.1

File Matrix View Plots HelpFile Matrix View Plots Help

Method Name

Show all lines ...

Cr Mn

Full spectrum acquisition (120–800 nm)

ACTIV

A M

SOSSOS (Statistical Outlier Survey) is a statisticalprocess of the multi-line results, for the rejection ofpossible outliers, to provide a single reliableelement concentration. SOS copes with bothpositive and negative bias, and avoids recalcula-ting the results.

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In our example, if Zn is present in one sample andwas not expected, bias will occur: the right back-ground of chromium 205.571 nm line is slightlyincreased and the 206.164 nm line is interfered.Both lines are rejected and three remain for thereliable calculation of Cr concentration.

SOS helps the analystto optimise the method,

as well as to performroutine analysis withsecurity, by detectingoutliers if unexpectedinterferences occur.

Number of results

Conc

entr

atio

n

Outlier

CALSTATThe development of the method is completed after-wards with a statistical evaluation of the calibrationprocedure. Once the calibration is realised, auto-matic calculations in the CALSTAT tool helps theanalyst to evaluate the following criteria: verifica-tion of linearity, estimation of uncertainty due to the

calibration procedure, determination of limits ofquantitation, validation of background correction,and advice for weighting the regression.

Wavelength (nm)

Inte

nsity

Inte

nsity

Wavelength (nm)

205.7205.6205.5 206.0 206.1 206.2 206.3205.4

10e4

20e4

30e4

40e4

0e0

10e5

20e5

30e5

Cr 205.571 Cr 206.164

Cr 0.05 mg/LCr 0.05 mg/L Mn 500 mg/L Zn 300 mg/L

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IMAGE, MASTER,CALSTAT

and SOS are majortools for method

development,validation and

routine analysis.

As a whole, the strong interaction between instru-mental configuration and software tools is the es-sence of this revolutionary approach. ACTIVA Moffers an incomparable and practical use of multi-line analysis, regardless of the expertise of the

user. The instrument is used at its best throughtime saving and user-friendly step-by-step opera-tions. Everyone can easily become an expert inICP analysis.

ACTIV

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The Art of CCD-based ICP-OESACTIVAnalyst software, to operate the instrument atits bestAvailable in multi-language versions, the softwareprovides a practical use for first-time operators, aswell as optimisation capabilities for trained users.

Some software functions are keys to a secure multi-user operation of the instrument: on-line laboratorynotebook; multi-user and multi-level security (biome-tric signature log-on available); computer program-mable plasma conditions by method.

First-time users quickly become confident throughassistance functions along the analytical methodo-logy process: IMAGE for automatic semi-quantita-tive analysis; MASTER for lines selection; aDatabase of matrices, wavelengths and spectrosco-pic data, quality controls, sample tolerance tablesand standards; optimization of integration time foreach element based on sensitivity, speed andprecision criteria from user’s input; SOS for evalua-tion of results.

High sample throughput is achieved with the auto-sampler (benefiting from bar code identification ofsamples) and with automated analysis using a multi-method sequence for samples of various matricesrequiring different methods. Programmable calibra-tion re-sloping and QC checks, with user-defined ac-tions, ensure the automatic sequence processing,and the SOS tool guaranties the quality of results.The ICP system offers increased productivitythrough automatic user programmable start up andshutdown. This also minimizes argon gas consump-tion.Urgent samples can be easily inserted at any time ina sequence in-run, using either the current methodor other methods.

Analytical criteria (accuracy, repeatability…) can beoptimised if required using various correction me-thods: controlled Standard Addition Method; auto-matic calculation of additive and multiplicative

Inter-Element Correction factors; Internal Standardcorrection; auto-dilution process; drift correction &high precision data processing; results reprocessingafter calibration or parameters changes.

The simultaneous measurement allows visualisingthe spectra of lines and their vicinity during analysisfor confirmation or identification of unexpected spec-tral interferences.

Results are fully utilised through :

l Data transfer and import/export of sampleinformation compatible with LIMS or third partysoftware

l Results exporting and/or printing in real time,through batch reprocessing or on a sample-by-sample bais

l Wide range of industry compliant reports,as wellas additional reports such as stability report

l Full data archiving capabilities

Diagnostics of the instrument can be performed indifferent ways:

lTimeScan, transient signal acquisition (real-time out-put of instrument signal for troubleshooting or optimi-sation)

l Automatic export and calculation of parametersfrom Figures of Merit measurements

l Remote control and PlasmaCam remote plasmaviewing for Service assistance

l SPC (Statistical Process Control) for X, R, SD andhistograms charts of user selected solutions

The ACTIVAnalyst software is FDA 21 CFR Part 11compliant, with electronic signature of a dedicatedresults report.

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The Czerny-Turner optical system is equipped witha megapixel, unequalled low-noise CCD detector,leading to spectral windows up to 8 or 16 nm withsimultaneous measurement of multiple lines andbackgrounds.

Based on dual large back-to-back gratings, the re-solution is, then, constant not only within a windowbut also over the spectral range. It is better than10 pm with the 4343 grooves/mm holographicgrating (in the range 120-430 nm), and better than18 pm with the 2400 grooves/mm grating.

Considering the ACTIVA M low-noise, high-speedCCD detector, combined with possible exposuretimes in the range 1:1000, a practical dynamicrange (signal before saturation-to-readout noiseratio) of 107 can be achieved. Such a dynamicrange is usually higher than the ratio of the maxi-mum concentration to the limit of quantitation, withthe maximum concentration corresponding to thebeginning of graph curvature.

Expanding your capabilities !While the S3-base and assistant software toolsmake multi-line analysis a reality, without theadvanced detector technology, optics and torchsystem of ACTIVA M, the assistance would bemore limited in capability.

ACTIVA M maintains the strengths of HORIBAScientific ICP spectrometers, while incorporating ad-vanced CCD technology.

1000000000

10000000

100000

1000

10

100

100000000

1000000

10000

1

0.000

10.0

01 0.01 0.1 1 10 10

010

0010

000

Concentration (mg/L)

Inte

nsity

Sr 407.771 nm Cu 327.396 nm Pb 220.353 nm

Calibration graphs: linear response range of 5 decadesminimum (first point of each calibration graph corres-ponds to the limit of quantitation of the element)

ACTIV

A M

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The addition of adjacent spectral windows allowsthe system to cover the entire 120-800 nm range:each entire spectrum is stored, allowing recalcula-tion at any time on any element.

This configuration offers :l Minimised spectral interferences, thanks to high

and constant resolutionl Excellent limits of detection, regardless of the ma-

trix complexity, thanks to high light throughput l Ability to determine halogens in the far UV

The unique megapixel CCD based-camera allowsobservation of the Normal Analytical Zone of theplasma. This vertical torch-based Total PlasmaView provides instrumental limits of detection com-parable to axial or dual view systems, but is super-ior in terms of:lWarm-up time of typically 15 min (computer

controlled automatic solid-state RF generatorrunning at 40.68 MHz)

lLow argon consumption (12 L/min) and a quick-mount demountable torch with less parts replace-ment

lPerfect reproducibility in torch positioning and sto-red operating parameters, facilitating multi-useroperation

lLong-term stability even for difficult matrices,offered by the configuration of the torch associa-ted.

lMinimised matrix effects and few memory effects• Allowing complex matrix, high dissolved solids

or organic sample analysis (thanks to the largeinternal diameter, 3 mm, of the injector and tothe unique sheath gas device)

• Providing better limits of detection l Linear concentration range over a minimum of

five decadesl High sample throughput with minimal re-sloping

effortl Incomparable ICP-OES performance for alkaline

elements

Long-term stability for 1 mg/L of elements in 30% NaCl sample (average RSD < 1 % over 3 hours without re-sloping orinternal standard correction)

1.200

1.150

1.100

1.050

1.000

0.950

0.900

0.850

0.8001 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Number of runs

Nor

mal

ized

Int

ensi

ty

As 188.983 nmSe 196.026 nm

Pb 220.353 nm

Mn 259.373Zr 343.823

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A Platform of supportHORIBA Scientific,the solution for inorganic analysisBesides our ACTIVA M, HORIBA Scientific proposes afull range of ICP-OES instruments, offering the bestconfiguration suitable to your requirements.

ACTIVA family and ULTIMA 2 family provide alarge choice of solutions for a laboratory.ACTIVA S combines simplicity of operation toge-ther with robustness and stability. Based on CCDdetection, it offers performance and flexibility. ACTIVA M expands the application capabilitiesthrough assistant tools and enables the analyst toeasily become an expert, regardless of the com-plexity of the application. High quality of results isachieved, ensuring optimum routine analysis condi-tions. Alternative wavelengths and halogens aremeasurable thanks to far UV capability.ULTIMA 2 features the lowest detection limits avai-lable today, with single view radial plasma and thebest optical resolution. Adding a direct viewed si-multaneous optical system to this model (ULTIMA2C and ULTIMA 2CHR) provides a complete solu-tion for a laboratory with the speed and flexibilityrequired for many applications where the need fora fast analysis time must not compromise instru-ment performance.

The simultaneous system also achieves excellentprecision on major elemental determinations, andwith ULTIMA 2CHR, optimum analytical perfor-mance is gained for the most complex materials.

HORIBA Scientific is completing the offer in ICPanalysis with 2 separate ranges of inorganic stan-dards, SPEX Certiprep (triple checked) standardsand Précis standards. One can use different lotssupplied by 2 sources for calibration and validation,as recommended by Good Laboratory Practices,ordered from a single vendor.

ACTIV

A M

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ICP spectroscopy is also used for WEEE/RoHS/ELVcompliance testing when XRF screening indicatesthat a hazardous substance is present at or abovethe limit, or when the detection capability of XRF isnot sufficient to detect the low level of these subs-tances.The XGT-WR series, EDXRF analytical ImagingMicroscope, also offered by HORIBA Scientific,provides very good sensitivity for compliancescreening and is complementary to the ICP perfor-mance.

HORIBA Scientific is also a major supplier forsystems dedicated to Solid analysis. GDS (GlowDischarge Spectrometry, based on optical emis-sion) is the ideal technique for both bulk analysis insolids (conductive or not) and depth profiling forlayer characterisation of coatings or surface treat-ments.

For elemental analysis, HORIBA Scientific givesyou the opportunity to choose the instrument thatfits your needs for Carbon/Sulfur analysis (EMIAseries) or Oxygen/Nitrogen/Hydrogen analysis(EMGA series). From ppm to 100%, C/S andO/N/H are analyzed in solids or powders, as a

complement to ICP-OES, for applications like steel,pure and precious metals, cement, alloys, soil…There is also the SLFA series to determine Sulfurfrom 0.03 ppm up to 10% in a wide variety ofpetroleum based products.

Our commitment to support our users is expandedto the offer of both analytical and technical assis-tance directly or through our global network ofrepresentatives. A wide range of documents isavailable, including user and technical manuals aswell as application and technical notes, for yoursupport.

Training (on-site or at HORIBA Scientific applica-tion laboratories) and analytical assistance give theoperators the help and knowledge to perform ana-lysis under optimum conditions.

HORIBA Scientific, a broad range of support

Refer to ACTIVA M Pre-Installation Guide for more details.

Depth 698 mm (27.5 in)

Width 1321 mm (52 in)

Height 604 mm (23.8 in)

Weight 195 kg (430 lb)

Power Single-phase, 220-240 V, 50/60 Hz, 4 kVA

Specifications subject to change without notice.

PHYSICAL DATA

Generator Radio frequency, solid-state 40.68 MHz, water cooled

Cooling system GenCo water chiller for the generatorand the coil

Exhaust Direct exhaust connection forplasma compartment

Plasma Fully demountable torch, 3 mm i.d.,alumina injector, 12 L/min plasmagas, 0.2 L/min sheath gas

Sample introduction Concentric glass nebulizer, cyclonicglass spray chamber, 3 channelsperistaltic pump

Optical system Thermo-regulated, 0.64 meter focallength, dual back-to-back gratings,4343 g/mm and 2400 g/mm used inthe 1st order with optical resolution<10 pm for 120-430 nm and <18 pmfor 430-800 nm

Wavelength range 120-800 nmDetection Back thinned illuminated CCD,

2048x512 pixels, pixel size 13.5x13.5 µm, Peltier cooled

TECHNICAL SPECIFICATIONSAS-500 Autosampler with rinse stationAr humidifierMicro / high dissolved solids / inert material / organicnebulizersScott / HF resistant / cooled spray chambersUltrasonic nebulizerCMA for simultaneous measurement of hydrideforming elements and other elementsOxygen kit for organic samplesLaser ablation system

OPTIONS

France: HORIBA Jobin Yvon S.A.S., 16-18 rue du Canal, 91165 Longjumeau CedexTel: +33 (0)1 64 54 13 00 - Fax: +33 (0)1 69 09 07 21 - Email: info-sci.fr@horiba.com

USA: HORIBA Jobin Yvon Inc., 3880 Park Avenue, Edison, NJ 08820-3012. Toll-free: +1-866-jobinyvonTel: +1-732-494-8660 - Fax: +1-732-549-5125 - Email: info-sci.us@horiba.com

Japan: HORIBA Ltd., Scientific Instruments Sales Dept., Alte-Building Higashi-Kanda, 1-7-8 Higashi-Kanda, Chiyoda-ku, 101-0031 Tokyo - Tel: +81 (0)3 3861 8231 - Fax: +81 (0)3 3861 8259 - Email: info-sci.jp@horiba.com

Germany: +49 (0)89 46 23 17-0 Italy: +39 0 2 57 60 30 50 UK: +44 (0)20 8204 8142China: +86 (0)10 8567 9966 Other Countries: +33 (0)1 64 54 13 00

www.horiba.com/scientific

Cooling water 2 to 3 L/min, 2 bar

Argon 99.995% purity

Nitrogen 160 to 190 nm, 99.999% purity

120 to 160 nm, 99.9995% purity

Exhaust 250 m3/h (150 cfm)

Environmental 20 to 80% humidity non-condensing,18-24°C at ± 2°C

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