W ater is the best-knowntest medium used in ele-mental measuring tech-

niques in instrumental analysis.However, modern instrument sys-tems such as Shimadzu’s AA-7000(atomic absorption spectroscopy,AAS) or ICPE-9800 (optical emis-sion spectroscopy with inductive-

- fo )SEO-PCI ,amsalp delpuoc ylfer considerably more applicationpossibilities.

What are these possibilities andwhat special solutions are avail-able? One answer is provided by

- revo noitacilppa gniwollof ehtview of the ICPE-9800, which canmeasure more than 70 elements atthe same time for any applicationwithin the shortest possible time(simultaneous elemental analysis).Due to the high dynamic measure-ment range of the ICPE-9800, it isirrelevant whether the elements tobe determined are present in thelower ppb range (µg/L) or in thehigher ppm range (mg/L).

The ICPE-9800 with its �exibleinstrument con�guration is a truemulti-tool. For instance, operationcan be switched between hydridesystem and ultrasonic nebulizer aswell as between the various sam-

- nagro dna retaw sa hcus ,sepytelpic samples.

Quality assurance of sulfuricacid for special applications

Sulfuric acid (H 2SO 4 - am a syalp )jor role in synthetically producedchemicals. Its application range is

Espresso in LakeConstanceFive application examples of simultaneous elemental analysis sensitivity

stnemeriuq er eht dna esrevid yrevfor high purity are not alwaysmet, as for instance in the produc-

muinom ma dna etahpsohp fo noitsulfate fertilizers. [1]

However, there are also many spe-cial application areas requiringhigh-purity sulfuric acids such assample preparation for instrumen-tal analysis. Here, the acid is, forinstance, used for sample diges-

- oeg emos ro staf ,sremylopfonoitlogical samples such as aluminumoxide. [2]

Using the ICPE-9800, a sulfuricacid sample was measured in a1 : 10 and 1 : 20 dilution. Using thestandard addition method as cali-

bration model, matrix e�ects canbe masked. When the results ofboth dilutions are comparable, itcan be assumed that the method isaccurate. In order to permit a �nalvalidated method, a certi�ed refer-ence material can be measured inaddition. The results (summary)are listed in table 1 and are deter-mined for each element at variousanalytical wavelengths.

Although the diluted sulfuric acidsolution still is quite aggressiveand its viscosity di�ers from thatof water, measurement can be car-ried out using the standard con�g-uration (Minitorch). In additionto the consistent results of the dif-ferent dilutions, the recoveries for

samples with added standard arealso very good (100 ± 3 %).

Rapeseed oil for biodiesel –determination of phosphorus,sodium and potassium

Vegetable oils in fuels contributeto the sustainable operation ofcombustion engines. However,they should not in�uence engineperformance and catalyst e�cien-cy in order to guarantee the envi-ronmental friendliness of biofuels.[3]

The determination of phosphorusin rapeseed oil is therefore essen-tial, as this element impairs thefunctioning of catalysts. High lev-els of calcium and magnesium arealso detrimental, since both are

- ed hsa desaercni htiw detaicossaposits in soot particle �lters. [3]

For measurement using ICP-OES,the sample only needs to be dilut-ed. The use of an additional com-bustion gas (oxygen) is not neces-sary in this case. Nevertheless, thehighly sensitive axial plasma

ICPE-9800 – the multi-tool

APPLICATION

APPLICATION

.deilppa eb nac edom noitavres boMeasurement results and detec-tion limits are compared in table2. When selecting a more sensitiveworking range, additional andmore sensitive wavelengths can be

used, whereby the detection limitis further reduced. The stability ofmeasured values for the analysisresults is 100 ± 2 % (measuringinterval 1 hour).

The results show that the limitvalue can be determined very sat-isfactorily using the ICPE-9800and that the broad measuringrange makes it possible to alsounequivocally and reliably meas-ure increased concentrations.

Based on the analysis results, thesample can be assessed and isfound to be clearly unsuitable foruse in biofuels. The considerablyincreased concentration of thethree elements may, for instance,be due to the increased proportionof immature seeds used in produc-tion. Other i uencing factors arethe shelling of the seeds and pro-portion of broken grains as well asthe pressing parameters such asthe pressure head temperature.

When using the ICPE-9800 foranalysis of other types of organicsamples, for instance samples fromthe petrochemical industry, the

use of an Ar/O 2 mixed gas supplykit is recommended.

Along with the standard argon- ni si sag lanoitidda na ,sag reirrac

troduced via the quadruple torchfor sample transport and mainte-

sesaerc ni tI .amsalp eht fo ecnanthe decomposition of the matrix,thereby reducing backgroundnoise.

By using this instrument con u-ration, the plasma can be observedaxially and radially despite thecarbon-rich sample material, anddetection limits in the lower ppbrange can be achieved. For exam-ple, for tin in toluene, a detectionlimit of 2.0 ppb could be attained.

- ni siht rof sepyt elpmas rehtOstrument con uration are, forinstance, kerosene, xylene, methyl

- orposi ,)KBIM( enotek lytubosipyl alcohol (IPA), ethyl alcohol oralso the volatile tetrahydrofuran(THF).

Table 1: Analysis results of sulfuric acid. For determination of the recovery, 0.5 mg/L (ppm) of the element was added. n.d. = not detectable.

H2SO4 Sample A

Spike Recovery

H2SO4 Sample A

Spike Recovery

20

10

n.d.

98 %

n.d.

97 %

2.62 ppm

102 %

2.62 ppm

97 %

0.052 ppm

99 %

0.073 ppm

99 %

0.056 ppm

100 %

0.038 ppm

98 %

1.68 ppm

100 %

1.79 ppm

98 %

0.032 ppm

99 %

0.033 ppm

97 %

Dilution factor Cadmium, Cd Chromium, Cr Copper, Cu Magnesium, Mg Nickel, Ni Zinc, Zn

Elemental analysis in limitedsample volumes – 1 mL andless!

The intelligent instrument design- er ylno ton 0089-EPCI eht fo

duces the consumption of argonvia its Minitorch, but also ensures

ciency in other aspects: a CCD- ne eht stceted ylsuounitnoc pihc

- ca erofereht dna murtceps eritquires information on the elementcontent of a sample cantlyfaster than the earlier sequentialICP-OES technique.

Unlike conventional sampleamounts of 5 - 10 mL, the ICPE-9800 only needs 1 mL or less sam-

- pa eht no gnidneped ,emulov elpplication. In this way, the smallestsample amounts can be investigat-ed without the need for dilution.

- fe gnivasemit eht ot noitidda nIfect, not having to dilute the sam-ples eliminates the danger of con-tamination and the loss of sensi-tivity. Within the shortest possibletime, it is possible to obtain mean-

- ed etacilpirt a morf stluser lufgni- ar dna laixa gnidulcni noitanimret

dial plasma observation.

The measurement of small sample- mil rof lufesu ylno ton si stnuoma

ited volumes. When larger vol-umes of test media are to be meas-ured for changes in element con-tent over a longer period of time,it is also advisable to only usesmall samples in order to mini-mize the on the test system.

Rare earths in electronic waste – an alternative source of raw materials?

Which elements are actually con-tained in waste? This is a keyquestion in a world with limitedquantities of raw materials andtheir continuously increasing con-sumption. Bottlenecks in the sup-

- mi ydaerla era shtrae erar fo ylp- em eht ni derevoc scipot tnatrop

dia.

Rare earths belong to a group ofelements that include neodymium,dysprosium or cerium, and addspecial features to advanced elec-tronic components. They make itpossible to design small and com-pact mobile phones that are, at thesame time, quite powerful. But

Table 2: Results obtained with the ICPE-9800. Analysis results of rapeseed oil as well as detec-

tion limits and maximum admissible content according to DIN 51627-6 (*dilution factor regarded).

PhosphorusCalciumMagnesium

3.0 mg/kg1.0 mg/kg1.0 mg/kg

0.085 [177.499 nm]0.025 [183.801 nm]0.005 [285.213 nm]

13.617.4

1.80

ElementLimit value toDIN 51627-6

Detection limit*[mg/kg]

Analysis result*[mg/kg]

these elements are also used atton-scale, for instance in the greenenergy sector as in generators ofmodern wind turbines.

- eb era secruos lairetam war sAcoming limited, recycling possibil-ities are moving into focus, espe-cially when extraction of rare

- irup tneuqesbus dna sedixo htrae- er mrof latem erup ot noitacif

quires extensive use of chemicals.In 2010, the EU classi rareearths as raw materials with a highsupply risk [5]. Todays REE recy-cling rate is around 1 %.

Is recycling from electronic scrapworthwhile? To answer this ques-tion, various electronic compo-nents were crushed (homoge-nized) and digested in a laborato-ry microwave oven. The digestionsolution can be measured using

- er eht sdleiy dna SEO-PCI ehtsults listed in table 3.

This study shows that the analysisof solids using the ICPE-9800 ispossible and that modern wastecontains many elements which arein high demand on the interna-tional raw materials market. Notevery sample may contain a vari-ety or a large amount of rare

- om desu fo gnilcycer tub ,shtraebile phones (> 1 g/kg Nd) couldbe quite conceivable after selectivepresorting. For more informationon analysis of REE in e-wasteplease see literature note.

References:[1] Schwefelsäure (sulfuric acid) In: Römpp

Online. Georg Thieme Verlag, retrieved

9 May 2014.

[2] Application database CEM Corporation

[3] Remmele, Die neue Norm für Rapsölkraft -

- redröF dnu -eigolonhceT ,50615 NID ffots

zentrum TFZ, Straubingen,

http://www.duesse.de/znr/pdfs/2010/2010-

11-25-biokraftsto�e-03.pdf

[4] Qualitätssicherung bei der dezentralen

P�anzenölerzeugung, 12. Bericht aus dem

TFZ, Straubingen

http://www.tfz.bayern.de/mam/cms08/biok

raftsto�e/dateien/12_bericht.pdf

[5] Report of the Ad-hoc Working Group on

de�ning critical raw materials: Critical raw

materials for the EU, 2010

http://ec.europa.eu/enterprise/policies/raw

materials/�les/docs/report-b_en.pdf

the environmental sector are notincluded in the above list. But it isalso possible for these elements toattain detection limits in the pptrange. In this case, the ability ofthe elements to pass from the liq-uid into the gas phase after con-version with sodium borohydrate(NaBH 4) is taken advantage of.Instead of the aerosol, the gasstream is introduced into the plas-ma, completely separated from thematrix. As, Sb, Se, Sn and Hg canbe detected in the ppt range usingthis variant.

ICPE-9800 is therefore a goodand economical alternative toICP-MS for detection in the ultratrace range in order to addressspeci�c analytical problems.

Ultra-trace analysis in the ppt range

When elemental analysis in the pptrange (ng/L) rather than in theppb range (µg/L) is required,questions can often be answeredusing ICP-MS. But this concen-tration range can also be coveredusing advanced ICP-OES such asthe ICPE-9800. In this way, detec-tion limits for more than 10 ele-ments (Ba, Be, Ca, Eu, Lu, Mg,Mn, Sc, Sr, Y, Yb) lie within singleor double-digit ppt range usingthe standard con�guration includ-ing the Minitorch. For more sen-sitive detection of other elements,various other approaches areavailable.

Special nebulizers generating sam-ple aerosols more e�ciently and

- pord rellams a htiw ylbicudorperlet size distribution reduce detec-tion limits very easily without theneed to signi�cantly change the

- da nA .noitarugifnoc tnemurtsniditional ultrasonic nebulizer can

Table 3: Analysis results in mg/kg for rare earths in electronic scrap.

n.d. = not detectable.

Mobile phone

LCD (Display)

Printed circuit board

Sample

1.040

33

n.d.

Nd

107

51

n.d.

88

n.d.

n.d.

48

n.d.

n.d.

4,6

7,8

1,3

4,6

n.d.

n.d.

n.d.

86

32

La Pr Dy Y Er Ce

be connected to the ICPE-9800,enabling more sensitive measure-

- eB .02 fo rotcaf a ot pu yb stnemsides the elements mentionedabove, which can be calibrated inthe ppt range using the standardcon�guration, 27 more elementswith detection limits in the dou-ble-digit ppt range and lower areadded (Ag, Cd, Ce, Co, Cr, Cu,Dy, Er, Fe, Gd, Hf, Ho, La, Li,Mo, Nb, Nd, Pd, Pr, Sm, Ta, Tb,Ti, V, Zn, Zr). Strontium has thelowest detection limit of 1 ppt(parts per trillion – this is theequivalent of a cup of espresso inLake Constance [Bodensee] sur-face area = 536 km2).

Elements such as arsenic and mer-cury that are highly important for

APPLICATION

Further information

on this article:

• Application Note

ICP-OES Spectroscopy

(PDF)

• Poster Rare Earth Elements in Electronic

Waste (PDF)

www.shimadzu.eu/shimadzu-news-2014