CHAPTER 2 Instrumentation 2.1 LIGHT SOURCES This Section i s concerned w i t h advances i n the design and operation o f a l l sources used i n AAS and AFS, except lasers which are discussed i n Sections 1.1.2 and 1.3.5. four s i g n i f i c a n t review a r t i c l e s were published. - a l . (1041) separately described the general development o f l i g h t sources f o r a n a l y t i c a l atomic spectroscopy.The spectral and physical properties o f HCLs were summarized by P i l l o w (430), and f a c t o r s which influence the i n t e n s i t y and shape o f l i n e p r o f i l e s o f AAS sources were reviewed by Falk (1995). The processes which occur i n hollow cathode lamps continue t o be o f major i n t e r e s t . Farnsworth and Walters (2234) applied time and space resolved emission spectroscopy t o investigate e x c i t a t i o n mechanisms i n a r.f.boosted pulsed HCL. Spectral measurements during the current pulse, r.f. boost and afterglow periods, suggested t h a t e x c i t a t i o n involved a combination o f charge exchange, electron impact and recombination processes. The short-term s t a b i l i t y o f pulsed HCLs was investigated by Kureichik (1527) who reported t h a t a t optimum pulse duration and r e p e t i t i o n frequency, emission s t a b i l i t y was almost an order o f magnitude b e t t e r than f o r continuous operation.r e l a t i o n between Ne l i n e i n t e n s i t y and HCL current varied depending on the lamp pressure, and was d i f f e r e n t f o r a number of l i n e s .increased more slowly, b u t i n a few cases more r a p i d l y , than the current. The trends were r e l a t e d t o e x c i t a t i o n conditions i n the discharge by a mathematical expression. Doppler broadening measurements. The r e s u l t s i l l u s t r a t e d t h a t the k i n e t i c tem- perature depended on the plasma radius and gas pressure i n the lamp. Although r e l a t i v e l y few novel concepts were reported during the year, S u l l i v a n (773) and Baranov et Howard and co-workers (C260) observed t h a t the I n most cases i n t e n s i t y The k i n e t i c gas temperature o f an A1 HCL was calculated (1382) from Additional references on the preceding t o p i c - C92, 817.An improved boosted discharge lamp w i t h demountable cathode was developed by Norris and Ross (C442), based on the p r i n c i p l e described by S u l l i v a n (see ARAAS, 1979, 9, Ref. 1559). Unlike e a r l i e r demountable systems, i t was a flow-through device g i v i n g l i t t l e o r no carry over from one cathode t o the next. The boosted discharge provided a high i n t e n s i t y spectral l i n e w i t h extremely narrow l i n e - width, and improved s e n s i t i v i t y was obtained f o r most determinations by AFS.S u l l i v a n and co-workers (C441) used f i n e metal powders t o prepare pressed s i n g l e 4748 Analytical Atomic Spectroscopy and mu1 ti-element interchangeable cathodes f o r boosted-output lamps. The per- formance in AAS and AFS was found t o be s a t i s f a c t o r y w i t h respect t o signal s t a b i l i t y and analytical s e n s i t i v i t y .The quest f o r high i n t e n s i t y discharge lamps has resulted i n the design of a number of i n t e r e s t i n g source geometries. Combined-discharge lamps were described t h a t operated on the basis of two separate e l e c t r i c a l discharge mechanisms (593). A sputtering discharge was i n i t i a t e d between a common anode and one, two o r four hollow cathodes, and a second boosting discharge was formed between a thermionic cathode and the anode.Lamps f o r u p t o 26 elements were prepared, some w i t h multi-element discharges. By application of s e l e c t i v e modulation t o i s o l a t e desired resonance l i n e s , an increased l i n e a r range a t h i g h absorbance was achieved.Controlled temperature gradient lamps, similar t o those described by Gough and Sullivan (see ARAAS, 1980, 10, Ref. C835), were used by Norris and co-workers f o r the determination of As and Se i n environmental samples by AFS (C68, C445). The performance of the lamps was superior t o t h a t o f EDLs i n terms of higher energy output, narrower line-width, and a reduced occurrence o f self-reversal.The usefulness of thermal gradient lamps f o r exciting the atomic fluorescence of As, P , S , Se and Zn in an ICP has a l s o been discussed (C92). envelopes was reported (592). High i n t e n s i t y discharges f o r a1 kaline-earth elements and L i were produced f o r use in AAS and AFS. developed a simple and inexpensive I c a p i l l a r y discharge lamp f o r AAS.The atmospheric pressure discharge was generated between two Nb electrodes i n a stream of He and I flowing through a quartz tube. Preparation of a sinter-cathode HCL : 1207. Regenerated HCLs i n a demountable system : 2000. The construction of r . f . electrodeless discharge lamps w i t h molybdenum-glass Lowe and co-workers (545) Other references of i n t e r e s t - 2 . 2 OPTICS 2.2.1 Background Correction A new technique f o r single lamp background correction i n AAS was developed by Smith and colleagues i n co-operation with Hieftje (C56, C1437, C2138, C2194, C2298, C2464). l i n e p r o f i l e s a t high current. l i n e passing through an atom c e l l i s reduced by analyte absorption and background e f f e c t s .l i n e i s mainly reduced by the background processes. absorption in a flame o r furnace a t low and then a t high HCL currents, i t was possible t o account f o r non-specific absorption by electronic subtraction of the two measurements. correction occurs a t wavelengths close t o the analyte resonance l i n e , optimal The concept i s based on the broadening and self-reversal of HCL A t low current, the i n t e n s i t y of the narrow HCL However, a t high currents, the i n t e n s i t y of the broadened and reversed Hence by comparison of The inventors suggested t h a t since t h i s form of backgroundInstrumentation 49 correction o f both broad-band and structured background absorption can be achieved.and imaging problems,and avoids atomization c e l l modifications.It was predicted t h a t t h i s new form o f correction would be p a r t i c u l a r l y useful f o r elements w i t h wavelengths i n the v i s i b l e region, and f o r the correction o f background absorp- t i o n caused by transition-metal matrices. No c o n e n t s were made as t o the l i k e l y e f f e c t o f pulsed high and low current operation on HCL l i f e t i m e .De Gal an and co-workers described ( 1 489) t h e i r previously reported magnet power supply f o r a.c. modulated Zeeman-effect AAS which allowed an extended 0.5 ms measurement time a t zero f i e l d strength (see ARAAS, 1981, 11, Ref. C808). The same authors a1 so recommended (C252 , 1501 ) an a d d i t i o n a l t h i r d absorbance measurement a t a f i e l d strength intermediate between zero and the 10 kG maximum f i e l d .l i g h t , and extended the dynamic range and r o l l - o v e r p o i n t t o higher concentrat- ions. An apparent disadvantage o f the three f i e l d Zeeman procedure was halved a n a l y t i c a l s e n s i t i v i t y . A method f o r the i d e n t i f i c a t i o n o f solutions w i t h analyte concentrations greater than the r o l l - o v e r p o i n t was devised by Koizumi -- e t a l .(1149). t r a n s i e n t absorption peaks (width a t h a l f height) which appeared a t the beginning and end o f s o l u t i o n a s p i r a t i o n i n t o a flame, during the b u i l d up and decay o f the atom concentration. The authors applied a permanent magnetic f i e l d t o the flame, and d i f f e r e n t i a l absorption (411) was observed f o r HCL r a d i a t i o n p o l a r - ized perpendicular and p a r a l l e l t o the magnetic f i e l d by a b i r e f r i n g e n t Rochon prism.r o t a t i o n a l l i n e s o f OH which e x h i b i t Zeeman s p l i t t i n g were evaluated by Massmann (1400). l o n g i t u d i n a l a.c. magnetic f i e l d s .The c h a r a c t e r i s t i c s o f d i f f e r e n t configur- ations f o r Zeeman AAS have also been compared (C2465). Several ETA-AAS a p p l i c - ations were used t o i l l u s t r a t e the advantages o f the Zeeman technique, operated i n conjunction w i t h platform atomization (see also Section 1.4.4.1). Methods were described f o r the determination o f P i n s t e e l (1581), and f o r various trace metals i n body f l u i d s (C58, C61, 391, C1435), transition-metal matrices (C61 , 391 ) and water samples (C1435).s i 1 i cate analysis was reported by P i n t a and co-workers (1 714). (324) who modified an echelle spectrometer t o include an o s c i l l a t i n g quartz r e f r a c t o r p l a t e for the production o f a second d e r i v a t i v e I C P spectrum.The use o f a r o t a t i n g quartz chopper f o r background correction i n FAES, FAFS and ETA-AES was b r i e f l y reviewed by Ottaway and co-workers (544). was f u r t h e r developed by McCaffrey and Michel (C2120) who employed a double modulation procedure t o detect the fluorescence signal i n continuum source AFS. The procedure i s a t t r a c t i v e i n t h a t i t eliminates source alignment This a1 lowed simultaneous correction f o r background absorption and s t r a y Fast time constant electronics were used t o detect 110 t o 250 ms Systematic e r r o r s due t o the coincidence o f analyte l i n e s and sharp The e f f e c t was studied f o r transverse d.c., transverse a.c., and The use o f Zeeman background correction i n Wavelength modulation was used f o r background correction by I s h i i and Satoh This form o f modulation50 Analytical Atomic Spectroscopy Downey and H i e f t j e (C184, 2258) achieved e f f e c t i v e background correction i n ICP-OES w i t h a moderate r e s o l u t i o n monochromator by application o f t h e i r s e l e c t i v e s p e c t r a l - l i n e modulation procedure (see ARAAS, 1981 , lJ, Ref. 165). Line, band, and scattered 1 i g h t interferences were almost completely removed by passing the I C P r a d i a t i o n a l t e r n a t i v e l y through and around a flame containing a high concen- t r a t i o n o f analyte atoms. Other references o f i n t e r e s t - B r i e f reviews o f current status o f Zeeman AAS : 468, 1679. Compari son o f background correction procedures : C1440.On-line Zeeman AAS determination o f Hg i n shale gases : 352 Patent f o r Zeeman AA spectrometer w i t h r o t a t i n g p o l a r i z i n g f i l t e r : 903. Tunable Zeeman atomic-line spectrometer f o r molecular absorption : 1370. 2.2.2 Optical Systems A v a r i e t y o f i n t e r e s t i n g o p t i c a l modifications were described which may give some idea o f 1 i k e l y f u t u r e spectrometer developments i n atomic spectroscopy.A m u l t i p l e echelle g r a t i n g arrangement (MEGA) was constructed (C2479) which gave a p r a c t i c a l r e s o l u t i o n o f 1.5 m i l l i o n w i t h only a r e l a t i v e l y s h o r t focal length (1.2 m). Four i d e n t i c a l gratings were mounted i n such a way t h a t t h e i r disper- sions co-acted t o give an e f f e c t i v e spectral r e s o l u t i o n equivalent t o the sum o f the i n d i v i d u a l g r a t i n g resolutions.A v e r s a t i l e double monochromator spectrometer was designed (C2171, C2480) which incorporated two focal planes on the Rowland c i r c l e , both covering the range 165-500 nm. An incremental angle encoder monitored the p o s i t i o n o f the microcomputer-controlled arm which could p o s i t i o n up t o ten e x i t slit/PMT mounts on each f o c a l plane. was exclusively used t o scan the spectrum before positioning o f the s l i t assemblies.This system had the advantage t h a t a n a l y t i c a l programmes could be automatically changed without breaking the vacuum. A s i m i l a r degree o f f l e x i - b i l i t y was achieved (C2483) w i t h a monochromator which had a f i x e d g r a t i n g and moveable photomultiplier tubes.exhibited precision equivalent t o a d i r e c t reading spectrometer and t h a t l i n e peaks o r background positions could be accurately located i n less than 1.5 s . The micrometer-driven entrance s l i t , normally used t o optimize o p t i c a l a l i g n - ment o f a d i r e c t reader, was purposely realigned t o detect spectral l i n e s w i t h i n 2 0.10 nm o f one o f the wavelengths i n the f i x e d array (C187).the spectrum was s h i f t e d r e l a t i v e t o the e x i t s l i t s and the number o f elements t h a t could be determined w i t h the instrument was increased from 29 t o 59.An a u t o - p r o f i l i n g system was developed (C188) t o c o r r e c t wavelength d r i f t i n a d i r e c t reading spectrometer. entrance s l i t was used t o check the coincidence o f the peak wavelength o f an I C P A r l i n e and the p o s i t i o n of the e x i t s l i t f o r t h a t l i n e . An a d d i t i o n a l e x i t s l i t It was suggested t h a t t h i s arrangement By t h i s procedure A quartz r e f r a c t o r p l a t e mounted behind the I f d r i f t wasInstrumentation 51 detected, the p o s i t i o n o f the p l a t e was automatically a l t e r e d t o s h i f t the e n t i r e spectrum t o the corrected p o s i t i o n f o r a l l the analyte l i n e s .reported t h a t had a unique g r a t i n g d r i v e capable o f scanning from 170 - 800 nm i n under one second.than conventional drives and f u r t h e r reports are awaited w i t h i n t e r e s t . A new design of computer-control l e d scanning monochromator (C19, C20) was This remarkable feature i s orders o f magnitude f a s t e r Harnly and O'Haver have continued t o investigate the c h a r a c t e r i s t i c s o f wavelength modulation as applied i n continuum source AAS.an o s c i l l a t i n g quartz r e f r a c t o r p l a t e r a p i d l y scans the absorption p r o f i l e t o calculate analyte absorbance and automatically compensate f o r background absorption by the matrix (see ARAAS, 1980, 10, 70). Harnly (972) measured the e f f e c t o f three modulation waveforms on the SNR o f continuum source AAS signals and found t h a t f o r detection frequencies below 80 Hz, a three-step square wave and a bigaussian wave gave a 1.6 times improvement over sine wave modulation.Above 80 Hz the advantage decreased t o a f a c t o r o f 1.1-1.2 a t 160 Hz, due t o d i s t o r t i o n o f the more complex waveforms a t higher frequencies. The frequency t h a t gave the optimum SNR varied w i t h the waveform, the s l i t parameters, and the source i n t e n s i t y a t the analyte wavelength.I n a sub- sequent i n v e s t i g a t i o n (1 145) Harnly examined the influence o f the sl i t para- meters on SNR i n greater d e t a i l . a maximum as the s l i t width decreased, and the absorbance noise asymptotically approached a constant as the s l i t width and height were increased.parameters f o r optimum SNR varied from element t o element, b u t generally a 50 o r 100 pm s l i t width w i t h a 200 o r 300 pm s l i t height was best. r e p o r t (see ARAAS, 1981, 11, 51) Harnly and O'Haver described a procedure which used a bigaussian waveform t o make edge-of-profile measurements f o r the conout- a t i o n o f s i x absorbance c a l i b r a t i o n curves g i v i n g a combined l i n e a r concentration range o f 6 orders o f magnitude (C111).concept was also applied (C270) t o extend the l i n e a r range o f ETA-AES measure- ments obtained w i t h the same instrument system. f u r t h e r r e f i n e d (C2158) by use of a "staircase" modulation waveform which gave r i s e t o only two absorbance curves while s t i l l providing a l i n e a r range o f 4-6 orders.The primary advantages o f the new waveform were decreased computation time, and the provision o f improved SNRs f o r the less s e n s i t i v e absorbance measurements. The r a r i t y o f spectral interferences i n continuum source AAS has been confirmed (C102, 888) i n an extensive study o f 67 p o t e n t i a l i n t e r - ferences f o r 17 elements.Only two examples o f d i r e c t spectral overlap and two cases o f non-analyte absorbing l i n e s occurring w i t h i n the modulation i n t e r v a l were observed. The effectiveness o f the technique f o r the simultaneous AAS determination o f up t o 10 elements i n manganese nodules (1589), f r u i t j u i c e (C1427, C2292) and environmental water samples (1572) was demonstrated by the I n t h i s technique The absorbance signal asymptotically approached The s l i t I n a previous With minor software modification t h i s The absorption procedure was52 Analytical Atomic Spectroscopy authors.transmitted the atomic spectra of elements introduced into a flame f o r both absorption and emission studies.i n the opti cal beam provided the t u n i n g mechanism. A Voigt e f f e c t optical f i l t e r was described (1590, 1906) which selectively ----- Rotation of a retardation p l a t e inserted Other references of i n t e r e s t - Book on d i f f r a c t i o n gratings : 822. Optical arrangement f o r end-on viewing of an ICP : C18. Patent f o r AA spectrometer optical system : 359.Prevention of d r i f t i n a 1 m monochromator : 2324. Stray l i g h t measurement f o r an echelle spectrometer : C48. 2.3 DETECTORS No s i g n i f i c a n t advances i n the design of array detectors were reported i n 1982, so for the present, t h e i r SNR c h a r a c t e r i s t i c s remain i n f e r i o r t o PMTs even when the image i s i n t e n s i f i e d (2243).T h i s comparison i s apparently well understood by most workers because few analytical applications of array detectors appeared in the atomic spectroscopy l i t e r a t u r e . papers were presented which indicated the usefulness of sol i d - s t a t e image sensors as mu1 t i channel detectors , p a r t i c u l a r l y f o r fundamental studies w i t h emission sources, and f o r the rapid scanning of t r a n s i e n t o r b r i e f signals (C2315).Self-scanni ng 1 inear photodiode arrays can greatly faci 1 i t a t e a variety of spectrochemical measurements when used as detectors i n dispersive spectrometers. Horlick and co-workers (C145) continued t o investigate vertical s p a t i a l vari- ations of ICP spectra t o explain c e r t a i n widely observed inter-element e f f e c t s , and determine the energy p r o f i l e experienced by analyte species in the plasma (see Section 1.2.2.2).reading spectrometer w i t h s i x 128-element photodiode arrays t o improve the recognition and correction o f spectral background problems i n ICP-OES (C55, C1262). Each array simultaneously monitored 1.7 nm o f spectral information. I t was necessary t o r e s t r i c t the operation of the array clocking system t o only the readout period i n order t o prevent crosstalk between clock and video signals A similar study was undertaken by Powell and Goode (C2185).The performance of unintensified l i n e a r photodiode arrays was considered (C23, C2468) , from a theoretical basis, t o assess the usefulness of t h i s type of detector i n ICF studies.Arrays were used in AAS (C2195) t o measure simultaneously atomic absorption a t two analyte wave1 engths of d i f f e r e n t s e n s i t i v i t y t o extend the e f f e c t i v e l i n e a r range of AAS measurements. Charge injection and charge coupled devices ( C I D and CCD) w i t h 60 K pixel In c o n t r a s t , a number of conference They a l s o replaced the PMT detectors of a 1.5 m d i r e c tInstrumentation 53 ( p i c t u r e element) capacity were used (C2311 , C2312) as mu1 tielement detectors i n DCP and I C P spectrometry.The authors claimed t h a t these camera detectors were a t t r a c t i v e f o r t r a c e analysis since reasonable SNRs and l i n e a r i t y o f response could be achieved. Detection l i m i t s f o r a DCP were reported t o approach, and sometimes surpass, those o f a PMT i n p r a c t i c a l analysis.This form o f detector my be worthy o f f u r t h e r consideration. Although the use o f vidicon cameras appears t o be i n decline, three q u i t e d i f f e r e n t applications were reported during 1982. the forward s c a t t e r i n g spectra o f atoms i n the range 260-330 nm f o l l o w i n g ETA i n a transverse magnetic f i e l d .Busch and Benton (C2314) compared PMT and vidicon detectors f o r flame emission measurements w i t h a m u l t i p l e entrance s l i t spectrometer. Le Toulouzan e t a l . (862) investigated the c h a r a c t e r i s t i c s o f a He plasma by an Abel inversion procedure. 380-780 nm by sequential recording o f e i g h t 50 nm sections w i t h a vidicon tube.During the year s u r p r i s i n g l y l i t t l e reference t o optogalvanic (1479) and resonance (861) detectors was made i n the l i t e r a t u r e (see Section 1.3.5.2). Other references o f i n t e r e s t - Factors which influence photographic detection o f l i n e spectra : 432, 436, 1496. I n t e g r a t i o n read-out systems f o r PMT detectors : 364.Measurement of I C P background f l u c t u a t i o n s w i t h a photodiode array : 1490. Photodiode array system f o r measurement o f laser-induced fluorescence p r o f i l e s o f flame species : 1459. Wirz e t a l . (C263) measured Spectra were obtained i n the range 2.4 INSTRUMENT CONTROL 2.4.1 Computer Control and Data Processing 2.4.1.1 Emission I n I C P spectrometry the two main t o p i c s t o receive a t t e n t i o n were software developments f o r improved control and data processing, and intercomputer com- munication f o r data management.the s t a t i c f i x e d measurement p o s i t i o n method o r the dynamic p r o f i l e scan method may be used f o r the measurement o f peak emission i n t e n s i t y .o f both approaches were considered by B a r r e t t e t a l . (C75, C193, 1205, C2435) who described the dynamic measurement system incorporated i n the Perkin-Elmer ICP/5500. Attention has been drawn t o the l i m i t a t i o n s o f peak search and measurement routines when working close t o the instrument detection l i m i t i n I C P analysis (C239, C2182).complex spectra, without considering possible e r r o r s i n the measurement o f weak With slew scanning programmable monochromators, The r e l a t i v e merits Workers who accept the v a l i d i t y o f computer data obtained from54 Analytical Atomic Spectroscopy analyte s i g n a l s , have been c r i t i c i z e d (968, C1338). reported improvements in ICP instrument performance through the introduction of computer automation, and by the expansion of software routines.Weissman and Wolcott (C2186) simplified the automation of t h e i r laboratory constructed ICP spectrometer by selecting hardware which could be used w i t h comnercially avail- able software. s l i t t o permit a wavelength scan across an emission l i n e profile. movement was controlled by a stepper-motor and PDP 11/23 computer. (566) upgraded the performance of t h e i r scanning monochromator by combining a Z i log Z80A microcomputer w i t h a Hewlett Packard 9825A desk-top calculator t o control the grating stepper-motor drive.reading spectrometer were expanded by Petrie and Petrie (C1320) t o allow real- time analytical quality control of ICP data.the instrument computer t o another computer f o r data management. microcomputer was interfaced (C185) t o the minicomputer of a plasma spectro- meter t o improve sample organization, q u a l i t y control and data manipulation. Sample information was compiled w i t h the Apple prior t o analysis, sent t o the ICP minicomputer using a high speed s e r i a l interface, and stored on the ICP floppy disk system.Data obtained during the analysis could be transferred from the minicomputer t o the Apple a t the end of a measurement sequence f o r storage on the Apple disk. The ICP computer could then be used f o r the next s e t of analyses, while the Apple performed additional calculations, arranged the r e s u l t s and prepared a printout. ation t o other computers via a telephone link.A s i m i l a r form of data management was described by Demko e t a l . (C2066) who used a TRS-80 microcomputer and commercially available software i n conjunction w i t h an IL 100 ICP spectrometer. A microcomputer system was a l s o described (C1239) which combined data from ICP and AA spectrometers i n a s i n g l e report. preferred mainframe computers f o r data manipulation, p a r t i c u l a r l y i f a general integrated sample management system was desired.large "host" computer receives information from a variety of instrument computers f o r t r a n s f e r of data between laboratory centres and f o r long-term storage of r e s u l t s . The authors suggested t h a t these functions can be more e a s i l y achieved i f the analytical instrument software provides disk data storage in a format t h a t i s acceptable t o the host computer.I t i s a l s o necessary t o have comnunications software f o r the t r a n s f e r of the analytical data from the instrument computer disk t o the host system. computer network was also described by Duursma e t a l . (2260). emission spectrometry were described (C29, 1569).A number of,-workers They mounted a r e f r a c t o r plate behind the monochromator entrance Burman e t a l . The p l a t e The software routines of a d i r e c t To a s s i s t the rapid handling of ICP data, a number o f workers have interfaced An Apple The Apple could a l s o transmit the inform- Ediger and Barrett (C191, 2278) In t h i s case, a r e l a t i v e l y The use of a micro-mini-mainframe Hardware and software s u i t a b l e f o r source and instrument control i n spark T i m i n g was synchronized t oInstrumentation 55 b e t t e r than The computer functioned l i k e a multiplexer i n t h a t i t co-ordinated timing sequences instead o f merely i n i t i a t i n g them.chronization o f multi-sequence events. 0.1 PS f o r t h e operation of the spark, and f o r o p t i c a l measurements. This provided f o r b e t t e r syn- Other references o f i n t e r e s t - Abel inversion : 860, 1477, 1492. Computer automation o f a DCP echelle spectrometer f o r improved data hand- l i n g : C8, 973. Computer program f o r data a c q u i s i t i o n w i t h TRS-80 interfaced t o a d i r e c t reading spectrometer : 171 7.Computer-control l e d microdensi tometer f o r spectrographic analysis : 1573. Correction o f spectral interference e f f e c t s by regression analysis : C2168. F a c t o r i a l analysis o f matrix interference e f f e c t s : 323. Semi-quanti t a t i v e program f o r I C P spectrometry : C1242. User orientated software f o r sequential and simultaneous I C P instrument- a t i o n : C194.Simplex optimization procedures : C161, C162, 553, 1098, 1416, 2223, C2391. 2.4.1.2 Absorption No major new developments i n the computer c o n t r o l o f AAS instruments were reported i n 1982. Pye Unicam (C310, C2432) continued t o promote the h i g h l y automated PU 9000 series (see ARAAS, 1981, 2, 61), while Perkin-Elmer ex- pounded the b e n e f i t s o f the 3600 Data Station (C2184, C2460) and associated procedures f o r the video display o f signals (C112). Desantis e t a l .(C118) attempted t o couple two AA spectrometers t o the Perkin-Elmer Data s t a t i o n , b u t found t h a t the manufacturer's software could n o t cope w i t h t h i s requirement. Additional programs had t o be w r i t t e n t o provide an organized format f o r t h e e n t r y o f data, and t o allow the desired f l e x i b i l i t y i n instrument operation.The revised software could also be used f o r manual e n t r y o f absorption data. Gower and Shrada (C2065) discussed the advantages obtained i n signal measurement and data management f o r ETA-AAS, when a Hewlett Packard Series 80 computer was connected t o a Varian AA-975 spectrometer.The computer c o n t r o l l e d operation o f two AA spectrometers by a process computer (641) was described. was developed (403) t o allow data t r a n s f e r between an AA spectrometer and a desk-top computer v i a IEEE-48 o r RS 232 output l i n e s . The i n t e r f a c e could be used w i t h any spectrometer w i t h a d i g i t a l (BCD) output, and t r a n s f e r r a t e s o f 5000 bytes s - l (100 bytes s - l i n BASIC) were achieved.Improved ETA-AAS detection l i m i t s were obtained (988) by use o f an EG + G PARC 4202 signal averager. were proportional t o 14, where 1 was the number o f r e p e t i t i v e measurements. Subtraction o f one signal-time curve from another could provide blank o r back- An i n t e r f a c e Within c e r t a i n l i m i t s , improvements i n SNR could be achieved t h a t56 Analytical Atomic Spectroscopy ground c o r r e c t i o n f o r some a p p l i c a t i o n s .ager would be o f p a r t i c u l a r value i n t h e measurement o f f a s t ETA s i g n a l s when no e l e c t r i c damping o f t h e a m p l i f i e r c o u l d be t o l e r a t e d .t h e measurement o f f a s t ETA s i g n a l s w i t h slow response i n s t r u m e n t a t i o n were discussed by Routh (1567) and Grant (C2212). Problems mainly a r i s e due t o l a r g e time constants a t t h e o u t p u t o f t h e demodulator i n o l d e r spectrometers. Improved accuracy w i t h such instruments was obtained (C2212) by a p p l i c a t i o n o f t h e " r a t i o n a l method" a l g o r i t h m i n o f f - l i n e data r e d u c t i o n .A s p e c i a l c i r c u i t f o r measurement o f t r a n s i e n t s i g n a l s o f g r e a t e r than 0.5 ms d u r a t i o n was designed (1716). The r e c o r d i n g u n i t consisted o f a demodulator, a l o g a r i t h m i c convertor, a d r i f t compensator and an A/D convertor.a t concentrations g r e a t e r than t h e r o l l - o v e r p o i n t has been developed (see Section 2.2.1). AAS were published by Harnly and O'Haver (1770). The programs a r e f o r t h e a c q u i s i t i o n , i n s p e c t i o n and e d i t i n g o f data, and f o r a n a l y t i c a l c a l c u l a t i o n s (see Section 2.2.2). The authors suggested t h a t t h e aver- E r r o r s introduced by A microprocessor u n i t (1149) f o r t h e i d e n t i f i c a t i o n o f Zeeman FAAS s i a n a l s D e t a i l s o f t h r e e F o r t r a n computer programs f o r continuum source Other references o f i n t e r e s t - A u t o m a t i c a l l y t r i g g e r e d d i g i t a l i n t e g r a t o r f o r FAAS and FAES : 1546, 1729.C i r c u i t f o r t h e compensation of d r i f t i n a single-beam AA spectrometer : 245.E f f e c t o f A/D convertor r e s o l u t i o n on absorption measurements : C93. Functional n a t u r e o f m i c r o - c i r c u i t s f o r a n a l y t i c a l i n s t r u m e n t a t i o n : 245. L i m i t a t i o n s o f programmable c a l c u l a t o r programs f o r AAS : 1999. 2.4.2 Automated Sample I n t r o d u c t i o n - An automated s t a n d a r d i z a t i o n manifold f o r ICP-OES (C237, 872) consisted o f branched glass-tubing, f o u r two-way valves, two three-way valves, and f i v e s o l u t i o n r e s e r v o i r s .computer based on t h e DEC LSI-11 processor, w i t h software w r i t t e n i n assembly coding. combination o f t h e r e s e r v o i r s o l u t i o n s i n t o t h e n e b u l i z e r f o r s t a n d a r d i z a t i o n .The same authors (777) a l s o modified a Technicon I 1 AutoAnalyzer f o r automatic i n t r o d u c t i o n o f water samples i n t o a J a r r e l l - A s h 975 I C P . sequence was c o n t r o l l e d by t h e instrument computer w i t h e x i s t i n g software. An almost i d e n t i c a l approach was r e p o r t e d (C213) f o r t h e a n a l y s i s o f s o i l e x t r a c t s o l u t i o n s w i t h s i m i l a r i n s t r u m e n t a t i o n .Operation was c o n t r o l l e d by a H e a t h k i t H-1J micro- S e l e c t i v e a c t i v a t i o n o f t h e s o l e n o i d system pumped a p a r t i c u l a r The sampler o p e r a t i o n D i s c r e t e sample n e b u l i z a t i o n i s w i d e l y used i n FAAS and I C P spectrometry when -~ o n l y l i m i t e d sample volumes are a v a i l a b l e , and when continuous i n t r o d u c t i o n o f s o l u t i o n s may l e a d t o blockage o f t h e n e b u l i z e r .This procedure normally i n - volves manual i n j e c t i o n o f m i c r o l i t r e volumes, b u t attempts have been made t oInstrumentation 57 automate the method t o improve precision, and increase sample throughput, Goeringer and Klatt (598) constructed a microcomputer controlled p i p e t t e , based on liquid displacement via a calibrated screw-driven plunger, f o r the delivery o f volumes between 1 and 1000 u l .valve system f o r the nebulization of microsamples in FAAS was described (1968) and an 8-way motor-driven rotary valve device was developed by I t o e t a l .(977) f o r microlitre sample injection i n t o an ICP. Flow injection i s more f l e x i b l e than d i r e c t d i s c r e t e sampling since i t allows sample d i l u t i o n , the addition of releasing agents, and the use of a variety o f calibration procedures such as sample o r standard addition. ages were discussed by Tyson e t a l .(C261, 405) who a l s o proposed a liquid dispersion model t o account f o r the absorption-time behaviour observed when FI techniques a r e used i n FAAS. Greenfield e t a l . (C215, C1229) discussed the application of flow injection f o r ICP spectrometry and described the use of e i t h e r commercial sampling valves o r a computer controlled multi-way valve system introduction.f o r addition of u p t o 500 ~1 sample volumes i n t o reagent o r solvent ICP c a r r i e r streams. See also Section 1.2.1.2. Bi by hydride generation (see Section 3.1.4.1). Attempts have been made t o combine the determi nation of hydri de and non-hydri de formi ng elements i n order t o maintain t r u l y simultaneous analysis by ICP emission and fluorescence spectro- metry.which allowed conventional ICP analysis t o be performed concurrently w i t h hydride generation, without modification of the plasma assembly. Lancione (C2081) used a dual sample stream approach f o r the simultaneous deter- mination of hydride and non-hydride forming elements by ICP-AFS. stream was pumped t o a conventional nebulizer, and the other stream was acidified, mixed with reductant and then pumped t o a gas-liquid separator. sample channels were combined via a T-junction a t the base of the ICP torch. A 3-way d i s t r i b u t o r and electromagnetic These advant- Injection valves and HPLC pumps were used (C1246, 1540) Astrom (1450) published d e t a i l s of a method of FI f o r the determination of Schleicher e t a l .(C2179) described a continuous flow hydride generator Demers and One sample The Other references of i n t e r e s t - Automated hydride generation : 1773. Determination of As and Se by hydride generation w i t h comnercial accessory : 700. Discrete sampling w i t h an autosampler i n ICP emission spectrometry : C13. On-line d i l u t e r f o r AAS : 1517. On-line d i l u t e r f o r ICP spectrometry : 2241.Time-sequencer module f o r hydride generation : 1782.58 Analytical Atomic Spectroscopy 2.5 COMPLETE INSTRUMENTS 2.5.1 Emission Instruments Lang e t a l . (C45, C190) introduced hhe new Jobin Yvon JY-38 VHR sequential scanning I C P emission spectrometer which i s claimed t o have a p r a c t i c a l r e s o l - u t i o n b e t t e r than instruments w i t h echelle g r a t i n g and prism dispersion.A second monochromator i s provided which can be used as a reference channel t o give a r e l a t i v e precision o f 0.1%. A sequential I C P spectrometer designed by Bausch and Lomb (C2183) required l e s s than 1.5 s t o scan between wavelengths. The instrument's remarkable p o s i t i o n i n g accuracy o f 2 0.0005 nm i n second order allowed d i r e c t peaking and eliminated the need t o scan across each l i n e .An unusual design o f monochromator developed by Applied Research Laboratories was o p t i c a l l y l i n k e d (C28, C77) t o a 60-channel polychromator t o provide a h i g h l y f l e x i b l e integrated emission spectrometer. The programmable monochromator was based on a Paschen-Runge mount and had 250 equally spaced s l i t s arranged on the f o c a l curve.By micrometer displacement o f the entrance s l i t , i t was possible t o p o s i t i o n a spectral l i n e o f i n t e r e s t over one o f t h e s l i t s f o r measurement w i t h one o f two moveable PMTs mounted behind the s l i t assembly. be moved from s l i t t o s l i t i n less than 1.5 s .Wohlers e t a l . (C19, C20, C1323, C2188) described a sequential I C P emission spectrometer which could scan the e n t i r e wavelength range o f 170 t o 700 nm i n less than 1 s t o give a q u a l i t a t i v e p i c t u r e o f the sample spectrum. The exceptional scanning speed was due t o a new concept i n g r a t i n g movement d i f f e r e n t t o the conventional lead screw and sine bar d r i v e .The PMTs could New computer-control l e d I C P d i r e c t reading spectrometers were introduced by Jarrell-Ash (C73), and by Jobin Yvon (C44, C189, C195). Jobin Yvon also launched the JY 32E spark emission spectrometer (C46), which i s a d e r i v a t i v e o f the JY 48. The main features o f these instruments are considered i n Section 2.6.1.I n s t r u - mentation f o r separate sampling and e x c i t a t i o n analysis (SSEA) was described (C40 t o C43). Small amounts o f metal o r powdered samples were vaporized by a spark and transported i n t o an I C P by the A r c a r r i e r gas (see also Sections 1.2.1.2 and 3.1.4.3). (324, see also ARAAS, 1981, lJ, Ref. C723). The monochromator was a modified Czerny-Turner configuration (0.8 m f o c a l l e n g t h ) equipped w i t h an o s c i l l a t i n g quartz r e f r a c t o r p l a t e a t the entrance s l i t f o r the measurement o f d e r i v a t i v e spectra by wavelength modulation. g r a t i n g combination s i m i l a r t o t h a t o f the Spectraspan instrument series, a l - though the o p t i c a l alignment was s l i g h t l y d i f f e r e n t .A t the 1981 Pittsburgh conference an echel l e grating/prism spectrometer was introduced by Leeman Labs Inc. which used a continuous graphite b r a i d f o r sample i n t r o d u c t i o n i n t o a DCP. D e t a i l s o f a previously reported I C P echelle spectrometer were published Dispersion was achieved w i t h a prism andInstrumentation 59 An independent evaluation of this instrument was made by Gilbert e t a l .(978, C1274), and detection l i m i t s comparable t o o r b e t t e r than those of a convention- a l DCP o r ICP spectrometer were reported. also been developed (975) f o r the measurement of spectra from a r e f . boosted pulsed hollow cathode lamp (see ARAAS, 1981, 11, Ref. C17). polychromator was used f o r simultaneous mu1 ti-element analysis by ETA-AES (C270).(see Section 2.2.2), following minor a l t e r a t i o n s t o the computer software. The coup1 i ng of chromatographic separation w i t h microwave i nduced plasmas has been reported previously (see Section 1.2.2.3 and ARAAS, 1981, lJ, 22). Cerbus and Gluck (C170) described the construction and operation of two computer controlled GC-MIP instruments t h a t were used f o r the determination of chlorine and other non-metals i n pesticide residues, organometallics and chlorinated organic liquids. 1449, C2187). across small spectral i n t e r v a l s . Applied Chromatography Systems have extended the application of the MPD 850 spectrometer t o allow operation w i t h MIP and ICP sources (C69). An echelle grating spectrometer has A modified echelle Measurements were made with the SIMAAC instrument of Harnly and O'Haver Similar instruments were developed by Caruso e t a l .(C167, Both groups of workers used wavelength modulation t o scan rapidly Other references of i n t e r e s t - Development of an " i n t e l l i g e n t " spark emission spectrometer : C30. Double monochromator ICP spectrometer : 1772.Emission spectrometer f o r the determination of 15N : 1798. Patent f o r emission spectrometer w i t h f i l t e r i n g and resolving mono- chromators i n s e r i e s : 1816. Patent f o r flame photometer : 376. Patents f o r ICP Spectrometers : 1811 , 1812, 1930. Patents f o r l a s e r microanalyzer : 1934, 1935, 1936. Patent f o r low-voltage spark spectrometer : 1005.Spectrochim Acts "Instrument Column" a r t i c l e s on emission spectrometers : 1361, 1507. Spectrometer f o r measurement of ICP V . U . V . l i n e s : C238, 1223. 2.5.2 Absorption Instruments Pye Unicam continued t o promote the sophisticated PU 9000 spectrometer (C99, C103, C309) which i s the current state-of-the-art in automated atomic absorption instruments.Several patent applications were submitted f o r atomic absorption spectrometers designed f o r flame (695, 826, 904, 939) and electrothermal (902, 1057, 1172) atomization. Shimadzu patented an instrument (930) t h a t produced an intense l i n e spectrum and continuous spectrum w i t h a single l i g h t source. A potentially portable Zeeman atomic absorption spectrometer, the Sintrex AAZ-2, was described (C279).Samples were atomized by a U-shaped tungsten60 Analytical Atomic Spectroscopy filament placed between the poles of an a . c . electromagnet. be operated w i t h a portable 0.5 kW generator. spectrometer (1931) was submitted by Hitachi. performance and design features of three commercial Zeeman AA spectrometers i n a Spectrochimica Acta "Instrument Column" a r t i c l e .A previous note in this s e r i e s (438), by the same author, provided a survey of currently available AAS instrumentation. Three instruments were developed f o r the determination of Hg by cold vapour - AAS. f o r the determination of Hg i n a i r (1829), and an analyser (1058) based on the incineration/amalgamation principle of sample preparation.The instrument can A patent f o r a Zeeman flame Brockaert (552) compared the They were a non-dispersive V . U . V . spectrometer (421), a portable instrument 2.5.3 Fluorescence Instruments Additional information regarding the s u i t a b i l i t y o f inductively coupled plasma atomic fluorescence spectrometry for simultaneous mu1 tielement analysis was published by Demers e t a1 .(452, 729, 1089 see also ARAAS, 1981 , lJ, 60). Relative freedom from spectral interference e f f e c t s may be the main advantage of ICP-AFS over ICP-OES. conference presentations by Demers and col 1 eagues (C140, C1333, C2482). Attempts were made by these workers (C92) t o improve the ICP-AFS detection l i m i t f o r As, P , S and Se by the use of high i n t e n s i t y thermal gradient lamps f o r excitation.They a l s o reported (C92) the advantages of hydride generation sample intro- duction f o r As, Se and Te, and evaluated an ICP torch which had an HF-resistant aerosol tube made from glassy carbon. Improved detection of V . U . V . l i n e s of P and S was achieved by Ar flushing of the excitation and collection optics (C2482). instrumentation f o r mu1 tielement atomic fluorescence spectrometry w i t h p a r t i c u l a r emphasis on recent work w i t h ICP sources, including the use of l a s e r s f o r excitation.Although a pulsed dye l a s e r i s f a r superior t o a pulsed HCL f o r AFS, lasers a r e too expensive and too complex t o be included i n commercial instru- ments a t present. Fredeen and Bastiaans (C108) , however, indicated the advantages of l a s e r excitation f o r the determination of C1 and other non-metals i n an ICP by nonresonant AFS.was employed t o e x c i t e non-metal atoms i n a 1.5 kW Ar plasma. could be made f u r t h e r from the load-coil than i s possible f o r AES detection of C 1 , and so the influence o f the ICP background continuum on the detection l i m i t was l e s s .This point has featured as the central theme of many Winefordner (C139 , C1689) , and U1 lman (484) reviewed the development of A tunable dye l a s e r pumped w i t h an N2 l a s e r Observations Hieftje e t a l . (C200) developed an instrument f o r the measurement of sub- nanosecond atomic fluorescence 1 ifetimes. synchronously pumped dye l a s e r , extremely f a s t photodetection, and an opto- The spectrometer consisted of aTable 2.6A COMMERCIALLY AVAILABLE EMISSION SPECTROMETERS Supplier ~ ~ ~ ~ ~ _ _ _ _ _ Reciprocal Wavelength Focal dispersion/ range/ length/ Type of Model nm per mm nm m Source Special features Bausch & Lomb (UK) Ltd., 3650* 0.465 170-406 1.0 Low voltage spark, Instruments & Systems Quantovac 0.60/0.30 170-526 d.c.arc, GDL, HCL Wingate House, 0.93/0.46/0.3 1 170-81 2 Wingate Road, Luton, Bedfordshire, LU4 8PU, England Division, 0.69/0.35 170-810 Bausch & Lomb Ltd., 3580* as 3560 En Vallaire, Quantovac CH 1024, Ecublens, Lausanne, Switzerland 3600 Bausch & Lomb Ltd., 9545 Wentworth Street, PO Box 129, Sunland, California. USA 0.84 as 3560 240-450 as 3560 0.5 as 3560 Low voltage spark Baird Corporation, Spectromet 0.6 or 0.3 210-590 1 .o Arc or spark; 125 Middlesex Turnpike, 1000 190 -295 rotating disc; Bedford, MA 01730, USA modular Baird-Atomic Ltd., Spectrovac 0.6 or 0.3 173 -767 1 .o Arc or spark; Warner Drive, 1000 modular Springwood Industrial Estate, Rayne Road, Spectromobile 0.3 or 0.6 200-600 1 .o Low-voltage 3-step Braintree, Essex, MS2 d.c.arc CM7 7YL, England Baird-Europe BV, FAS 2 0.6 or 0.3 1 .o Rotrode 210-590 PO Box 737, FAS 2GT and 766.4 2501 CS The Hague, The Netherlands FAS 2C Fully computer controlled system to provide elemental concentration printout. Range of computer systems include dual cassette, floppy and hard disc and Winchester drive systems. A full range of options including VDUs, inter-computer links, remote terminals, is available.Twin stand excitation facility available allowing a choice of Ar standlair stand/GDL/Hollow Cathode/lCP/Rotrode/d.c. arc. Maximum capacity of 60 element channels measured simultaneously As 3560 with the addition of a single-channel sequential spectrometer system Transportable optical emission spectrometer system suitable for analysis of ferrous and non-ferrous alloys.Will determine up to 20 different elements simultaneously and can operate in one of four modes: instantaneous sorting/ pass-fail sorting within tolerance limits/alloy grade identification/% analysis of elements. Comprises hand held spark pistol coupled to a mobile cabinet by a 5/10 metre optical fibre cable Compact, low cost direct reader with minimum air conditioning requirements; extensive self-testing diagnostics and auxiliary testing programs to check performance of hardware functions; built-in backup in event of printer, keyboard or display problems; sample stand and excitation source selected for analytical program; CPU R6502 microprocessor; 50 channels; 130 exit slits; new system Baird Graphicomp using HP-86 computer introduced March, 1983 As Spectromet 1000; logarithmic readout; dual stand option; 50 channels Mobile spectrometer for metal sorting or checking; 24 channels Three fluid analysis spectrometers for SOAP program.No special environmental facilities required; readout ranges from 0-99.8 and 0-999.8 or 0-999.8 and 0-9998 depending on instrument; manual readout, typewriter or computer interface for most minicomputersTable 2.6A COMMERCIALLY AVAILABLE EMISSION SPECTROMETERS-conrinued Reciprocal Wavelength Focal dispersion/ ransel length/ Type of Supplier Model nm per mm nm m Source Special features Hilger Analytical Ltd., El000 0.293-1.155 156-880 1.5 Various including Direct reader, solid state electronics, microprocessor Westwood, Margate, polyvac high repetition control available.Dual gratings give 12 standard systems Kent, CT9 4JL, England condensed arc, ICP, GDL to select optimum dispersion and wavelength coverage. Special grating if required; dual spark stands and inert gas discharge stands E970 0.546 01 0.741 174.0-447.7 0.75 As El000 Curved entrance and exit slits, microprocessor control, air Jarrel-Ash Division) 78-090 1.1 or 0.54 420-970 1.5 Varisource unit Wadsworth spectrograph; 20-inch camera; choice of 3 Fisher Scientific Co., 210-485 includes: spark, gratings; N, purging extends range to 175 nm; optional 590 Lincoln Street, 70-113 1.0 or 0.2 180-3000 3.4 low and high voltage accessories permit use as direct reader or scanning Waltham, MA 02254, USA depending on 180-1500 d.c.arcs; also spectrometer grating 180-750 controlled wave excitation source Jarrel-Ash (UK) Ltd. 96-750 0.54 168-500 0.75 As above except Direct reader, computer controlled Concorde House, 96-785 0.54 168-500 0.75 electronically Concorde Street, controlled peak Luton, Bedfordshire, current LU2 OJE, England 1500 0.56 or 0.28 200-800 or 1.5 As above Choice of two gratings 190-400 0.34 or 0.17 200-510 or Labtest Equipment Co., 310 0.56 190-900 1.5 ‘Transource’ (high 11828 La Grange Ave., 190-250 voltage triggered Los Angeles, CA 90025, USA triggered d.c.arc; Labtest Equipment V25 0.46 170-428 or 1 .o ‘Transource’ (Europa) GmbH, 170-770 4030 Ratingen, 0.34 or 0.68 185-680 1 .o ‘Transource’ Til Str. 35, Ratingen, 2100 West Germany 71 0.52 170-900 1 .o ‘Transource’ discharge low voltage ICP) V82* 0.42 or 1.68 1 70- 1040 0.75 Universal source Direct reading air path spectrometer for use in non- ferrous applications; 60 channels; archpark stand Ar or N, flushed; solution stand, pin stand; CRT-1000 computer readout; IOOOB data acquisition and printout optional Direct reading vacuum spectrometer for analysis of ferrous and non ferrous alloys including C, P, S ; 48 channels; other details as for model 3 10 Direct reading air path spectrometer for non-ferrous applications; 30 channels; other details as for model 310 Low cost microprocessor controlled foundry spectro- meter for all ferrous and non-ferrous alloys; 16 channels; display or printout; readouts on CRT or teleprinter optional flexibility, autosampler, built-in VDU, possibility of photon counting, printer 120 cps Optical Emission OES4500 0.45 or 0.225 170-450 1 .o Arclspark, ICP Direct reader, additional monochromator for extra Services Ltd., 104 Tanners Drive, Blakelands, Milton Keynes, MK14 5BP, EnglandPhilips Industrie SA, PV8020/01 Spectrometry Department, 131 Boulevard de l’Europe, B-1301 Wavre, Belgium Philips Analytical Dept., PV8350 Pye-Unicam Ltd., vacuum York Street, Cambridge, CBI 2PX England PV8250 air PV8210 air Siemens AG, Spectrumat Instrumentation and lOOOA 0.46 0.46 0.69 0.59 0.92 0.46 0.55 177-410 177-410 190-6 15 190-531 190-410 190-700 190-820 0.78 Spectrumat 0.36 Analytical Section, Ostl, Rheinbriickenstr. 50, loooV West Germany Spectrumat 0.36 Control Division, lOOOHV 220-750 1 .o Monoalternance Computerized emission spectrometric system fitted with s 50 Hz spark with high energy conditions 50Hz spark; d.c.arc, GDL, HCL, or ICP 20 pre-selected lines for steel and iron program. g. 1.0 Monoalternance Integrated spectrometer system with optional dual air/Ar excitation stand; choice of programmable calculator or computer; configurations with dual cassettes or floppy discs; rapid printer, VDU extension options 1 .o As for PV8350 As for PV8350 1.5 As for PV8350 As for PV8350 1.0 Floating anode, Direct reader, microcomputer controlled, maximum of 63 GDL, spark, arc channels 150-450 1 .o As above As above; optional special channels for lines above 110-450 1.0 As above As above; special computer and software system for 450 nm surface analysis (depth profile analysis) available ~~ VEB Carl Zeiss Jena, PG5 2 0.74 or 0.37 200-2800 2.075 Arc or spark Atlas for spectra evaluation; wide choice of precision 69 Jena, Carl-Zeiss Str. 1, diffraction gratings; high resolving power; dispersion German Democratic Republic doubling or multiplying as required; automatic transport of cassette; wavelength scale for quick orientation of the user within the spectra; wide range of accessories available Carl Zeiss Scientific including LMAlO laser-microspectral analyser Instruments Ltd., PO Box 43, 2 Elstree Way, Borehamwood, Herts, WD6 lNH, England *New equipment since publication of Volume 11 t No up to date information suppliedGenerator Table 2.6B COMMERCIALLY AVAILABLE PLASMA SPECTROMETERS Supplier Reciprocal Focal output dispersion/ length/ power/ Model nm per mm m kW Operating frequency/ MHz Special features Bausch & Lomb (UK) Ltd.* 3510* 0.51 1 .o 0.90-1.5 27.12 3520* 0.93/0.46/0.31 1.0 0.90-2.0 27.12 3560* 0.93/0.46/0.31 1 .o 0.90-2.0 27.12 3580* 0.93/0.46/0.31 1.0 0.90-2.0 27.12 Completely integrated sequential instrument for routine elemental analysis and non-routine problems; Czerny- Turner optical mount with full computer control of grating scanning of selected wavelength profile High speed fully computer controlled automated liquids analysis system for precise quantitative elemental analysis or qualitative elemental survey and monitoring. Based on a new sequential scanning monochromator utilising a Paschen-Runge optical mount Direct reading spectrometer with Paschen-Runge optical mount.Full computer control to provide direct concen- tration printout.Features a full range of options including cassette system, floppy discs, hard discs, Winchesters, VDUs, fast printers, remote terminals and computer links. Up to a maximum of 60 channels can be measured simultaneously Combines all the features of the 3520 and 3560 into a single instrument Baird Corporation* Plasma/AFS 1 .o 40 Plasma 0.66 Spectromet 0.33 0.22 1 .o 2.5 or 5.0 27.12 40.68 Plasma as Spectromet as Spectromet as Spectromet Spectrovac Hilger Analytical Ltd.* El000 0.293 - 1.155 1.5 - 27.12 polyvac Multielement AFS spectrometer with plasma atom cell: offers multielement capabilities of ICP-OES with selectivity of AAS with almost no spectral or matrix interferences.Crossflow nebulizer; AI purged modules for P and S; automated continuous flow hydride generator; HF resistant torch with central carbon tube One-metre polychromator with 120 exit slits in rigid focal curve.Tektronic 4052 graphic computer controls data acquisition; optional scanning monochromator; optional remote transmission of data to CRTs, printers or other computers; automatic injection and dilution systems for analysis of viscous fluids available Vacuum ICP spectrometer with same features as Spectromet Paschen-Runge direct reading spectrometer; solid state electronics; dual gratings give 12 standard systems to select optimum dispersion and wavelength coverage; special grating if rquired; dual spark stands; micro- processor control available; crossflow or concentric glass nebulizerE970 0.546-0.741 0.75 - 27.12 Paschen-Runge direct reading spectrometer; curved entrance and exit slits; microprocessor control; crossflow or concentric glass nebulizer $ Hitachi Ltd. 8 3061 ICP 0.49 0.75 2.5 27.12 See Section 2.6.1 3 Q 3 Nissei Sangyo Co. Ltd. Instrumentation Plasma 200* Laboratory Inc., 68 Jonspin Road, Wilmington, MA 01887, USA Instrumentation Laboratory (UK) Ltd., Kelvin Close, Birchwood Science Park, Warrington, Cheshire, England Jobin Yvon, JY 38P Division d’lnstruments, 16-18 Rue du Canal, 91 160 Longjumeau, France - - 2.5 27.12 Microcomputer controlled scanning double mono- chromator for sequential multielement analysis.Instructions for programming appear on video display with a single keystroke operation; emission profiles of analytical line appear on video screen for selection of wavelength, for background correction, for study of inter- element effects and observation of spectral interferences; all circuitry for r.f.power generation, monochromator optics and microcomputer are built into the instrument; crossflow nebulizer. System available with optional vacuum monochromator for second channel. Multi-quant program allows for fast measurement of up to 87 elements in an unknown sample.Alpha-numeric printer supplied as standard; 2 data management systems available EDT Research, JY 48P 0.39 14 Trading Estate Road, London NWlO 7LU, England 0.4 (0.27) 1 .o 2.2 56 1 .o 2.2 56 Sequential operation direct reading spectrometer; Czerny- Turner monochromator, large aperture (f.5.4) grating size 120 X 140 mm; very high resolution version available; manual or computer controlled; constant time integration or in ratio mode; choice of concentric glass nubulizer, adjustable concentric nebulizer in zirconium, or ultrasonic nebulizer.Plasmatherm generators, 1.5 and 2.5 kW, are available as options Simultaneous operation air or vacuum spectrometer; 86 positions of photomultipliers; fully automatic read-out option; computer option; choice of two standard gratings (or specials if necessary), 1800 grooves/mm (wavelength range 180-590 nm, reciprocal dispersion 0.55 nm/mm) or 2500 grooves/mm (wavelength range 130-415 nm, reciprocal dispersion 0.39 nmlmm); alkali metals are determined by using interference filters; scanning entrance slit under computer control for identification of interfering spectral lines, background correction and analysis of elements not installed in the program. Paschen- Runge monochromator; choice of nebulizers as for JY 38P; Plasmatherm generators, 1.5 and 2.5 kW, are available as options; arc/spark excitation source either in addition to or in replacement of the ICP sourceTable 2.6B COMMERCIALLY AVAILABLE PLASMA SPECTROMETERS-continued Generator JY 70* Scanning 0.4 Simult. 0.55 Scanning 2.2 1 .o Simult. 0.6 56 86-731 0.45 0.75 2.5 27.12 SSEA/100 0.36 95-631 0.75 2.5 27.12 ~~ Reciprocal FOCal output Operating dispersion/ length/ power/ frequency/ Supplier Model nm per mm m kW MHz Special features JY 32P 0.55 0.6 2.2 56 Air or Ar purged simultaneous spectrometer; 50 positions of photomultipliers covering the wavelength range 170- 800 nm; full computer controlled system including background correction by scanning primary slit.Grating is 3600 groovesjmm, master holographic. Flying channel monochromator easily incorporated for elements not in the basic program. Can be combined with mono- chromator and detection system of JY 38P (see also JY 70); 52 photomultiplier positions of which any 32 can be measured simultaneously; alkali metals are determined using a second flat field polychromator; software based on a Silex microcomputer.Full range of nebulizers and torches including demountable torch as for JY 38P; Plasmatherm generators, 1.5 and 2.5 kW, are available as options; arc/spark excitation source, either in addition to or in replacement of ICP source Concurrent sequential and simultaneous spectrometer. Essentially a fully integrated combination of the JY 32 and JY 38 spectrometers with a common excitation source and a single computer to control both modes of analysis simultaneously.Overall performance details are those given for the two separate systems. Plasmatherm generators, 1.5 and 2.5 kW are available as options trademark.ICAP 9000 Solid Sampling system direct reading air spectrometer for determining up to 50 elements simultaneously. Cross-flow nebulizer of corrosion resistant polymer; quartz torch; HF resistant torch and spray chamber available ICAP solid sampling system direct reading vacuum spectrometer for elements with wavelengths below 190nm. Same as 86631 except with vacuum pump system for spectrometer elements simultaneously, ICAP and ECWS (Electronically controlled wave-form source) sampling system are housed in sample instrument. Solid sampling stand and all necessary hardware and interfaces allow solid sampling and conventional ICAP operation are provided ICAP 9000 0.45 0.75 2.5 27.12 ICAP (Inductively Coupled Argon Plasma) is Jarrel-Ash Jarrel-Ash Division* Fisher Scientific Co.Ltd. 86631 $ $ 2 6' - b Direct reading air spectrometer determines up to 61 % +2 a 995-73 1 0.36 0.75 2.5 ATOMSCAN 0.18-0.36 0.75 2.5 2000 Kontron GmbH, Plasmakon* 0.6 0.6 3.5 Postfach 8057, S35A Eching bei Miinchen, Oskar-von-Muller Str. 1, West Germany Plasmakon* 0.5 0.75 3.5 Linton Instrumentation, S35A/B Hysol, Harlow, Essex CM18 6QZ, England Labtest Equipment C O .~ Plasmascan - 0.35 2 700 27.12 27.12 27.12 Direct reading vacuum spectrometer. Same as 95631 except with vacuum pump system for spectrometer Sequential spectrometer for up to 70 elements Sequential system; scanning Czerny-Turner mono- chromator; wavelength range 170-550 nm; Kontron microcomputer KDT, CPUZSOA; printerlplotter as standard; autosampler option available 27.12 Combined sequential and simultaneous system; as S35A but including Paschen-Runge polychromator; wavelength range 200-520nm; maximum 48 channels 27.12 Czerny-Turner monochromator; microprocessor control; enclosed sample pumping system; computer read out; crossflow, concentric glass or ultrasonic nebulizer Perkin-Elmer Corp. 8 ICP 5500 U.V. 0.65 0.4 2.5 27.12 Completely automated sequential ICP system which can vis. 1.3 determine up to 80 elements in an operator-selected multi-element program; analytical parameters including wavelength selection, background correction, intervals, and signal handling are programmable via Model 3600 Data Station included in the system; optical path purgable permitting analyses to 175 nm; software permits develop- ment of analytical methods in Develop mode and operation of system in Analysis mode; five report formats are available at the choice of the operator, including reports with statistics and volume and weight correction if desired.Analytical speed up to 15 elements per min can be selected by the operator. Maximum precision of 1% relative is claimed at an analytical speed of 5 elements per min. Demountable torch using precision bore quartz tubing and alumina injectors standard.Cross-flow nebulizer made of corrosion-resistant material and corrosion resistant spray chamber are also standard Completely automated sequential ICP System which can determine up to 108 elements in an operator-selected multi-element program; analytical parameters including wavelength selection, background correction intervals, and signal handling are programmable via the Model 7500 laboratory computer included in the system; multicolour graphic display of spectral data with printout in colour on auxiliary printer included; 10 megabyte hard disc for automatic data storage and archiving simultaneous operation with a printer and graphics plotter; multiple bottle standardization; soft keys for use with page o\ 4 ICP 6000* U.V. 0.65 vis. 1.3 0.4 2.5 27.12Table 2.6B COMMERCIALLY AVAILABLE PLASMA SPECTROMETERS-continued Genera tor Reciprocal Focal output dispersion/ length/ power/ Model nm Der mm m kW Operating frequency/ MHz Swcial features orientated screen displays and multicolour screen; ability to run analyses at any wavelength without prior wavelength calibration; choice of report formats available with statistics and volume and weight corrector, if desired.Analytical speed up to 18 elements per min can be selected by the operator. Precision of approximately 1% relative is claimed at analytical speed of 5 elements per min. Demountable torch using precision bore quartz tubing in alumina injector is standard. Cross-flow nebulizer made of corrosion-resistant material and corrosion-resistant spray chamber are also standard.Philips Indutrie SAS PV8210 Air 0.55 or 0.28 1.5 2 50 Direct-reader; Paschen-Runge spectrometer; wavelength range covered in first order; remote controlled roving detector; readout by printer; teletype or digital computer systems; crossflow nebulizer; computer controlled background correction optional readout options, spectrometer and nebulizer as for PV8210; computer controlled automatic background PV8250 Air 0.69 or 0.35 1 .o 2 50 Integrated spectrometer system with built-in source and 0.59 or 0.35 0.92 or 0.46 0.46 or 0.23 correction optional PV8350 0.46 1 .o 2 50 Integrated spectrometer system including source and read Vacuum out options; spectrometer and nebulizer as for PV8210; computer controlled automatic background correction optional - Spectra Metrics Inc., Spectra Span 0.06 (200nm) 0.75 - d.c.Single channel module, sequential operation with 204 Andover Street, IV 0.27 (800nm) background correction facility. High sensitivity with d.c. Andover, MA 01810, USA matrices plasma and echelle spectrometer, even in refractory ; $+ 2 Beckman-R1lC Ltd., Spectra Span as IV as IV - d.c.Optimized AE system using a high dispersion, high energy Sands Industrial Estate plasma source. Computer controlled with background b Progress Road, V DCP* throughput echelle spectrometer; high temperature d.c. k High Wycombe, Bucks., HP12 4JL, England operation correction facility. Modular and expandable simultaneous %. Spectra Span as IV Optimized AE system using a high dispersion, high energy r, v ICP* throughput echelle spectrometer; ICP source.Computer controlled with background correction facility. Modular f and expandable simultaneous operation 5 0 Q k! as IV 1.5 to 5.0 27.12Spectra Span as IV as IV Vl* d.c. Computer controlled rapid scanning echelle spectrometer coupled with d.c. plasma source. Floppy disc data acquisition system Spex Industries Inc., 1870 1.6 1.1 3880 Park Avenue, Metuchen, NJ 08840, I7O2 USA 1704 0.8 Glen Creston 1269 0.65 Instruments Ltd., 16 Dalston Gardens, Stanmore, Middlesex, HA7 lDA, England 0.5 0.75 1 .o 1.26 - - - - Plasmatherm 27.1 2 Czerny-Turner spectrograph/monochromator as above Slew-scan monochromator as above As 1702 as above High-Resolution slew-scan monochromator * New equipment since publication of Volume 11 Address as in Table 2.6A 5 Address as in Table 2.6C 69Table 2.6C COMMERCIALLY AVAILABLE ATOMIC ABSORPTION SPECTROMETERS Model Resolution/ Type of data Supplier single/double nm wtput Special features Baird Corporation$ Alpha 1 (single) 0.1 Bit parallel BCD (TTL levels) Single lamp turret; fail/safe gas safety; digital concentration readout As Alpha 1 plus 4-position lamp turret As Alpha 1 plus automatic D, HCL background correction and 2-speed wavelength scanning As Alpha 3 plus 4-position lamp turret Colour or monochrome video display, unlimited curve and report storage on floppy disc; printer option GBC Scientific Equipment Pty.Ltd., GBC SB900 (single) 0.5 IEEE-488 2 lamp supply; optional background correction; hydride 1/63 Park Drive, generator and calculator available; length 700 mm, width Dandenong, Victoria 3 175 200 mm, height 225 mm Australia emission; peak height; absorption expansion to 30 times, direct concentration readout.Ti burner, safe burnerlgas system; 2 lamp supply; 3 point curve control; background correction; graphite furnace and hydride generator available correction; integration; programmable calculator; printer available Hitachi Ltd., 180-30 (single) 1.2 4-lamp turret; water cooled premix burner; air/C,H, or Nissei Sangyo Co.Ltd., N,O/C,H, selection by synchronized valve system, (C,H, Mori 17th Building, automatically increased when using N,O); AA with D, 26-5 Toranomon l-chome, arc background correction and emission: measurement, Minato-ku, Tokyo 105, direct, integration (0.5-16 s continuously variable); Japan absorbance linear.Meter display. GA-2B graphite analyser b available, auto-measuring system, As and Hg analyser available 4-lamp turret; water cooled premix burner, air/C,H, or N,O/C,H, selection by synchronized valve system, (C,H, automatically increased when using N,O); AA with D, arc background correction and emission; measurement, direct integration, peak height, peak area, absorbance and concentration; auto zero; CRT, LED and printer display: microcomputer; GA3 graphite analyser available; automeasuring system; As and Hg analyser available analytical modes Baird-Atomic Ltd.Alpha 2 Alpha 3 Alpha 4 Alpha Computer Systems GBC 901 (single) 0.1 IEEE-488 2 integration times, all reflective optical system; flame EDT Research, 14 Trading Estate Road, London NWlO 7LU, England - Hilger Analytical Ltd.Atomspek H1580 0.2 6-lamp turret: autozero and flame ignition; curve (single) - s Q a, Nissei Sangyo America Ltd., 460E Middlefield Road, Mountain View, CA 94043, USA 2. 5 3. ? - 2 8 180-60 (double) 1.2 Polarized Zeeman atomic absorption and flame emission s -u k! 180-50 (single) 1.2180-80 (single) 551 (single) 0.04 951 (double; dual channel) 0.04 2 2 180-70 (double) 1.2 - Polarized Zeeman AA graphite furnace and emission; i! 7 steps and ramp, temp.range 0-3000°C; measurement, direct, peak height, peak area; integration, conventional flame burner without Zeeman effect Fully equipped instrument incorporating Zeeman AA graphite furnace and Zeeman flame system; furnace programmable, 7 steps and ramp; temp.range 0-3000°C; measurement, direct, peak height, peak area; integration Video terminal on all models; complete data processing; computer assures precise control of selected operating parameters; auto process As analyser available, Hg analyser available using 2 standards. Fully automatic gas box is standard feature: optional D, arc background correction, optional 4-lamp turret and wavelength scan 5 9 Nissei Sangyo GmbH (Deutschland), Ross-strasse 74, 4000 Dusseldorf 30, West Germany 6’ Nissei Sangyo Co.Ltd., London Road, Sutton Industrial Park, Reading, Berks. RG6 lAZ, England Instrumentation Laboratory Inc. 5 15 7 (single) 0.04 - Microcomputer controlled; calibration curve linearized 357 (single) 0.04 RS 232C As for 457 451 (single) 0.04 RS 232C As for 551; CRT video readout; D, arc background correction 457 (double) 0.04 RS 232C Microcomputer controlled; calibration curve linearized using up to 5 standards: provides full statistics on results: fully automatic gas box is standard feature; optional D, background correction: 4 lamp turret, wavelength scan and alphanumeric printer Microcomputer controlled; calibration curve linearized using up to 5 standards; memory will store up to 10 calibration curves simultaneously: VDU displays standard conditions for each element, the working curve and will show transient signals; fully automated-safe gas box is standard feature; optional background correction, 4-lamp turret, wavelength scan and alphanumeric printer Microcomputer controlled; calibration curve linearized in both channels using up to 5 standards; CRT video readout will display 2 elements simultaneously, A, B, A/B or A-B; internal standard and non-absorbmg line background correction: VDU displays standard signals; automatic gasbox is standard feature: optional 4-lamp turret: wavelength scan and built in alphanumeric printer RS 232C RS 232CTable 2.6C COMMERCIALLY AVAILABLE ATOMIC ABSORPTION SPECTROMETERS -continued 4 t4 2380 (double) 0.2 4000 (double) 0.3 EIA-RS 232C 2 way EIA-RS 232C 5000 (double) 0.3 2 way EIA-RS 232C Type of data RS 232C Model Resolution/ Video 22* 0.04 Special features Microcomputer controlled; calibration curve linearized in both channels using up to 5 standards and blank; CRT video readout wiU display 2 elements simultaneously (A, B), provides capability of internal standard operation (A/B) and non-absorbing line background correction (A/B); VDW provides graphic display of transient peaks and calibration curves.Standard features include the new Smith-Hieftje background correction system, a fully automated gas box and storage of 10 pairs of calibration curves together with cookbook conditions for flame and furnace operation.Options include a 4-lamp turret, wavelength scan and built in alphanumeric printer Supplier single/dwble nm output Perkin-Elmer, 2280 (single) 0.2 EIA-RS 232C High energy optical system, microprocessor controlled; Spectroscopy Division, autozero, autoconcn; autocurve with up to 3 standards; 901 Ethan Allen Highway, peak height; peak area; integration selectable from 0.2 to Ridgefield, CT 06877 60 s; statistics;flameignition optional; auto N,O switching USA and burner head safety interlocks; optional flame and pressure sensing by microcomputer.D, arc background correction optional As Model 2280 but all mirror optics; automatic gain control; auto N,O switching; burner head safety interlocks; D, arc background correction optional Semi-automated sequential AA system; automatic gain control; instrument can analyse up to 6 elements with little operator participation; analytical parameters including standardization and signal readout can be entered and stored internally; digital stepper motor wavelength selection; flame ignition, auto N,O switchover, burner head interlocks; optional flame and pressure sensing by microcomputer, burner control; optional double beam background correction for all U.V.and visible wavelengths with automatic intensity control; lamp turret available Completely automated sequential AA system; instrument can analyse up to 6 elements with minimum operator participation; all parameters including lamp current, resolution, gas flows, standardization and signal readout can be entered and stored using magnetic cards; optional double beam background correction for all U.V. and risible wavelengths; when used in conjunction with HGASOO it will provide sequential analysis for up to 6 elements with the same analytical ease as flame; when used with ICP- element analysis for up to 20 elements with operator selected background parameters Bodenseewerk Perkin-Elmer & Co.GmbH, Postfach 1120, D7770 Uberlingen West Germany Perkin-Elmer Ltd., Post Office Lane, Beaconsfield, Bucks. HPO lQH, England 3 % 3 fi’ emission accessory it will provide sequential multi- I? s 2 23030 (double) 0.07 2 way EIA-RS 232C SP9 computer RS 232C PU9090 PU9000 0.2 2 way RS 232C ..* 2 Zeeman 5000 (double) 0.3 2 way EIA-RS 232C Flame operation both with and without background $ correction as for Model 5000.The instrument can be equipped simultaneously for Zeeman-corrected graphite 5. furnace AA. 0 Contains built in CRT, software inoluding all cookbook ’ information; optional graphics display facilities instrument set-up; grapics are available for flame, furnace or MHS system and may be printed on an external printer.Exclusive soft keys change function as operator steps through a program facilitating instrument set up. 4-lamp turret standard, double beam background correction available; interlocked gas control system available. Automatic calibration with up to 8 standards built in; integration time selectable from 0.2 to 99 s.Operator may select averaging and RSD if desired. Software resident on floppy disc for easy updating and available in five languages. Quick change mount available for flame to graphite furnace auto-gas control module with full safety interlocks; scale expansion; 2-standard curvature correction; burner interlock; output for SP9 computer and PU9090 Data graphic system and 0-IOmV (0-1 A) analog output as standard Microprocessor data processing and control of flame automatic system for SP9.Curve correction with 5 standards in fixed and variable ratios. Peak height and/or peak area full statistics, running mean, error warnings, built-in self test routines. Integration and peak read times 0.1-100s As SP9 computer, with PU9095 video display of flame and furnace cookbook calibration curves and transient peak profiles with automatic scaling.Printout of furnace parameters Fully automatic, multi-element microprocessor controlled AA system. Capable of selecting and then optimizing appropriate instrumental conditions for each element and mode of operation. Electronically coded HCLs allow the instrument to detect element and maximize current. Novel double-beam system eliminates SNR degradation of coventional double-beam systems.A double-beam reference channel checks and corrects the base line prior to each measurement. The double-beam optics are then automatically switched out of the beam during the measurement period itself. Master holographic grating. Pye-Unicam Ltd., SP9 (single) 0.2 - 8 modules available with combinations of 4-lamp turret; York Street, Cambridge CBI 2PX England 4 w4 P Table 2.6C COMMERCIALLY AVAILABLE ATOMIC ABSORPTION SPECTROMETERS-continued PU9007 AA data/ - control system Resolution/ Type of data Supplier single/double nm output Special features Model The intelligent system will select and set-up wavelength, band pass, lamp current, flame type, gas flow and read time for each element and sample.All of this information is contained in the memory system and the operator is not required to program the instrument. The conditions are then modified, e.g., alternative wavelength selected automatically in response to the sample signal. Gas control is via a binary flow switching system with feedback of absorbance signal to set automatically the optimum fuel flow. The instrument detects the presence of the burner or furnace and switches programs auto- matically.Up to 8 elements are sequenced automatically for flame and furnace analysis; a flame auto-sampler is built into the instrument. A universal burner is used for all flames. Built-in printer, 4 controllable formats for multi-element reports, prints out full conditions programs, error messages and provides hard copy of the video display, including graphics from the PU 9007 AA datalcontrol station.Automatic control of programs from PU9095 in multi-element furnace analysis Interfaces with the PU9000 microcomputer system with 12-in. video display. QWERTY keyboard and twin floppy disc drives. High resolution graphics, user programming in all common high level languages.Comprehensive software package for flame and furnace work. Menu driven selection of all parameters for multi-element analysis runs. Total control of the PU9000. Video display of graphics including transient peaks, calibration curves, and ash/ atomize curves. Comprehensive post-run result computing and formatting. Floppy disc storage of all programs and data.Any video display including graphics may be dumped on the PU9000 printer 26 kg; tungsten ribbon furnace, fast rise atomization temp. 800-2500°C; minature off-axis Ebert-type monochromator, wavelength range 180-400 nm, optional monochromators up to 800 nm available; digital readout; oscilloscope output and trigger signal (BNC) provided for direct observation of signal; BCD and computer output; interface for Apple I1 Microcomputer Scintrex, AAZ-2* (single) 4.3 - Portable Zeeman modulated AA spectrometer weighing $ ? $ 2 222 Snidercroft Rd., Concord, Ont., Canada L4K IB5 2, Techmation Ltd., 58 Edgware Way, Edgware, Middlesex HA8 8JP, England Shinjuku Mitsui Bldg., 1-1 Nishi Shinjuku 2-chome, Shimadzu Corporation, AA630 (single) 0.19 Analog (100 mV) AA/flame emission spectrometer; dual HCL; scanning 2 capability, security system for flame and pressure monitor; built in pressure regulator 0 -u \Tokyo 160, Japan Shimadzu Europa GmbH, Ackerstr. 11 1, 4000 Dusseldorf, West Germany V.A. Howe & Co. Ltd., 12-14 St. Anne’s Crescent, London SW18 ZLS, England Varian-Techtron Pty. Ltd., 679/701 Springvale Road, Mulgrave, Vic. 3170, Australia Varian Associates Ltd., 28 Manor Road, Walton-on-Thames Surrey KT12 ZQF, Eneland AA646* (single) 0.19 - AA/flame emission spectrometer with D, background correction; microcomputer; dual HCL; scanning capacity, full security interlock gas box; RSD calculation; auto- sensitivity drift correction; built in pressure regulator; three point calibration.Graphite furnace GFA3, As and Hg analysers and autosamplers available Varian Associates Ltd., Genesis Centre, Birchwood Science Park South, Birchwood, Warrington, Cheshire, WA3 7BM, England Varian Instruments Div., 81 1 Hansen Way, Pal0 Alto, CA 94303.USA AA127S (single) 0.2 1EEE-488, RS 232C and 2-lamp turret; overcoated reflected optics; automatic gas parallel BCD control system, compatible with samplers; printer; hydride generator and furnace atomization systems available; Intel 8080 with 10K ROM provides signal processing; background correction absorbance conversion, integration; 3 standard curve fitting; peak height, peak area measurement, lamp current control, D, arc background correction; integrated high sensitivity atomization system AA147S (double) AA875 (double) AA97S (double) 0.2 0.05 0.2 As for AA1275 but double beam Computer compatible via two-way RS 232C for real time signal acquisition, comprehensive report generation and instrument control; integrated high sensitivity atomization system. 4-lamp turret; compatible with desk top computer, printer, samplers, hydride and furnace systems. Intel 8080 with 15K ROM provides double beam background correction, absorbance conversion; integration; 5-standard curve-fitting; peak height and peak area measurement; statistics; self test and error detection IEEE-488, RS 232C and parallel BCD IEEE-488 Stores up to 100 sets of operating parameters on in-built floppy disc.Provides capability for automatic sequential analysis of up to 12 elements by AA or emission using the compatible PSC 55 flame sample changer or the GTA-95 furnace and sample dispenser.Optics are all reflective and hard-dielectric coated; 12-lamp turret; real time signal and result processing by an 8-bit microprocessor with 24K memory which also controls lamp supplies, turret, photo- multiplier supply, monochromator, floppy disc and the data base. Four modes of integration; operator controlled single reading; accessory controlled multiple reading; automatic continuous reading; operator controlled running mean.Peak detector measures peak height and area in absorbance, concentration and emission. Direct concentration readout using a blank and 3 standards; curve fitting by rational function algorithm. Calibration reslope; fully programmable gas controlTable 2.6C COMMERCIALLY AVAILABLE ATOMIC ABSORPTION SPECTROMETERS-continued Supplier VEB Carl Zeiss h a , 69, Jena,Carl-Zeiss Str. 1, German Democratic Republic Carl Zeiss Scientific Instruments Ltd., PO Box 43, 2 Elstree Way, Borehamwood, Herts., WD6 INH, England Type of data Model Resolution/ single/double nm output AASlN (single) - 100 mV (600 ohms) for (N,O equipment) potentiometric recorder and absorbance converter.TEC 1 printer or computer, VIDTEC 1 ; signal output 775 mV (5 kohms) for linear recording of absorbance AAS3 * (double or single) 0-10 V, lOOohms 0-2.5 V, 750 ohms Special features 4-lamp turret; single or triple pass optics; autozero; titanium burner heads flow lines for air, C,H,, N,O;gas pressure monitor; gas flow monitor; burner head safety interlock; automatic flame ignition Microcomputer; double-single beam, both with or without uv-vis background correction; “background only” mode; automatic calibration by a blank solution and up to 9 standards; automatic standard additions, calibration from 1 to 5 addition standards; built in video display and printer; gas control system with automatic flame ignition and burner head interlock; flow lines for air, C,H,, C,H, and N,O; variable nebulizer rates * New equipment since publication of Volume 11 *Address as in Table 2.6A §Address as in Table 2.68 bTable 2.6D COMMERCIALLY AVAILABLE ELECTROTHERMAL ATOMIZERS AND AUTOSAMPLERS Ramp rate range Special features Supplier Model TYPe Control unit Baird Corporation$ A170 Graphite rod Programmable, dry, ash - Fits most AA spectrometers; air cooled; uses mains (2 stages) atomize, max.temp. 3500°C power; inert gas shielding; pyrolytic graphite coating for rods in situ; rapid interchange between flame and electro- thermal methods GBC Scienti IC Equipment GF900 Graphite furnace 4 temperature cycles (dry, - Continuous digital temperature read-out to 3000°C; ash 1, ash 2, atomize); temp. water, gas and electrical safety interlocks; automatic ramp capabilities on each cycle switch off of inert gas or H,; H, shielding available at push of a button; push buttom program advance accelerates proper cycle for cleaning or aborting run Pty.Ltd.f: Hilger Analytical Ltd.$ H1475 Graphite furnace Programmable, dry, ash, wait, - Current stabilized Hitachi Ltd.? GAZB Tube or cup Programmable, end-point up to 7 steps Manual program change.Applicable to Hitachi Models atomize, max. temp. 2600°C temp., time. Dry up to 300°C (1 80 s), ash up to 2000°C (120 s), atomize up to 2800°C (30 s) Programmable, max. temp. 3000"C, time 0-99 s ,80-30, 170-10/30/50A; Measuring modes, direct, peak-hold up to 7 steps Write into CRT Screen via keyboard program change; measuring modes direct peakhold, peak area.Applicable to Models 180-50,170-40 volume; automatic stop on detection of gas or water - - Up to 31 samples: 10, 20, 30, 40,pl sample injection GA3 Tube or cup Autosampler for graphite atomizer pressure drop or abnormal furnace temperature interlock system; automatic cell door; automatic cleaning; cell pressurization; solid sampling capacity using Instrumentation 655 Graphite furnace Programmable, 6 stages, ramp - True on temperature read-out; LED display; safety Laboratory Inc. 8 or step for autozeroing and autocalibrating the spectro- meter microboats 254 Autosampler for Digital timers for sample - flame or furnace operation for autozeroing and auto- deposition, trigger circuitry calibrating the spectrometer Flame/furnace autosampling technique (FASTAC) with autocalibration employs an aerosol deposition technique of introducing aerosol into cuvette which is at elevated temperature; the sample volume, which evaporates on contact with graphite surface is controlled by length of time; sample is sprayed into furnace allowing operator to control sensitivity by varying deposition time 1-99 s.Table 2.6D COMMERICALLY AVAILABLE ELECTROTHERMAL ATOMIZERS AND AUTOSAMPLERS-continued Special features Supplier Model Type Control unit Ramp rate range Perkin-Elmer C0rp.z HGA400 Graphite furnace Microprocessor unit provides From 2O0O0C/s to High speed temperature accessory permits rapid heating up to 8 steps of controlled heating; temp., ramp time, 2 temps atomization hold time, gas and other furnace and spectrometer control functions are programmed by direct keyboard entry; digital displays provide readout of temp., time, and prog.status 999 between any to temperature between 800 and 3000°C for optimum Autosampler - A540 - _ _ _ _ _ ~ Pye-Unicam L t d J HGASOO Graphite furnace Microprocessor unit provides As for HGA400 up to 9 steps of controlled heating; temp., ramp time, gas and other furnace and spectrometer control functions are programmed for each step by direct keyboard entry; digital displays provide readout of temp., time, and prog.status; up to 6 progs. can be stored and recalled at the touch of one key PU9095 video Graphite furnace Microprocessor control of 6 18 ramp rates, 9 furnace SP9 furnace phases and ramps to 3000°C. Voltage or temp. control, no adjustment of photodiode sensor necessary linear 2-20OO0C/s and 9 exponential Graphite furnace 4 phases, each programmable to 9 ramp rates 3000°C.Voltage or temperature 2-20OO0C/s controlino adjustment of photod ode sensor necessary Automatic insertion of up to 35 samples and blank and 35 standards into the furnace; will also perform automatic methods of addition; automatic matrix modification; recalibration; automatic triggering of furnace and instrument read cycle for unattended operation Furnace controls programs for up to 6 different elements may be stored in 6 program memories; program param- eters for more than 6 elements may be stored on magnetic cards and recalled at the touch of one button; the optical temperature sensor and digital gas !low control for 2 different purge gases add versatility; when used with the A540 microcomputer furnace autosampler and the Model 5000 AA, up to 35 samples, blank and 3 standards may be analysed for up to 6 elements each without operator attention.Accommodates the new Totally Pyrolytic Cuvette (TPC) in addition to conventional electrographite and pyrolytically coated cuvettes. Microprocessor selection and control of all functions including built-in autosampler controls, video displays of parameters and status.Non- violate storage of 10 programs. Gas stop and recorder control on all phases. Video display of peak shapes calibration and cookbook conditions when used with PU9090 Data Graphics System: fits all current Pye- Unicam spectrometers Accommodates the new TFT in addition to conventional electrographite and pyrolytically coated cuvettes, digital parameter selection, comprehensive status indication.Fits all Pye-Unicam spectrometers $ 2 33 - 3 3" 3 3 3 SP9 furnace autosampler Automatic takes 38 samples and 2 wash portions, selectable number of readings and volume for each sample; positive identification of blanks, standards and samples atomize; max.temp. 3000°C 20-3O0O0C, up to 20 temp. steps. Programmable heating rate to 20OO0C/s. Heat injection from 40-150°C 3 Shimadzu-Seisakushot GFAZ Graphite furnace Programmable, dry, ash, - Current stabilized Varian-Techtron Pty. Ltd.? GTA95 Graphite tube Programmable, temp. range 0-20OO0C/s Designed primarily for Varian 75 series spectrometers. furnace Graphite tube isolated in enclosed cell.VDU gives tables for programming graphical displays of temperature/time profile with automatic ranging and instantaneous numerical display. Operator can select the number of steps displayed. Analytical signal superimposes on temperature profile. Optional programmable sample dispenser provides blank, 5 standards, 45 samples and chemical modifier.Programmable volume from 2-70 r l in 1 pl steps; 4 solutions can be dispensed together. Up to 99 multiple injections before atomization; up to 99 replicates on each sample determinations. Sampler has 5 standard and 67 sample positions. Keyboard allows program to be loaded directly into the sample changer. Interfaces with all current Varian AA spectrometers - PSC55 Sample changer - Microprocessor controlled autosampler for flame t Address as in Table 2.6C Address as in Table 2.6A $Address as in Table 2.6B80 Analytical Atomic Spectroscopy e l e c t r o n i c cross-correlation signal processing u n i t (see ARAAS, 1981 , lJ, 55).The equipment was used t o study the time-resolved fluorescence o f Na i n He and A r M I P S sustained by a Beenakker TMOIO c a v i t y .the determination o f As, B i , Sb and Se f o l l o w i n g hydride generation. l i m i t s were found t o be about 10-times b e t t e r than equivalent AA hydride methods (see Section 1.5). A non-dispersive atomic fluorescence spectrometer was constructed (1 506) f o r Detection 2.6 NEW COMMERCIAL INSTRUMENTS The accompanying tables describe the current commercially available instrumen- t a t i o n , detai 1s having been supplied by manufacturers o r t h e i r UK and European agents.The most s i g n i f i c a n t developments are summarized below and where they have been described a t s c i e n t i f i c meetings, d e t a i l s w i l l be found i n Section 2.5. 2.6.1 Emission Spectrometers Applied Research Laboratories Ltd., now t r a d i n g under the name o f t h e i r parent company, Bausch and Lomb (UK) Ltd., have introduced a new numbering system.The 3560 Quantovac i s o f s i m i l a r s p e c i f i c a t i o n t o the previous simultaneous instrument, the 3400 Quantovac, as i s the 3580 which has the added f a c i l i t y o f a s i n g l e sequential spectrometer system. spectrometers i s offered. The 3510, a f u l l y integrated lower priced sequential instrument f o r r o u t i n e and non-routine use has a Czerny-Turner o p t i c a l mount which allows computer c o n t r o l l e d scanning o f the selected wavelength p r o f i l e .The 3520, a high-speed computer c o n t r o l l e d instrument f o r automated analysis o f l i q u i d s , i s based on a new sequential scanning monochromator which has a Paschen-Runge o p t i c a l mount.Rank H i l g e r Ltd. have changed t h e i r name t o H i l g e r Analytical, but w i l l continue t o o f f e r the same range o f instruments as a t present . The JY 70 from Jobin Yvon i s e s s e n t i a l l y a f u l l y integrated combination o f the JY 32 and JY 38 spectrometers, w i t h a common e x c i t a t i o n source and s i n g l e computer control f o r concurrent use o f sequential and simultaneous modes o f analysis. Jobin Yvon have also introduced the JY 32E which i s a d e r i v a t i v e o f the JY 48.o f sparks f i r s t t o melt and then vaporize the sample f o r e x c i t a t i o n . Improved spectral e f f i c i e n c y i n the f a r U.V. region i s achieved w i t h high luminosity holographic gratings. available from Labtest Equipment Co. Ltd. The V82 i s a 16-channel instrument intended f o r the analysis o f ferrous and non-ferrous a l l o y s . A new model from Jarrell-Ash, the ICAP 9000, i s a d i r e c t reading spectrometer t h a t incorporates i n t e r a c t i v e programming and on-line diagnostics f o r ease o f operation. A completely new range o f plasma The spark generator o f the new instrument creates a double series A new low-cost microprocessor c o n t r o l l e d spectrometer i sInstrumentation 81 Hitachi have introduced the 306 I C P i n Japan. It i s hoped t h a t the i n s t r u - ment, based on a r a p i d scanning double monochromator, w i l l be introduced t o the European market l a t e r i n 1983. Instrumentation Laboratory Inc. are replacing the Plasma 100 w i t h the new Plasma 200 which has a "multi-quant" programme f o r the r a p i d measurement o f up t o 87 elements i n an unknown sample. Kontron GmbH have introduced the Plasmakon S35A, a sequential jnstrument w i t h microcomputer i n t e r a c t i v e programming, c r y s t a l control l e d 3.5 kW generator and mass-flow con- t r o l l e r s on a l l three gases. simultaneous system, has a maximum o f f o r t y e i g h t channels and the same features. The Perkin-Elmer I C P 6000, introduced a t the Pittsburgh Conference, i s an auto- mated sequential system f o r the determination o f up t o 108 elements. The Model 7500 laboratory computer, included i n the system,gives a multi-colour graphic display o f spectral data w i t h p r i n t o u t i n colour. archiving are among the many options available. elements per minute can be selected by the operator, and 1% precision i s obtainable a t an a n a l y t i c a l speed o f 5 elements per minute. The Spectraspan V DCP i s a sequential instrument w i t h DCP, computer c o n t r o l l e d and capable o f modular and expandable simultaneous operation. The SpectraSpan V I C P i s a s i m i l a r instrument w i t h I C P source,and both have high energy through- p u t echelle spectrometers. scanning echelle spectrometer coupled w i t h a DCP. Baird Corporation introduced, a t the Pittsburgh Conference, a new readout system c a l l e d the Baird Graphicomp, combining a Hewlett-Packard HP-86 computer w i t h Baird m u l t i - m a t r i x spectrochem- i c a l software f o r a wide range o f a n a l y t i c a l applications. An Automatic In- j e c t i o n and D i l u t i o n System (AIDS) f o r I C P analysis o f viscous f l u i d s was also introduced, enabling the Baird Spectromet t o analyse 60 elements i n 80 samples per hour. The Plasmakon S35A/B, a combined sequential/ Automatic data storage and An a n a l y t i c a l speed o f 18 SpectraMetrics , now a subsidiary o f Beckman Ltd. , have three new instruments. The Spectraspan V I i s a computer c o n t r o l l e d r a p i d 2.6.2 Absorption Spectrometers The Video 22 introduced by Instrumentation Laboratory has the new Smith-Hieftje background correction system (see Section 2.2.1), and the CRT video w i l l display two elements simultaneously. Both the Pye-Unicam PU 9095 and SP9 graphite furnaces accommodate the new T o t a l l y P y r o l y t i c Cuvette (TPC) i n a d d i t i o n t o conventional cuvettes. The Shimadzu AA646 i s a single-beam microcomputer- c o n t r o l l e d instrument f o r AA o r flame emission, w i t h D2 background correction and available w i t h graphite furnace, As and Hg accessories and autosampler. new microcomputer-controlled instrument from VEB Carl Zeiss Jena, the AAS 3, i s a double/single beam spectrometer w i t h u.v./visible background correction, b u i l t - i n video display and novel i n t e r l o c k s . A82 Analytical Atomic Spectroscopy 2.6.3 F1 uorescence Spectrometers Baird Corporation introduced three new advances t o extend the capabilities of the Plasma/AFS. the simultaneous determination of hydride and non-hydride forming elements. Argon purged detection modules f o r P and S extend the number of elements routinely analysed t o 67 (no vacuum system i s required). i s available f o r emission plasma systems with a replaceable central carbon tube. A completely automated continuous flow hydride generator permits A HF r e s i s t a n t torch