University of North Florida
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Stuart Chalk, Ph.D.
Department of Chemistry
University of North Florida
Phone: 1-904-620-1938
Fax: 1-904-620-3535
Email: schalk@unf.edu
Website: @unf

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Manganese

  • IUPAC Name: manganese
  • Molecular Formula: Mn
  • CAS Registry Number: 7439-96-5
  • InChI: InChI=1S/Mn
  • InChI Key: PWHULOQIROXLJO-UHFFFAOYSA-N

@ ChemSpider@ NIST@ PubChem

Citations 154

"Metals Determination In Wines By Sequential Injection Analysis With Flame Atomic Absorption Spectrometry"
Am. J. Enol. Vitic. 2000 Volume 51, Issue 2 Pages 131-136
Rui Cerdeira C. Costa, M. Isabel Cardoso, and Alberto N. Araújo

Abstract: This paper describes the application of sequential injection analysis with flame atomic absorption spectrophotometric detection (SIA/FAAS) for the determination of Zn, Mn, Fe, and Cu in Portuguese Verde, Maduro, and Porto wines. The basic configuration of the system allowed the determination of Zn, Mn, Fe, and Cu, the latter in concentrations higher than 0.20 mg/L. Selecting a sample volume of 340 µL allowed the determination of Zn and Mn up to 1.50 and 3.00 mg/L, respectively. The Fe determination was accomplished using 85, 120, and 340 µL sample volumes for Fe contents in the range of 1.50 to 15.00 mg/L, 0.50 - 10.00 mg/L, and 0.25 - 5.00 mg/L, respectively. Wine samples with Cu contents in the 0.20 to 2.00 mg/L range were analyzed with a sample volume of 750 µL. The determination of Cu trace levels was carried out using an heterogeneous-phase pre-concentration unit composed of a commercial cartridge packed with silica C18 coupled to the system. Cu was retained as diethylammonium-N,N-diethyldithiocarbamate chelate. Using about 2 mL of sample allowed determination of Cu between 0.05 and 0.50 mg/L. A comparison of the results obtained by the proposed methodologies and the reference procedures presented relative deviations less than 5%. Repeatability of determinations was always better than 3% (RSD).
Wine Spectrophotometry Sequential injection C18 Method comparison

"Solid-phase Sodium Bismuthate As An Oxidant In Flow Injection Analysis: Determination Of Manganese In Effluent Streams"
Anal. Chim. Acta 2000 Volume 413, Issue 1-2 Pages 57-61
K. Kargosha and M. Noroozifar

Abstract: An alternative procedure for the flow injection spectrophotometric determination of manganese(II) using a solid-phase reactor is presented. Solid sodium bismuthate (50% m/m suspended on silica gel beads) is packed in a polyethylene column, which is then incorporated in a single-line flow system so that reagent dissolution is affected as the sample passes through the column. Mn2+ in samples injected into a carrier stream were oxidized by solid sodium bismuthate to form MnO4- which were detected spectrophotometrically at 526 nm. The linear range of the system is 1-20 mg L-1 with a 3s detection limit of 0.38 mg L-1. The proposed system is suitable for determination of manganese(II) in effluent streams with a relative standard deviation <1.35%.
Industrial Spectrophotometry Solid phase reagent

"Monosegmented Flow System Exploiting Multicommutation Applied To Spectrophotometric Determination Of Manganese In Soybean Digests"
Anal. Chim. Acta 1999 Volume 386, Issue 1-2 Pages 129-135
Marisa Smiderle, Boaventura F. Reis and F&aacute;bio R. P. Rocha

Abstract: A flow system combining binary sampling and monosegmented flow implemented by multicommutation was developed to improve sensitivity and sampling rate of spectrophotometric methods based on slow chemical reactions. The flow network was assembled from a set of computer controlled three-way solenoid valves. The spectrophotometric method was based on manganese (II) oxidation by periodate in phosphoric acid medium to form the permanganate anion. The reaction is relatively slow and at 47degC a sample residence time of ~5 min is necessary to attain equilibrium conditions. However, by exploiting binary sampling and monosegmented flow analysis, quantitative conversion with a sampling rate of 50 determinations per hour was achieved. The procedure was applied to Mn determination in soybean digests, showing as profitable features a linear response for sample concentrations ranging from 2.50 to 40.00 mg L-1 Mn2+, a relative standard deviation of 0.27% (n=9) for a sample solution containing 17.1 mg L-1 Mn2+, a low reagent consumption (30 mg NaIO4 per determination) and a detection limit of 1.2 mg L-1 (99.7% confidence level). Results agreed with those obtained by inductively coupled argon plasma atomic emission spectrometry at 95% confidence level.
Vegetable Sample preparation Spectrophotometry Multicommutation Computer Valve Method comparison Heated reaction Segmented flow

"Method Development For Measurement Of Elements In Hungarian Red Wines By Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES)"
Acta Aliment. 2000 Volume 29, Issue 2 Pages 105-122
Csiktusn&aacute;di-Kiss, G. A., Keszler, &Aacute;., Candeaias, M., Bronze, M. R., Boas, L. V., Spaugner, I.

Abstract: ICP-OES (inductively coupled plasma optical emission spectrometry) was used to determine the element content of red wines. Development of the method involves various procedures of sample handling as well as repeatability and reproducibility measurements. Measurements were made for the following 16 elements: Al, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, P, Sr and Zn. The relative standard deviation of repeatability ranged from 0.41% (potassium) to 27% (cadmium) and that of reproducibility varied between 0.73% (boron) to 52% (cobalt). Recovery of the elements was determined by standard addition with results ranging from 90.6% (phosphorus) to 116.2% (boron). After that, 15 red wine samples were measured. Significant differences were found in the Al, B, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, P, Sr and Zn (P<0.001) concentration of wine samples. Correlation studies revealed parallel changes in phosphorus-potassium, phosphorus-magnesium and zinc-manganese concentrations (r=0.857, 0.875, 0.838). According to principal component analysis, measurements of zinc-, sodium-, boron-, copper- and strontium content gave almost the same results as obtained with 16 different elements. According to a two dimensional non-linear map of absolute values of principal component analysis, wines from Szekszard and Eger could be differentiated, whereas the analysis of wines from Villany, the Matra Mountains and Lake Balaton showed overlapping results.
Wine Red Spectrophotometry Volatile generation Standard method

"An Injection Method For The Sequential Determination Of Boron And Several Metals In Waste-water Samples By Inductively-coupled Plasma Atomic Emission Spectrometry"
Anal. Chim. Acta 1979 Volume 109, Issue 1 Pages 73-83
J. A. C. Broekaert and F. Leis

Abstract: Boron and nine metals (Ba, Cd, Cu, Fe, Mn, Mo, Ni, Zn) can be determined in waste waters of medium and high salt concentration by inductively-coupled plasma atomic emission spectrometry. An injection method was applied in order to achieve analysis times of about 1 min per determination, and to allow trace analysis in solutions having salt concentrations up to 20 mg mL-1, when a Meinhard nebulizer is used with a low-power argon plasma. When 500-l aliquots are injected and the peak heights of the amplified photomultiplier signals are measured, the detection limits for the elements tested range from 0.05 to 0.4 µg mL-1. Matrix effects caused by sodium nitrate (20 mg mL-1) are less than 20%, provided that a peristaltic pump is used for feeding the nebulizer. Matrix effects can be decreased by using simultaneous background measurement. The plasma-injection method is applicable to boron and metals in the range 0.05-20 µg mL-1.
Waste Spectrophotometry

"Synchronization Of Signal Sampling With Liquid Pulsation In Systems With Peristaltic Pumps"
Anal. Chim. Acta 1981 Volume 127, Issue 1 Pages 239-243
F. Opekar and A. Troj&aacute;nek

Abstract: Method and electronic circuitry are described for synchronization of analytical signal sampling with pulsation of liquid flow in systems with a peristaltic pump. The technique is illustrated for cathodic stripping voltammetry of manganese.
Voltammetry Pump pulsations Apparatus Theory

"Selectivity In Flow Injection Analysis"
Anal. Chim. Acta 1983 Volume 148, Issue 1 Pages 111-125
E. H. Hansen and J. RikaF. J. Krug and E. A. G. Zagatto

Abstract: A generalized method for assessing the extent of interference of foreign species on a given chemical assay is proposed. The interference can be quantified by a parameter termed selectivity coefficient. The method is based on injecting the analyte and the interfering species simultaneuosly, and then letting them merge eithe synchronously or asynchromously; the analytical readout is taken from the element of fluid where the dispersion of the two species is identical. It is shown that this makes the accompanying calculations simple, because the selectivity coefficient can be related directly to the originally injected concentrations. The general method is demonstrated for a spectrophotometric procedure for the determination of manganese with formaldoxime, and the selectivity coefficients for various metal ion are determined. The applicability of three different f.i.a. manifold configurations is discussed.
General Selectivity coefficient Review Theory

"The Application Of Strongly Oxidizing Agents In Flow Injection Analysis. 1. Silver(II)"
Anal. Chim. Acta 1985 Volume 169, Issue 1 Pages 99-107
R. C. Schothorst and G. Den Boef

Abstract: A flow injection apparatus is described in which 1 or 2.5 mM AgNO3 was passed through an electrochemical reactor with a working electrode of a packed bed of gold powder, a platinum-wire counter-electrode and a SCE. The AgII formed was mixed with the sample in a stream of 2.9 M HNO3 in a single-bead-string reactor; detection was effected at 390 nm. Various organic and inorganic compounds were determined. Oxidizable compounds may be determined in the presence of Fe(III) or Cu(II) since neither species reacts with Ag(II). Selective determination of 60 µM-Mn(II) at 525 nm in the presence of 1 mM Co(II) was achieved.
Electrode Spectrophotometry Single bead string reactor

"Sequential And Differential Catalytic-fluorimetric Determination Of Manganese And Iron By Flow Injection Analysis"
Anal. Chim. Acta 1985 Volume 169, Issue 1 Pages 141-148
F. Lazaro, M. D. Luque De Castro and M. Valcarcel

Abstract: Two methods for the determination of Mn and Fe in mixtures by flow injection analysis are described, which are based on the catalytic action of Mn or Fe on the oxidation of salicylaldehyde thiosemicarbazone by H2O2. For method(I) a diverting valve is used to select the most appropriate carrier for the determination of one cation in the presence of the other. For method(II) a system with splitting and confluence points is used to obtain two different residence times for the two portions into which the sample is sub-divided. Simplex optimization was used to determine optimum conditions. The calibration graphs were rectilinear for 48 to 200 and 40 to 600 ng mL-1 for methods(I) and(II), respectively.
Water Fluorescence Catalysis Optimization Simplex Tecator Sample splitting

"Sequential Injections In Flow Systems As An Alternative To Gradient Exploitation"
Anal. Chim. Acta 1985 Volume 173, Issue 1 Pages 289-297
E. A. G. Zagatto, M. F. Gin&eacute;, E. A. N. Fernandes, B. F. Reis and F. J. Krug

Abstract: Because zone-sampling from a pronouced concentration. gradient (cf. Reis et al., Anal. Abstr., 1981, 41, 2J20; Gine et al., Ibid., 1984, 46, 7G1) is prone to imprecision due to flow fluctuations, sampling from a zone of virtually constant concentration. resulting from the merging of, e.g., three plugs of the sample solution injected simultaneously at different positions into the carrier stream ('sequential injections') has been investigated. Such a zone corresponds to one of the maxima or minima of the resultant concentration. - time profile, and the concentration. corresponding to this zone can be adjusted by varying the lengths of the mixing coils between the injection positions. An injection manifold is described for the determination of Mn in rocks by sequential-injection zone-sampling - AAS; output corresponding to a wide range of concentration. (e.g., 80 to 6000 µg g-1; up to 20 µg mL-1 injected) can be accomodated on a single recorder chart. A manifold is also described for the zone-sampling introduction of standard additions to the sample solution for the determination of Cu in ethanol by flow injection AAS.
Organic compound Geological Spectrophotometry Gradient technique Standard additions calibration Zone sampling

"Continuous-flow Determination Of Manganese In Natural Waters Containing Iron"
Anal. Chim. Acta 1987 Volume 199, Issue 1 Pages 221-226
D. J. Hydes

Abstract: Removal of interference by Fe in the formaldoxime method for Mn determination has been re-evaluated. Addition of EDTA at controlled pH after formation of the Mn - formaldoxime complex could remove interference from up to 100 µM-Fe. In the proposed procedure, the formaldoxime reagent is added at pH 9.9 to form both Mn and Fe complexes, and EDTA is added to pH 7.7 to break down the Fe complex at 37°C during 25 min before the absorbance is measured. The system could be operated at Mn concentration. up to 100 µM.
Environmental Spectrophotometry Complexation Heated reaction Interferences

"Trace Determination Of Some Heavy Metals In Waters By Flow Injection Spectrophotometry And Potentiometry"
Anal. Chim. Acta 1987 Volume 200, Issue 1 Pages 21-33
Yu. A. Zolotov, L. K. Shpigun, I. Ya. Kolotyrkina, E. A. Novikov and O. V. Bazanova

Abstract: Three automated flow injection manifolds are described for the determination of dissolved ionic or weakly associated Cu(II), Pb and Mn(II) in natural, potable and waste waters. The catalytic effect of Mn(II) on the oxidation of NN-diethylaniline by KIO4 at pH 6.86 to 7.10 and 30°C was used for the determination of 0.02 to 1.00 µg L-1 of Mn at 475 nm. The system used a three-channel manifold with reagent injection and stopped-flow. Interference by Fe(III) was eliminated by using phosphate (pH 6.86) or citrate - phosphate buffer (pH 7.10). Lead (0.7 to 100 µg l-1) was determined at 520 nm as its complex with 4-(2-pyridylazo)resorcinol (pH 9.8) after online pre-concentration. of the sample (5 to 50 ml) on a mini-column of Chelex-100 or Dowex 1-X8. Many interfering ions were masked with 10% KCN solution A potentiometric system with a Cu ion-selective electrode was used for the determination of Cu(II) (0.5 to 1000 µg l-1). Samples (50 to 500 ml), mixed with 0.5 M acetate buffer (pH 4.7), were subjected to online pre-concentration. on Chelex-100 resin.
Sea Water Waste Potentiometry Spectrophotometry Electrode Heated reaction Preconcentration Review Stopped-flow Catalysis Chelex Resin Interferences

"Determination Of Trace Manganese In High-purity Titanium, Silicon And Mineral Acids By A Flow Injection Method Based On A Catalytic Reaction"
Anal. Chim. Acta 1989 Volume 217, Issue 1 Pages 23-30
Chongliang Zhang, Susumu Kawakubo and Tsutomu Fukasawa

Abstract: Sample solution (1 to 2 ml; 1.5 M in HF and 0.2 M in HCl) was subjected to ion-exchange extraction on a column of Amberlite CG-120 (H+ form, 100 to 200 mesh), with elution of the Mn with 6 M HCl. The eluate was evaporated almost to dryness, and the residue was dissolved in acetate buffer (pH 4.4). Portions (100 µL) were injected into the flow injection system where they were mixed with reagent solution [0.26 mM malachite green (C. I. Basic Green 4) - 0.01 M KIO4] before passing to a reaction coil at 50°C. The absorbance of the solution was measured at 615 nm. The calibration graph was rectilinear for up to 7 ng of Mn and the coefficient of variation (n = 5) at 3 ng of Mn was 2%. The method was successfully applied in the analysis of HF, HCl and HNO3 and of Ti metals and Si (sample prep. described).
Inorganic compound Inorganic compound Inorganic compound Metal Metal Spectrophotometry Preconcentration Column Amberlite Buffer Catalysis Heated reaction

"Determination Of Boron In Water By Flow Injection Inductively Coupled Plasma Emission Spectrometry"
Anal. Chim. Acta 1989 Volume 218, Issue 1 Pages 69-76
Phillip L. Kempster and Henk R. Van Vliet, Jacobus F. Van Staden

Abstract: An 11 mL mini-cloud chamber, containing a tangentially attached aerosol exit tube that induced spiral motion in the aersol within the chamber, was incorporated into a flow injection ICP-AES system (illustrated) for the cited analysis. The carrier stream (H2O) was pumped through each 300 µL sample loop, or in turn to the ICP nebulizer, the opposite sample loop being filled via the sample via negative pressure. The carrier outlet port of the sampling valve was connected to the nebulizer by polyethylene tubing, and B was determined at 249.68 nm. The calibration graph was rectilinear from 0.5 to 25 mg L-1 of B, and the coefficient of variation for 2.5 to 25 mg L-1 were 5.4% (n = 10). 'Memory effects' were ~5-fold smaller with the mini-cloud chamber than with a 110 mL cloud chamber. Aluminum, Ca, Cr, Fe, Na and P did not interfere. Sample throughput was 320 h-1 at a carrier flow rate of 3.5 mL min-1. The method was also applied in the determination of Ca, Mg, Mn and Sr in water.
Environmental Spectrophotometry Nebulizer Interferences

"Trace Metal Enrichment By Automated Online Column Preconcentration For Flow Injection Atomic Absorption Spectrometry"
Anal. Chim. Acta 1989 Volume 221, Issue 1 Pages 65-76
Shizuko Hirata, Kazuto Honda, Takahiro Kumamaru

Abstract: Trace metals were pre-concentrated on a micro-column (7 mm x 4 mm) of Muromac A-1 (50 to 100 mesh) at a flow rate of 5 mL min-1. Ions were eluted with 2 M HNO3 (4.85 mL min-1), before analysis by flame AAS. Optimum pH was established for metal ion uptake from sample solution The coefficient of variation for 20 mL samples containing 5 to 100 µg L-1 of Cd, Cr, Cu, Fe, Mn, Pb or Zn were 0.7 to 1.7% (n = 3 or 4). Values for Cd and Cr in standard reference materials of plants, mussel tissue and pond sediment were within the specified range.
Mussel Pond Spectrophotometry Column Preconcentration Muromac Reference material Optimization pH

"Flow Injection Catalytic Kinetic Determination Of Manganese Using Stopped-flow And Gradient Calibration"
Anal. Chim. Acta 1990 Volume 235, Issue 1 Pages 323-327
Jiannan Yang, Chenglong Ma and Shuliang Zhang, Zhao Shen

Abstract: Sample solution was injected in to a carrier stream of borax - NaOH buffer (pH 9.5), mixed with two reagent streams of aqueous 0.5 M H2O2 and 0.1 M Tiron - 20 mM 1,10-phenanthroline, respectively, and the absorbance was monitored at 440 nm. Calibration was effected by the stopped-flow technique and only one standard was required. The calibration graph was rectilinear for up to 640 nM-Mn(II) and no interference was observed from Zn(II), Co(II), Ni(II), Fe(III), Cd(II) and Cu(II). The method was applied in the determination of Mn2+ in resevoir water; results agreed well with those by an alternative catalytic method. Throughput was 40 samples h-1.
Catalysis Kinetic Stopped-flow Calibration Buffer pH Interferences Gradient technique Tiron

"Online Electrolytic Dissolution Of Alloys And Multi-element Determination By Inductively Coupled Plasma Atomic-emission Spectrometry"
Anal. Chim. Acta 1991 Volume 251, Issue 1-2 Pages 187-190
Dongxing Yuan, Xiaoru Wang, Pengyuan Yang and Benli Huang*

Abstract: The method previously described (Ibid., 1991, 243, 65) for flow injection electrolytic dissolution - ICP-AES was applied to multi-element analysis of aluminum alloys. The electrolyte used was 1 M HNO3 and electrolysis was carried out at 1150 mA cm-2 for 20 s. For determination of Zn, Si, Fe, Mn, Cr, Mg and Cu, coefficient of variation were 1 to 6.5%. Up to 500 µg mL-1 of Al did not interfere in the determination of 1 µg mL-1 of the above elements. Results agreed well with certified values for standard samples.
Spectrophotometry Interferences Multielement Reference material

"Online Preconcentration System For Inductively Coupled Plasma Atomic Emission Spectrometry With Quinolin-8-ol And Amberlite XAD-2 Resin"
Anal. Chim. Acta 1992 Volume 258, Issue 2 Pages 237-244
Valerio Porta, Corrado Sarzanini, Edoado Mentasti* and Ornella Abollino

Abstract: An online pre-concentration. system implemented with inductively coupled plasma atomic emission spectrometry (ICP-AES) was studied for water anal. For the retention of metal ions, 8-hydroxyquinoline and Amberlite XAD-2 resin were used. This system improved the detection limits of Cd, Cu, Fe, Mn, Ni, and Zn by a factor of 100, compared with ICP-AES alone. The method was applied to the determination of the above metals in Antarctic seawater. The concentration. was 16 ng Mn/L and 0.4 µg Ni/L, with a precision of 10%.
Sea Spectrophotometry Amberlite Resin Preconcentration 8-Hydroxyquinoline

"Flow Injection Determination Of Subnanogram Amounts Of Manganese By Catalysis Of The Oxidative Coupling Of NN-dimethyl-p-phenylenediamine With M-phenylenediamine"
Anal. Chim. Acta 1992 Volume 261, Issue 1-2 Pages 183-188
Shigenori Nakano*, Masahiro Nozawa and Maki Yanagawa, Takuji Kawashima

Abstract: The sample solution (183 µL) is injected into a carrier stream of HCl (1 mM or 0.1M), which is merged with, first, 0.5 M H2O2 and then a pre-merged stream of (a) 6 mM NN-dimethyl-p-phenylenediamine - 0.8 mM tiron - 10 mM L-cysteine and (b) 3 mM m-phenylenediamine - 8 mM triethylenetetramine - 0.4 M NH3; each of the four solution is pumped at 0.8 mL min-1. The resulting solution is passed through a reaction coil (8 m) at 35°C and the increase in absorbance over a reagent blank is measured at 650 nm vs. air. The development of these optimum conditions is described. The calibration graph is rectilinear for 0.05 to 1.0 ng mL-1 of Mn(II), the detection limit is 10 pg mL-1, sample throughput is 25 h-1 and the coefficient of variation at 0.3 ng mL-1 was 1.5% (n = 10). Few foreign ions interfered seriously; Fe(III) was masked by the L-cysteine. The method was successfully applied to water samples pre-diluted 20 to 500-fold with 0.1 M HCl; results on tap-, river and lake water are tabulated. A spectrophotometric flow injection method was developed for the determination of subnanogram amounts of manganese(II) based on its catalytic effect on the oxidative coupling of N,N-dimethyl-p-phenylenediamine with m-phenylenediamine in the presence of hydrogen peroxide. The catalytic activity was greatly enhanced by the presence of triethylenetetramine and 1,2-dihydroxybenzene-3,5-disulfonate together. The proposed method allows the determination of as little as 50 pg mL-1 of manganese(II) with relative standard deviations below 3% at a rate of 25 samples h-1. The method can be applied to the determination of manganese in natural waters.
Lake River Water Spectrophotometry Catalysis Interferences Heated reaction Tiron

"Flow Injection Analysis Of Trace Elements By Use Of Catalytic Reactions"
Anal. Chim. Acta 1992 Volume 261, Issue 1-2 Pages 167-182
Takuji Kawashima*, Shigenori Nakano

Abstract: This review covers the mechanism of catalytic reactions involving trace elements, together with catalytic flow injection methods for the determination of Fe, Mn, Cu, Co, V, Cr, Mo and Se, as well as halides and other anions. Representative examples are given of organic compounds used in the indicator reactions. Comparison with batch methods shows that flow injection methods are sometimes less sensitive than their manual counterparts, but afford satisfactory accuracy and precision and have certain advantages (94 references). A review with 94 references. Catalytic reactions have importance in trace analyzes for elements, and kinetic-catalytic methods of anal. based on catalytic reactions have progressed recently. The change in a phys. property such as absorbance, fluorescence, chemiluminescence or electrode potential of a system with time is usually monitored in kinetic-catalytic methods, as these methods include time as a measured variable. Flow injection analysis (FIA) is considered to be a suitable technique for catalytic methods of analysis, i.e., the reaction can easily be controlled by fixing the flow rate of solutions and the length of the reaction coil, yielding reproducible mixing. The adaptation of FIA to catalytic methods can lead to many advantages such as higher precision, better detection limits and rapid sample throughput. After a brief review of the catalytic action of elements in redox reactions, the use of the catalytic reactions in FIA methods is discussed through representative examples.
Fluorescence Chemiluminescence Spectrophotometry Electrochemical analysis Review Catalysis Method comparison

"Simultaneous Determination Of Trace Metals In Human Hair By Dynamic Ion-exchange Chromatography"
Anal. Chim. Acta 1993 Volume 274, Issue 1 Pages 163-170
A. Sturaro*, G. Parvoli and L. Doretti, S. Zanchetta and G. Allegri, G. Battiston

Abstract: Sample was washed with non-ionic detergent solution, followed by Soxhlet extraction with ethyl ether. After drying at 105°C for 12 h, the sample was pulverized and digested with HNO3 - HClO4. The digest was evaporated to dryness and the residue was dissolved in mobile phase and mixed with Co solution (200 mg l-1; internal standard). Analysis was on a column (15 cm x 3.9 mm) of Waters Delta Pak RP-18 (5 µm) with aqueous 5% acetontrile containing 0.0433% sodium octanesulfonate and 0.6063% sodium hydrogen tartrate (adjusted to pH 3.65) as mobile phase (0.75 mL min-1) and UV and photodiode array detection at 546 and 492 nm, respectively. Online post-column derivatization with monosodium 4-(2-pyridylazo)resorcinol resulted in improved absorbance in the UV region. The simultaneous determination of Cu, Zn, Ni, Mn, Pb and Co was achieved with detection limits of ~1 µg g-1. Calibration graphs were rectilinear in the ranges 50 to 600 µg g-1, 2 to 80 µg g-1, 1 to 25 µg g-1, 5 to 200 µg g-1 and 0.1 to 2 µg g-1 for Zn, Cu, Ni, Pb and Mn, respectively. Results were confirmed by AAS and XRF.
Hair HPIC Spectrophotometry Multidetection Post-column derivatization Method comparison Simultaneous analysis

"Flow Injection Flame Atomic Absorption Spectrometry For Slurry Atomization. Determination Of Calcium, Magnesium, Iron, Zinc And Manganese In Vegetables"
Anal. Chim. Acta 1993 Volume 283, Issue 1 Pages 393-400
P. Vi&ntilde;as, N. Campillo, I. L&oacute;pez Garc&iacute;a and M. Hern&aacute;ndez C&oacute;rdoba*

Abstract: Washed cauliflower, bean, citrus and apple leaves were cut up, dried at 90°C, ground and calcined at 500°C for 1.5 h. The residue was ground and, for the determination of Fe, Mn and Zn with direct calibration, suspended in 10% glycerol solution containing 1% HCl, sonicated for 5 min and stirred for 10 min. The slurry was injected into a water carrier stream, which passed to the air-acetylene flame of the AAS instrument. The peak height of the transitory signal was measured. In the alternative standard addition method, the carrier was 10% glycerol/1% HCl containing added Mn(II), Fe(III) or Zn. For the determination of Ca and Mg, the ash was suspended in 1% HCl containing 1% La and 0.02% Triton X-100 and the slurry was injected into the online dilution device shown diagrammatically (Lopez Garcia et al., J. Anal. Atomic Spectrom., 1992, 7, 1291) with the same HCl-based solution as carrier. The determination limits were 12.4, 3.3 and 5.7 µg/g for Fe, Zn and Mn, respectively, and the corresponding RSD (n = 10) were 1.7, 0.9 and 0.8% at 57, 16 and 20 µg/g, respectively. In grapefruit leaves containing 0.4% Mg and 5.18% Ca, the RSD (n = 10) were 1.2 and 1.1%, respectively.
Vegetable Vegetable Leaves Plant Spectrophotometry Slurry Triton X Standard additions calibration Surfactant

"Online Trace Metal Ion Preconcentration In Ion Chromatography Using Carboxymethyl And Hydroxamate Dextran-coated Silicas"
Anal. Chim. Acta 1993 Volume 283, Issue 1 Pages 344-349
N. Ryan and J. D. Glennon*, D. Muller

Abstract: With use of a system incorporating a six-way valve, the metal ions were concentrated from aqueous solution adjusted with 0.5 M LiOH to pH 7 on a column (5 cm x 4 mm i.d.) of chelating adsorbent prepared by treating carboxymethyl dextran-coated silica with hydroxylamine [Srijaranai and Glennon, Analyst (London), 1990, 115, 627]. The metal ions were eluted on to a Dionex Analytical CS5 column for separation with 50 mM oxalic acid/95 mM LiOH of pH 4.8 as mobile phase (1 ml/min). A 0.3 mM 4-(2-pyridylazo)resorcinol solution (0.6 ml/min) was used for post-column derivatization and detection was at 520 nm. The method was used for the pre-concentration and determination of Pb, Cu, Cd, Co, Mn, Zn and Ni, and was applied to the determination of metals in domestic and laboratory tap-water and in river water. Limits of detection were 5-10 ng/ml of Cu, Mn, Co, Zn and Ni but >100 ng/ml for Pb and Cd.
Water River HPIC Spectrophotometry Preconcentration Silica Post-column derivatization Immobilized reagent

"Selective Stopped-flow Determination Of Manganese With Luminol In The Absence Of Hydrogen Peroxide"
Anal. Chim. Acta 1995 Volume 302, Issue 2-3 Pages 275-282
Abaji Gaikwad, Manuel Silva and Dolores P&eacute;rez-Bendito*

Abstract: A novel stopped-flow chemiluminescence method for the determination of manganese by reaction with luminol in the presence of high concentrations of sodium chloride and the absence of hydrogen peroxide is proposed. Light emission takes place over a very short interval (less than ~200 ms). The activity of other ions that react with luminol under the experimental conditions used in the absence of hydrogen peroxide is examined. The proposed method permits the sensitive determination of manganese (detection limit 1.8 x 10^-8 M), with high precision (RSD < 1%), selectivity (thanks to the presence of triethanolamine) and sample throughput (100 samples h-1). It was applied to the determination of manganese in certified biological samples. A possible mechanism for the sodium chloride effect was proposed.
Biological material Chemiluminescence Stopped-flow Selectivity

"Determination Of Trace Metals In Natural Waters By Flame Atomic Absorption Spectrometry Following On-line Ion-exchange Preconcentration"
Anal. Chim. Acta 1995 Volume 303, Issue 2-3 Pages 341-345
M. C. Yebra-Biurrun, A. Bermejo-Barrera, M. P. Bermejo-Barrera* and M. C. Barciela-Alonso

Abstract: An on-line column pre-concentration technique for flow-injection flame atomic absorption spectrometry has been developed for the determination of trace metals in natural waters. A minicolumn (20 mm x 2 mm i.d.) filled with a poly(aminophosphonic acid) chelating resin (PAPhA, 20-30 mesh) was used for the pre-concentration procedure. For 2 mL samples, detection limits of 0.5, 5.0, 1.5, 1.6, 3.5, 0.6, 3.2, 3.1 and 0.4 g 1-1 for Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, respectively, were achieved. The precision (coefficient of variation) obtained was in the range between 1.1 (Cd and Cu) and 3.3% (Co). Accuracy was also investigated and results agreed with the certified values of the reference material. The sampling rate was 48 h-1. The method was applied to the determination of trace metals in natural waters samples from Galicia (Spain).
Environmental Ion exchange Spectrophotometry Preconcentration Column Resin Reference material

"Continuous-flow Analysis: Simultaneous Spectrophotometric Determination Of Metals"
Anal. Chim. Acta 1995 Volume 308, Issue 1-3 Pages 386-396
Yu. A. Zolotov, E. I. Morosanova*, S. V. Zhalovannaya and S. S. Dyukarev

Abstract: Continuous-flow analysis methods for the simultaneous determination of (i) aluminum and manganese, (ii) aluminum and iron(III) and (iii) calcium and magnesium were developed. The methods were based on ligand-exchange reactions or reactions at different rates. For (i) the Al and Mn complexes with xylenol orange (XO) were formed and the combined adsorption was measured at 570 nm in the first detection cell. EDTA was added to the flow system to destroy the Mn-XO complex and allow the Al-XO complex to be determined in the second detection cell at 550 nm. A similar methodology was used for (iii) using eriochrome black T (EB) to determine the combined Ca and Mg concentration at 540 nm. EDTA was added to destroy the Ca-EB complex and allow the Mg-EB complex to be determined also at 540 nm. The different rate of reaction with XO were utilized for (ii). The signal recorded in the first cell at 560 nm was due to the Fe-XO complex while that recorded in the second cell at 550 nm was due to the combined absorption of the Fe-XO and Al-XO complexes. The full details of each method are presented along with the linear ranges and detection limits. The methods were tested on synthetic and real samples (soil extracts, sedimentary rocks). High accuracy and good precision were obtained with RSD of 1-6.5%. The sampling frequency was up to 32 samples/h.
Sedimentary Environmental Spectrophotometry Sample preparation Complexation Segmented flow Kinetic

"Flow Injection Sorbent Extraction With Dialkyldithiophosphates As Chelating Agent For Nickel, Cobalt, And Manganese Determination By Atomic Absorption Spectrometry"
Anal. Chim. Acta 1995 Volume 317, Issue 1-3 Pages 215-222
Renli Ma and Freddy Adams*

Abstract: Using octadecyl functional group (C18) bonded silica gel as sorbent and methanol or ethanol as eluent, the extractability of nickel, cobalt and manganese with diethyl-, di-n-propyl-, di-2-propyl-, di-n-butyl-, di-isobutyl-, di-2-butyl-, di-n-pentyl- and di-n-hexyldithiophosphates, (RO)2P(S)S-, was investigated in respect of the effects of pH, alkyl substituent group, reagent concentration and masking agent by flame atomic absorption spectrometry. The extractability increases with the chain length of the substituent groups in the reagents and is quantitative for alkyl groups larger than butyl at pH ~3. At a high concentration of di-n-pentyldithiophosphate, the metals are selectively extracted from coexisting cadmium, copper, lead and iron. As an analytical demonstration, di-n-pentyldithiophosphate was used for the determination of ultra-trace concentrations of nickel in two certified reference saline water samples (sea water and estuarine water) by graphite furnace atomic absorption spectrometry. Results were in good agreement with the certified values. The detection limit (3s) of peak area measurement was 0.07 µg L-1 with an enrichment factor of 10 for nickel with 20-s sample loading at 8.7 mL min-1 and 20 µL eluate injection.
Spectrophotometry Sample preparation Solid phase extraction Chelation

"Determination Of Manganese In Natural Water And Effluent Streams Using A Solid-phase Lead(IV) Dioxide Reactor In A Flow Injection System"
Anal. Chim. Acta 1997 Volume 350, Issue 1-2 Pages 15-20
J. F. van Staden*, and L. G. Kluever

Abstract: The determination of manganese(II) in natural water and effluent streams, using a solid-phase reactor incorporated into a flow-injection system, was investigated. Mn2+-ions in samples injected into a carrier stream, were oxidized by solid lead(IV) dioxide suspended on silica gel beads to form MnO4--ions which were detected spectrophotometrically at 526 nm. The linear range of the system is between 1 to 5 mg L-1 with a detection limit of 0.56 mg l-1. The proposed system is suitable for the determination of manganese(II) in natural water and effluent streams with a relative standard deviation of better than 1.8%.
Environmental Waste Solid phase reagent Reactor

"Flow Injection Spectrophotometric Catalytic Determination Of Manganese In Plants Exploiting The Aerial Oxidation Of Diphenylcarbazone"
Anal. Chim. Acta 1998 Volume 366, Issue 1-3 Pages 87-92
Nelson Maniasso and Elias A. G. Zagatto*

Abstract: The catalytic effect of Mn(II) on the aerial oxidation of diphenylcarbazone (DFC) becomes very pronounced in the presence of triethanolamine (TEA), whereas the influence of other potential interferents is strongly reduced. This feature was exploited to develop an improved flow injection procedure for Mn determination in plant digests. In view of the high variability of Mn contents in the sample batches, an approach involving two sampling loops was implemented to widen the dynamic range. The proposed system handles ~70 samples per h, requires only 0.13 mg DFC and 85.7 mg TEA per determination, and yields reproducible signals (relative standard deviation of peak heights usually<2%) within two different concentration. ranges (0.10-0.80 and 0.50-4.00 mg L-1 Mn). Detection limit is 0.03 mg L-1 Mn in the digest (3 µg g-1-dry basis). Results are in agreement with flame atomic absorption spectrometry. A noteworthy feature of this procedure is the negligible progress of the uncatalyzed reaction.
Plant Spectrophotometry Catalysis Interferences Method comparison Linear dynamic range

"A Polyvalent Flow Injection System For Multielemental Spectrophotometric Analysis Of Plant Materials"
Anal. Chim. Acta 1998 Volume 370, Issue 1 Pages 39-46
F. V. Silva, A. R. A. Nogueiraa,*, G. B. Souzaa and E. A. G. Zagattob

Abstract: A polyvalent flow injection system consisting of a single manifold suitable to perform different determinations after only minor adaptations was conceived. Its use is particularly attractive for labs. processing a large number of samples including several analytes. The system was applied to spectrophotometric determination of iron, copper, manganese and zinc (micronutrients) as well as calcium, magnesium and phosphorus (macronutrients) in plants. With the proposed system, slight variations in the coefficients of the calibration equations (usually <3%) were found after 4 h working periods. Results were precise (0.8% Plant Spectrophotometry Reference material Optimization

"Speciation Of Copper And Manganese In Milk By Solid Phase Extraction/inductively Coupled Plasma-atomic Emission Spectrometry"
Anal. Chim. Acta 1998 Volume 375, Issue 3 Pages 299-306
O. Abollino, M. Aceto*, M. C. Bruzzoniti, E. Mentasti and C. Sarzanini

Abstract: A speciation method was developed to study distribution of Cu and Mn species in cow milk. The method is based upon solid phase extraction of selective fractions of the analytes, followed by elution and determination by inductively coupled plasma-at. emission spectrometry (ICP-AES), using it as a flow injection detector. Fractions detected were cationic, anionic, neutral and casein-bound. A different behavior is observed for the 2 metals.
Milk Cow Spectrophotometry Speciation Solid phase extraction

"Rapid Determination Of Manganese In Seawater By Flow Injection Analysis With Chemiluminescence Detection"
Anal. Chim. Acta 1991 Volume 249, Issue 2 Pages 469-478
Thomas P. Chapin, Kenneth S. Johnson and Kenneth H. Coale

Abstract: The manganese was concentrated on a column of 8-hydroxyquinoline immobilized on Fractogel and was eluted with 0.0025 M HCl. The eluate at 2.7 mL min-1 was mixed with a reagent containing 0.25 mM 7,7,8,8-tetracyanoquinodimethane (I), 0.30 mM 2',4',5,7'-tetrabromofluorescein and 4 mM didodecylmethylammonium bromide and with 0.01 M NaOH, both at 1.3 mL min-1. The luminescence caused by the oxidation of I and catalyzed by Mn(II) was measured by a photomultiplier. The calibration graph was rectilinear from 1 to 100 mM, with a detection limit of 0.1 nM. In the analysis of standard sea-waters the results agreed closely with certified values and gave standard deviations (n = 3 and 4) of 2.8 and 0.07 for ~43 and 0.48 nM, respectively.
Sea Chemiluminescence Catalysis Column Reference material 8-Hydroxyquinoline

"Evaluation Of The Analytical Use Of The Manganese-catalysed Malachite Green - Periodate Reaction By The Stopped-flow Technique"
Talanta 1989 Volume 36, Issue 11 Pages 1091-1094
M. C. Quintero, M. Silva and D. Perez-Bendito

Abstract: Sample solution contained 2 to 200 ng mL-1 of Mn(II) and 0.1 M NaIO4 (0.7 ml); the reagent solution consisted of 0.22 mM malachite green (2.5 ml) and acetate buffer (pH 3.8; 4 ml). The solution were diluted to volume and mixed, and the decrease in absorbance was measured at 615 nm. The effect on reaction rate of temp., concentration. of reagents and pH were investigated; the detection limit depended on the presence of the activator nitrilotriacetic acid. The calibration graphs were rectilinear from 0.1 to 15 and 0.5 to 100 ng mL-1 of Mn(II), and precision was 2% (n = 11). The proposed method was more sensitive and rapid than reference batch and flow injection methods.
Buffer Dilution Detection limit Calibration Stopped-flow

"Photometric Detector Based On A Blue Light-emitting Diode"
Talanta 1993 Volume 40, Issue 8 Pages 1193-1200
Peter C. Hauser* and David W. L. Chiang,

Abstract: Various light-emitting diodes (LED) were evaluated, and a blue SiN-based LED (Radiospares RS 589-569) was incorporated into a transducer also fitted with a photodiode, which yielded direct absorbance readings by passing the photocurrent to an integrated circuit logarithmic converter. The output was digitized for computer processing. The optical cell (diagram given) had a path length of 1 cm, a volume of 8 µL and light was passed through it by plastic optical cables. The transducer was tested using common spectrophotometric procedures (details given) for Cr, Mn, Fe, Zn and Cl and, although less sensitive than a conventional spectrophotometer, it afforded good precision. Calibration graphs showed slight downward curvature at the upper end. The device was also applied successfully in flow injection analysis.
Light emitting diode Photochemistry Photodiode

"Flow Injection Online Column Preconcentration For Low Powered Microwave Plasma Torch Atomic-emission Spectrometry"
Talanta 1996 Volume 43, Issue 4 Pages 535-544
Ye Dongmei, Zhang Hanqi and Jin Qinhan*

Abstract: Sample solutions in 0.05 M NH4Cl/NH3 buffer of pH 9 were pumped at 1.7 ml/min through a column (3.5 cm x 3 mm i.d.) packed two-thirds full with a thiol resin (type 190) similar to Duolite ES-465. After 1 min, the adsorbed cations were eluted in the reverse direction with 1 M HCl (1.3 ml/min) into a desolvating system of a heated glass tube, a water-cooled condenser and a wash vessel of concentrated H2SO4. The concentration solution was then transported into a pneumatic concentric nebulizer with Ar as carrier gas. The microwave plasma torch conditions were optimized for the detection of Cd(II), Cu(II), Mn(II) and Zn(II). Enrichment factors of 4-5 were achieved. Calibration graphs were linear for 0.01-20 µg/ml (0.05-20 µg/ml for Mn), with detection limits of 1.8-3.6 ng/ml. For 0.3 µg/ml of Cd(II), Cu(II) and Zn(II) and 1 µg/ml of Mn(II) the RSD were 0.7-1.2% (n = 3). Large amounts of alkali metals, which can interfere with the plasma emission, were eliminated in the pre-concentration step.
Spectrophotometry Interferences Preconcentration

"Flow Injection Systems For Determination Of Trace Manganese In Various Salts By Catalytic Photometric Detection"
Talanta 1996 Volume 43, Issue 6 Pages 963-969
Takeshi Yamanea,* and Kazuo Koshinoa

Abstract: Solar salt was dissolved in water and filtered for soluble Mn determination and in water, 2 M HCl and 1.5% H2O2 with heating for 5-10 min followed by filtering for determination of total Mn. The sample containing 0.85 M NaCl was injected into a carrier stream (0.8 ml/min) at water. The stream merged with reagent streams (0.5 ml/min) of 0.26 mM 3,4-dihydroxybenzoic acid/0.75% H2O2 and 1 M sodium carbonate solution. The merged streams passed through a reaction coil (5 m x 0.5 mm i.d.) in a water bath at 40°C and the absorbance was measured at 480 nm. The same system was also used with an online separation step. The sample was injected into a carrier stream of 0.15 M sodium tartrate/4.5 mM tartaric acid/0.3 M NaCl which passed to a borosilicate glass column (7 cm x 4 mm i.d.) packed with 15.5 µm strong cation exchange resin before merging with the reagent streams as above. Calibration graphs were linear for 2-15 ppb Mn and 0-15 ppb Mn in the absence and presence of online separation, respectively, with corresponding detection limits of 2 ppb and 0.5 ppb. RSD (n = 5) was 0.9% for 8 ppb Mn without online separation and 1.4% (n = 5) for 7 ppb Mn.
Inorganic compound Ion exchange Spectrophotometry Heated reaction Column Resin

"Rapid Automated In-situ Monitoring Of Total Dissolved Iron And Total Dissolved Manganese In Underground Water By Reverse-flow Injection With Chemiluminescence Detection During The Process Of Water Treatment"
Talanta 1997 Volume 44, Issue 11 Pages 2041-2049
Yanxiu Zhou and Guoyi Zhu*

Abstract: Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL). The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10^-6 µg mL-1 for Fe(II) and the linear range extents up to 1.0 x 10^-4 and 5 x 10^-6 µg mL-1 for Mn(II) cover a linear range to 1.0 x 10^-4 µg mL-1. This method was used for automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water during water treatment.
Environmental Chemiluminescence Reverse

"Immobilization Of 8-hydroxyquinoline Onto Silicone Tubing For The Determination Of Trace Elements In Seawater Using Flow Injection ICP-MS"
Talanta 1998 Volume 47, Issue 2 Pages 439-445
S. N. Willie*, H. Tekgul and R. E. Sturgeon

Abstract: A rapid and simple online method is described for the pre-concentration of Mn, Co, Ni, Cu, Zn, Cd and Pb from seawater using 8-hydroxyquinoline immobilized onto silicone tubing (Sil-8-HQ) via the Mannich reaction. Recoveries 35-95% and limits of detection in the ppt range were obtained using a 2 m long Sil-8-HQ tube with a sample flow rate of 1.0 mL/min. A tube could be subjected to sample loading and elution cycles over 200 times. The capacity was 1.5 and 1.3 µg/cm2 for Cu and Mn, respectively. Cu, Cd, Co, Pb, Mn, Zn and Ni were determined in coastal and open ocean seawater using flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS). Good agreement with certified values for the certified reference materials NASS-4 and CASS-3 was demonstrated when quantitation was undertaken by the method of additions
Sea NRCC NASS-4 NRCC NASS-3 Mass spectrometry Tube wall immobilization Silicone tubing 8-Hydroxyquinoline Preconcentration Reference material Standard additions calibration

"Semiautomatic Determination Of Manganese In Natural Waters And Plant Digests By Flow Injection Analysis"
Analyst 1979 Volume 104, Issue 1237 Pages 371-375
M. F. Gin&eacute;, E. A. G. Zagatto and H. Bergamin Filho

Abstract: Mn was determined in water and plant digests by the formaldoxime method by a semi-automatic process. The sample was injected onto a stream of carrier (water for water samples, and a suitable acid solution for plant digests prepared by HNO3 + HClO4 treatment). This was mixed, in an automatic analyzer, with 5% ascorbic acid and this stream was then mixed with a premixed stream of reagent, neutralizing solution (aqueous NaOH), and masking agent (KCN, which suppressed interference from Fe up to 20 ppm). With an injected volume of 0.35 mL, about 135 samples per h could be analyzed, with a standard deviation of better than 1% over the range 0.2-2 ppm of Mn.
Plant Environmental Sample preparation Interferences

"Use Of Flow Injection Flame Atomic Absorption Spectrometry For Slurry Atomization. Determination Of Copper, Manganese, Chromium And Zinc In Iron Oxide Pigments"
Analyst 1991 Volume 116, Issue 5 Pages 517-520
gnacio L&oacute;pez Garc&iacute;a, Francisca Ortiz Sobejano and Manuel Hern&aacute;ndez C&oacute;rdoba

Abstract: Dried samples were ground in a ball mill for 5 min and 0.5 g of the sample was treated with 0.5 g of hexametaphosphate and diluted to 50 mL with water. After stirring for 10 min, the sample was injected into the flow injection manifold for flame AAS detection. Matrix effects were avoided by calibration with use of slurries prepared from previously analyzed iron oxide samples. Excellent agreement was found between the results of the slurry procedure and those obtained by conventional acid-dissolution in the determination of Cu, Mn, Cr and Zn in iron oxide pigments.
Inorganic compound Spectrophotometry Automation Slurry Method comparison Interferences

"Shipboard Flow Injection Method For The Determination Of Manganese In Seawater Using In-valve Preconcentration And Catalytic Spectrophotometric Detection"
Analyst 1991 Volume 116, Issue 7 Pages 707-710
I. Ya. Kolotyrkina, L. K. Shpigun, Yury A. Zolotov and G. I. Tsysin

Abstract: Sample was applied to a micro-column (1 cm x 2.5 mm) of DETATA fibrous sorbent (H+ form; cf. Tsysin et al., Zh. Neorg. Khim., 1990, 34, 960) and the Mn adsorbed was eluted with 0.5 M HCl or HNO3. The eluate was mixed with 10 mM KIO4 in phosphate buffer solution and NN-diethylaniline in dilute HCl amd the increase in absorbance at 470 nm was recorded. Preconcentration times of 10 s to 10 min allowed determination of 20 µg L-1 to 10 ng L-1 of Mn. The coefficient of variation were 5 to 8% and a sampling rate of 15 h-1 was achieved. Recoveries of 50 ng L-1 to 10 µg L-1 of Mn were 97 to 118%. The method was applied to the direct shipboard measurement of Mn in deep seawater samples.
Sea Spectrophotometry Buffer Catalysis Column Preconcentration

"Flow Injection Sample-to-standard Additions Method Using Atomic Absorption Spectrometry Applicable To Slurries"
Analyst 1991 Volume 116, Issue 8 Pages 831-834
Ignacio L&oacute;pez Garc&iacute;a, Francisca Ortiz Sobejano and Manuel Hern&aacute;ndez Cordoba

Abstract: The flow injection sample-to-standard additions method of Israel and Barnes (Ibid., 1989, 114, 843) has been extended and tested on aqueous slurries of iron oxide pigments by using a standard analyte solution as carrier. The equation derived allows the calculation of analyte concentration. in a sample from only the signal from injection of the slurry and that from a standard solution The equation was applied to 0.2% slurries of Zn and 1% slurries of Cu, Mn and Cr. Results agreed well with those obtained by conventional methods.
Inorganic compound Spectrophotometry Slurry Method comparison Standard additions calibration

"Trial Measurements In Flow Analysis"
Analyst 1993 Volume 118, Issue 6 Pages 719-722
Boaventura Freire dos Reis, Elias Ayres Guidetti Zagatto, Patricia Benedini Martelli and Sandra Maria Boscolo Brienza

Abstract: In flow analysis trial measurements can be obtained by sequential injection or gradient exploitation. The potential and limitations of both strategies were evaluated. Both methods were applied to the determination of Mn in rocks by AAS. Different set ups were designed with the main reactor of the flow systems being connected to the aspiration tubing of the spectrometer. For trial measurements with sequential injections, peak maxima were quantified following an increasing concentration. sequence and measurements were compared with a threshold value which was selected as an absorbance of 0.3. The system was set-up to provide three overlapping peaks with heights in a ratio of approximately 10:3:1. In gradient exploitation the peaks were also quantified so that no modifications to the detector were needed. The results were in agreement with those obtained by ICP-AES.
Geological Spectrophotometry Method comparison Gradient technique

"Sensitive Determination Of Manganese Using Flow Injection And Chemiluminescent Detection"
Analyst 1995 Volume 120, Issue 8 Pages 2119-2127
Andrew R. Bowie, Peter R. Fielden, Roger D. Lowe and Richard D. Snook

Abstract: A reagent stream (3.7 ml/min) consisting of 0.25 mM 7,7,8,8-tetracyanoquinodimethane/4 mM didodecyldim ethylammonium bromide/0.3 mM Eosin Y and a stream (3.7 ml/min) of 0.01 M NaOH were mixed in a 2 m coil. The mixed stream was transferred to a spiral flow cell where it was mixed with an aqueous carrier stream (3.7 ml/min) into which the sample (90 µL) had been injected. The chemiluminescence intensity produced was measured. Three flow regulators (each consisting of 1 m of coiled tubing) were employed on each of the stream lines to act as pulse dampeners. Diagrams of the manifold and spiral flow cell used are given. The calibration graph was linear from 0-100 ppb of Mn, the detection limit was 4.5 ppb and the RSD (n = 20) was 4.9-5.3%. Interference from Fe was masked with desferrioxamine and the standard additions method was used for quantification of Mn. The method was applied to the analysis of Mn in potable water. The results obtained showed reasonable agreement with those obtained by electrothermal AAS.
Water Chemiluminescence Method comparison Interferences Pulse dampener Standard additions calibration

"Automation In Element Preconcentration With Chelating Ion Exchangers"
J. Anal. At. Spectrom. 1987 Volume 2, Issue 6 Pages 611-614
G&uuml;nter Knapp, Kurt M&uuml;ller, Martin Strunz and Wolfhard Wegscheider

Abstract: A microprocessor controlled pre-concentration system that permits the automated off-line pre-concentration of several samples at the same time is described. Trace elements pre-concentrated from sample volumes of up to several hundred millilitres can be eluted by 5 mL of 2 M nitric acid. It is therefore possible to achieve pre-concentration factors of up to 100. In contrast to FIA methods all ICP-AE spectrometers can be used for the measurements. Four different chelating ion-exchange materials, Chelex 100, oxine cellulose, CPPI resin and Hyphan cellulose, were compared. Trace elements were enriched from concentrated salt solutions and from NBS standard reference materials following decomposition in the High Pressure Asher. After elution the elements were measured by ICP-AES (Plasma II) and by graphite furnace AAS (HGA-500/Zeeman 5000). Under the conditions tested, Chelex 100, the oxine cellulose and the CPPI resin can be employed satisfactorily in the automated pre-concentration of a number of elements.
Biological Environmental Rice Flour Water Ion exchange Spectrophotometry Spectrophotometry Chelation Computer Preconcentration

"Impulse Nebulization Atomic Absorption Spectrometry. 1. Model For The Response Of A Flame Atomizer"
J. Anal. At. Spectrom. 1988 Volume 3, Issue 1 Pages 217-225
L&aacute;szl&oacute; Bez&uacute;r

Abstract: A model for predicting the instrumental response with impulse-nebulization or flow injection sample introduction is developed, based on the mass balance of the atomizer, axial dispersion and the time constant of the spectrometer, and involving all the important parameters, e.g., sample concentration, volume and flow rate, nebulization efficiency and gas flow rate. It gives good agreement with experiment for impulse nebulization, and shows that the dispersion increases from the front to the rear of a flow injection AAS peak.
Spectrophotometry Dispersion Modeling Nebulizer Theory

"Direct Atomic-spectrometric Analysis By Slurry Atomization. 8. Flow Injection Inductively Coupled Plasma Atomic-emission Spectrometry"
J. Anal. At. Spectrom. 1989 Volume 4, Issue 2 Pages 219-222
Andrea J. Ambrose, Les Ebdon, Michael E. Foulkes and Philip Jones

Abstract: The analysis of slurries by flow injection ICP-AES was studied, with particular reference to the controlling parameters, viz, spray chamber design, sample injection volume, carrier stream flow rate and effect of torch injector size. A novel low-volume spray chamber was developed. Sample injection volume of 500 µL gave equivalent sensitivity to that of continuous nebulization; the optimum torch injector tube i.d. was 3 mm. By using this technique, excellent agreement with certified values and precision of 2% were obtained in determination of Ca, Fe, Mg, Mn, Cu and V in reference soils. (For Part VII see Anal. Abstr., 1989, 51, 1B192).
Environmental Spectrophotometry Slurry Nebulizer Optimization Reference material

"Inductively Coupled Plasma Spectrometry In The Study Of Childhood Soil Ingestion. 2. Methodology"
J. Anal. At. Spectrom. 1989 Volume 4, Issue 8 Pages 727-735
Xioaru Wang, Alexandra L&aacute;sztity, Mikl&oacute;s Viczi&aacute;n, Yescheskel Israel and Ramon M. Barnes

Abstract: In a study aimed at quantifying the amount of soil ingested by infants and toddlers, faeces and urine collected in commodes or on diapers, together with home and pre-school dust, soil and food samples, were analyzed for Al, Ba, Mn, Si, Ti, V, Y and Zr by ICP-AES with multi-channel and sequential instruments, and V, Y and Zr were also determined by ICP-MS with flow injection sample introduction. Protocols are described for sample prep., and for online dilution and calibration for ICP-MS. Results obtained on standard solution and on reference soil and dust were in good agreement with certified or recommended values, and results by ICP-AES and ICP-MS were not statistically different, although those by ICP-MS were more precise. Flow injection ICP-MS is recommended for determining V, Y and Zr, which are present at low concentration.
Food Human Faeces Urine Environmental Environmental Sample preparation Spectrophotometry Mass spectrometry Reference material

"Rapid Stopped-flow Microwave Digestion System"
J. Anal. At. Spectrom. 1991 Volume 6, Issue 6 Pages 457-463
Vassili Karanassios, F. H. Li, B. Liu and Eric D. Salin

Abstract: A prototype system for stopped-flow microwave assisted wet digestions has been developed. A coiled Teflon PFA tube serves both as a sample container and as a digestion vessel. A sample plug, consisting of a water slurry mixed with an acid mixture, is pumped into the coil. Sample flow is stopped, the coiled tube is sealed (by closing an input and an output valve) and microwave power is applied for 2 min for digestion of the sample. Methodology was developed using powdered botanical reference samples and was tested with powdered botanical and biological reference materials. The digests were analyzed by inductively coupled plasma atomic emission spectrometry. In addition to comparisons with certified values, the results were compared with those obtained by conventional open-vessel hot-plate digestions, by open-vessel microwave digestions and by digestions taking 32 min by using the coiled tube system. Precise, and in many instances, quantitative digestions were obtained using a net digestion time of 2 min. Elemental recoveries were sample type and digestion time dependent and were found to be comparable with, and sometimes, superior to those obtained when using a 3 h long hot-plate digestion. In this preliminary study, characteristics, limitations and future directions are discussed.
Geological Plant Sample preparation Microwave Online digestion Stopped-flow

"Preconcentration And Inductively Coupled Plasma Atomic Emission Spectrometric Determination Of Metal Ions With Online Chelating Ion Exchange"
J. Anal. At. Spectrom. 1992 Volume 7, Issue 1 Pages 19-22
Valerio Porta, Corrado Sarzanini, Ornella Abollino, Edoardo Mentasti and Enzo Carlini

Abstract: An online pre-concentration method utilizing a microcolumn of XAD-2 resin functionalized with 1-(2-thiazolylazo)-2-naphthol was developed. Preconcentration factors of 125 were obtained for injection times of 5 min. The detection limit ranged between 2 for manganese and 40 ng/L for nickel. The resin was used to pre-concentrate Cd, Cu, Fe, Mn, Ni, and Zn from river water and Antarctic seawater (Ross Bay) prior to their determination by inductively coupled plasma atomic emission spectrometry. The precision of the technique is ~10% relative standard deviation at concentrations below the µg/L level and 5% for higher concentrations.
River Sea Ion exchange Spectrophotometry Preconcentration Amberlite Resin Chelation

"Determination Of Trace Metals In Uranium Oxide By Inductively Coupled Plasma Mass Spectrometry Combined With Online Solvent Extraction"
J. Anal. At. Spectrom. 1992 Volume 7, Issue 3 Pages 565-569
S. Vijayalakshmi, R. Krishna Prabhu, T. R. Mahalingam and C. K. Mathews

Abstract: An online solvent extraction technique for the determination of trace elements in uranium by inductively coupled plasma mass spectrometry is described. An aqueous solution containing uranium (2% m/v) in 1 mol L-1 nitric acid and an organic solvent that can effectively ext. uranium, viz., trioctylphosphine oxide in cyclohexane (0.2 mol L-1), are pumped alternately through a poly(tetrafluoroethylene) (PTFE) tube where they mix thoroughly. The organic phase containing the extd. uranium is removed online by allowing the solution to pass through a microporous PTFE tube which, being hydrophobic, selectively allows the organic phase to permeate through its walls. This technique facilitates rapid and sensitive determination of trace elements in uranium with detection levels in the range 1-45 ppb for La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Ag, Ba, Cd, Co, Cr, Cu, In, Li, Mn, Ni, Pb, Sr, Ti, V and Y, 0.1 ppm for Al and 0.5 ppm for Fe. flow rate of about 4 mL min-1 was used.
Inorganic compound Mass spectrometry Sample preparation Solvent extraction Teflon membrane

"Multipurpose Flow Injection System. 1. Programmable Dilutions And Standard Additions For Plant Digests Analysis By Inductively Coupled Plasma Atomic-emission Spectrometry"
J. Anal. At. Spectrom. 1992 Volume 7, Issue 6 Pages 865-868
Boaventura Freire dos Reis, Maria Fernanda Gin&eacute;, Francisco Jos&eacute; Krug and Henrique Bergamin Filho

Abstract: Combinations of the injector commutator and solenoid valves provided a simple way of achieving different flow injection configurations for standard additions and dilutions. Results for Ca, Mn and Zn in three vegetable samples agreed well with reported values. A flexible flow injection system to perform multipurpose functions related to sample handling is proposed. The flow network consists of a sliding injector commutator, solenoid valves, and other minor components. A dedicated microcomputer controls these devices, facilitating the definition of different flow configurations. Merging zones, zone sampling, intermittent flow, sequential injections, zone trapping, and stopped-flow are possible. Online programmed dilutions and standard additions for simultaneous determinations on plant digests by inductively coupled plasma atomic emission spectrometry were chosen to demonstrate some features of the system. Sample dilutions were accomplished by confluence at different points along the analysis path through a proper programming of the solenoid valves. Standard additions were performed by merging the sample zone with an aliquot delivered from a trapped standard zone in a modified version of the zone sampling process. To minimize matrix effects from the nitric-perchloric acid digests, a sequential dilution procedure is proposed for the major elements and standard additions for the minor constituents. No other standardization procedure was necessary and results were calculated by using the least squares regression method. Results obtained with the proposed procedure compared well with the reported values for plant reference materials.
Vegetable Sample preparation Spectrophotometry Standard additions calibration Merging zones Reference material Commutation Stopped-flow Zone sampling Zone trapping

"Atomic Absorption Spectrometric Analysis Of Solids With Online Microwave-assisted Digestion"
J. Anal. At. Spectrom. 1992 Volume 7, Issue 7 Pages 1085-1089
V. Carbonell, A. Morales-Rubio, A. Salvador, M. de la Guardia, J. L. Burguera and M. Burguera

Abstract: A description is given of a procedure for online microwave-assisted digestion of solid samples prior to analysis by flame AAS as described previously (Anal. Chim. Acta, 1990, 238, 417). A slurry of the sample is transported in HNO3 - H2O2 (1:1) to extract Cu and Mn quantitatively in a few min. Digestion times vary from 4 min for sewage sludges to 2 min for matrices like artichoke. Detection wavelengths were 324.7 nm for Cu and 279.5 nm for Mn. A closed flow injection system allows digestion to be conducted online. Sample flow rate was 2.8 mL min-1. Over 15 samples h-1 can be analyzed using the procedure which allows for sequential treatment of different samples. A procedure was developed for the online microwave-assisted digestion of solid samples and their anal. by flame atomic absorption spectrometry. The method involves the transport of a slurry of the sample in a 1+1 mixture of concentrated HNO3 and H2O2, which provides quant. extraction of Cu and Mn in a few minutes. Real samples of sewage sludges dispersed in 20 mL of HNO3 and H2O2 can be digested in 4 min and other matrixes, such as artichoke and diet samples dispersed in 10 mL of HNO3 and H2O2 are digested in only 2 min. A closed flow injection system permits the online digestion to be carried out; the use of two interconnected injection valves allows the measurement of standards during the digestion of samples. The method permits the anal. of more than 15 samples per h and provides accurate results, as demonstrated by the anal. of certified samples of sewage sludges and tomato leaves.
Sludge Vegetable Leaves NIST 1573 Food Sample preparation Spectrophotometry Microwave Online digestion Slurry Reference material

"Online Removal Of Interferences In The Analysis Of Biological Materials By Flow Injection Inductively Coupled Plasma Mass Spectrometry"
J. Anal. At. Spectrom. 1993 Volume 8, Issue 5 Pages 691-696
Les Ebdon, Andrew S. Fisher, Paul J. Worsfold, Helen Crews and Malcolm Baxter

Abstract: Interference trace metals Cd, Cu, Mn, Pb, V and Zn were removed by chelation with 0.1 g of iminodiacetate-based resin (Na+ form; 50-100 mesh) in a micro-column. The metals were eluted into the VG PlasmaQuad PQ2 spectrometer with 3 M HNO3 by a flow injection procedure. Test recoveries were nearly quantitative except for V (90%) and Zn (85%) and the limits of detection were 0.6-9.9 ng/ml, equivalent to 75-1800 pg of element. Results were tabulated for the determination of the cited elements in five reference materials. The method was not suitable for the determination of Cr.
Biological Mass spectrometry Interferences Reference material Iminodiacetate

"Online Ion Exchange For The Removal Of Sulfur Anion Interference On The Determination Of Manganese In Geothermal Fluids By Flow Injection Electrothermal Atomic Absorption Spectrometry"
J. Anal. At. Spectrom. 1995 Volume 10, Issue 7 Pages 479-482
J. L. Burguera, M. Burguera, C. Rivas, P. Carrero, M. Gallignani and M. R. Brunetto

Abstract: Geothermal waters (1 l) were collected (details given) and mixed with 20 mL 1 M triethanolamine. The solution was injected into a flow system (schematic shown) with water as carrier (2.5 ml/min) and drawn through an online anion-exchange column packed with Dowex-1 X8 (NO3- form; mesh size 100-200). Manganese was eluted from the column with 2 mM HNO3 and trapped in a coil. The carrier transferred the analyte to the sample arm assembly and 20 µL portions of the analyte were deposited into the graphite tube atomizer under control of the AAS computer (details given). The analyte was atomized (temperature program details given) and the absorbance of Mn in the vapor produced was measured at 279.5 nm. The calibration graph was linear up to 15 µg/l of Mn and the detection limit was 0.2 µg/l. Inter- and intra-day RSD (n = 10 and 6, respectively ) were 2.8 and 3.2%, respectively, at ~ 5 µg/l Mn. Recoveries were 95-104%. Results agreed well with those obtained by an atomic absorption chelation-liquid-liquid extraction method.
Geological Geothermal Ion exchange Spectrophotometry Dowex Interferences Method comparison

"Direct Determination Of Trace-metals In Seawater Using Electrothermal Vaporization Inductively-coupled Plasma-mass Spectrometry"
J. Anal. At. Spectrom. 1996 Volume 11, Issue 8 Pages 549-553
Graeme Chapple and John P. Byrne

Abstract: A method is described for the direct analysis of five transition elements (Go, Cu, Mn, Ni, V) in sea-mater using ETV-ICP-MS, Interferences from the seawater matrix were eliminated by a combination of in situ separation of analyte and matrix components in the ETV, and use of nitric acid as a chemical modifier, The nitric acid facilitates the removal of chloride from the seawater matrix during the sample drying stage, whilst optimization of the ETV heating program allows for effective separation of residual matrix and analyte species, thus reducing ionization suppression and space charge effects in the ICP-MS, Calibration standards, prepared by spiking a seawater matrix stripped of trace metals by ion exchange, gave excellent linearity and allowed for direct determination of selected analytes without the use of standard additions, Detection limits ranged from 0.003 µg L-1 for V to 0.14 µg L-1 for Cu. The precision and accuracy of the method mere checked by analysis of two certified reference sea-waters.
Sea Mass spectrometry Reference material 8-Hydroxyquinoline Interferences Optimization

"Comparative Analysis Of Aluminum Oxide Powders By Inductively Coupled Plasma-mass Spectrometry With Low And High Mass Resolution"
J. Anal. At. Spectrom. 1996 Volume 11, Issue 9 Pages 797-803
Norbert Jakubowski, Wolfgang Tittes, Dagmar Pollmann, Dietmar Stuewer and Jos&eacute; A. C. Broekaert

Abstract: ICP-MS with low and moderate mass resolution was applied to the determination of trace elements (B, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Ba, La and Ce) in two different pare Al2O3 powders after decomposition. Four different sets of measurements were performed: (1) with quadrupole instrument in standard operation; (2) with the same instrument including an online matrix trace separation step; (3) with a double-focusing magnetic field instrument operated at;low resolution (R=300); and (4) with the same instrument operated with moderate resolution (R=3000). Generally, the quantitative results obtained with the four different techniques are in good agreement. Application of the double-focusing instrument with moderate mass resolution permitted the determination of spectrally interfering elements such as V, Cr, Mn, Fe and Ga in Al2O3 in the 0.04-10 µg g-1 range far above the detection limit. For all four applied techniques, blank values arising from the reagents and instrumentation were a major limitation for a number of elements, and the lowest detection limits were obtained in each instance for elements that do not suffer from limitations due to blank values.
Water Environmental Inorganic compound Mass spectrometry Interferences Method comparison

"Ultratrace Analysis Of Antarctic Snow And Ice Samples Using High Resolution Inductively Coupled Plasma Mass Spectrometry"
J. Anal. At. Spectrom. 1998 Volume 13, Issue 5 Pages 463-468
Ashley T. Townsend and Ross Edwards

Abstract: High resolution ICP-MS was used to determine the concentrations of Al, Sc, V, Mn, Fe, Co, Pb and Bi in snow and ice from Antarctica. To overcome some potentially problematic spectral interferences, measurements were acquired in both low and medium resolution modes. Small sample volumes were analyzed using a microconcentric nebulizer. After rigorous instrument cleaning and sample preparation, detection levels in the low and sub-pg g-1 range (0.3-48 pg g-1) were found for all elements. Concentration. values were determined for a continental snow, sea ice snow and a representative ice core. Concentration. ranges for all snow samples (n = 25) were (in pg g-1): Al (30-2000), V (2-16), Mn (2-30) and Fe (30-1500), while Sc and Co were typically below detection or blank limits. The ice core sample had Al, Mn, Fe and Pb concentrations of 90, 7, 110 and 1 pg g-1, respectively, while Sc, V, Co and Bi could not be quantified (below detection or blank limits). The reliability of the analytical method for Fe was confirmed by flow injection analysis with spectrophotometric detection.
Ice Snow Mass spectrometry Interferences Method comparison

"Determination Of Copper, Manganese And Nickel In Biological Samples And Sea-water By Flow Injection Online Sorption Preconcentration In A Knotted Reactor Coupled With Electrothermal Atomic Absorption Spectrometry"
J. Anal. At. Spectrom. 1998 Volume 13, Issue 6 Pages 527-531
Elissaveta Ivanova, Karima Benkhedda and Freddy Adams

Abstract: A flow injection system with online sorption pre-concentration of copper, nickel and manganese with ammonium pyrrolidinedithiocarbamate (APDC) or 8-hydroxyquinoline (HQ) in a knotted reactor (KR) coupled with electrothermal atomic absorption spectrometry was developed. APDC offered better performance characteristics than HQ for the pre-concentration of copper and nickel but could not be employed for manganese. The performance characteristics of the determination of copper and nickel with APDC were: detection limits (3s), 6.0 and 7.6 ng L-1, precision (relative standard deviation) 2.5% for 0.2 µg L-1 and 1.5% for 0.2 µg L-1 and enhancement factors 44 and 21 using a 30 s pre-concentration time. The corresponding parameters for the determination of manganese with HQ were detection limit 29.0 ng L-1, precision (relative standard deviation) 2.9% for 0.4 µg-1 manganese and enhancement factor 8 with a 30 s pre-concentration time. The sampling frequency was 26 h-1. The accuracy of the method was demonstrated by the anal. of certified reference materials and by recovery measurements on spiked samples.
Biological Sea Spectrophotometry Preconcentration Knotted reactor Tube wall immobilization Reference material 8-Hydroxyquinoline Pyrrolidine dithiocarbamate

"Determination Of Copper, Cadmium, Manganese, And Lead In Saline Water With Flow Injection And Atom Trapping Atomic Absorption Spectrometry"
J. Anal. At. Spectrom. 1998 Volume 13, Issue 7 Pages 631-634
Lyndon A. Ellis and David J. Roberts

Abstract: A flow injection device has been developed to sep. Cu, Cd, Mn and Pb from a solution of sodium chloride, thus minimizing interference and enabling their accurate determination in high salinity waters such as sea- or estuary water. Micro-columns of Chelex 100 resin were used and parameters of ammonium acetate buffer concentration, pH and the concentration. of a buffer flush have been optimized. Close to 100% recovery of the transition elements and 99.8% exclusion of sodium chloride was achieved. Atom trapping atomic absorption spectrometry (ATAAS) was used as the detection technique to determine concentrations. of the four elements at four sites on the Severn Estuary. In addition, a water cut-off device has been incorporated to improve the safety of the AT app.
Estuarine Sea Spectrophotometry Interferences Chelex Buffer

"Direct Determination Of Trace Metals In Sea-water By Inductively Coupled Plasma Mass Spectrometry"
J. Anal. At. Spectrom. 1998 Volume 13, Issue 11 Pages 1239-1244
Eivind Rosland and Walter Lund

Abstract: The direct determination of trace metals in seawater by inductively coupled plasma mass spectrometry (ICP-MS) is described, based on sample introduction by flow injection analysis (FIA) and electrothermal vaporization (ETV). FIA-ICP-MS was used for the determination of Mn, Mo and U; 500 µL of 1+9 diluted seawater were injected in a carrier stream of 0.028 mol/L HNO3. The detection limits were 0.7 µg/L Mn, 1.4 µg/L Mo and 0.10 µg/L U. ETV-ICP-MS was used for the determination of Cd and Pb. The analytes were vaporized as chlorides at 800°C, without interference from the matrix elements. The detection limits were 4.1 ng/L for Cd and 0.8 ng/L for Pb. The FIA-ICP-MS and ETV-ICP-MS results were validated by analyzing a reference seawater sample (NASS4).
NRCC NASS-4 Sea Mass spectrometry Interferences Reference material Method comparison

"Novel Approach To Reaction-rate Based Determinations By Use Of Transient Redox Effects"
Anal. Chem. 1975 Volume 47, Issue 2 Pages 357-359
V. V. S. Eswara Dutt and Horacio A. Mottola

Abstract: A novel approach to fast, continuous kinetic-based determinations of a variety of chemical species using a flowthrough cell system and transient oxidation-reduction signals is present here. All necessary reagents contained in a single reservoir are continuously circulated, at constant flow, through the cell into which an aliquot of the sample containing the species to be determined is quickly injected.
Environmental Spectrophotometry Kinetic Redox

"Sensitivity Enhancements For Flow Injection Analysis-inductively Coupled Plasma Atomic Emission Spectrometry Using An Online Preconcentrating Ion-exchange Column"
Anal. Chem. 1985 Volume 57, Issue 1 Pages 21-25
Steven D. Hartenstein, Jaromir Ruzicka, and Gary D. Christian

Abstract: The construction of 0.1 mL-capacity Chelex 100 ion-exchange columns for the pre-concentration of analyte elements is described. Separate, buffered (pH 9) samples are pumped through two parallel columns (to double the sampling frequency), and sequentially eluted directly into the nebulizer of the ICP by using a flow injection system. This method gives detection limits for simultaneous multi-element analysis that are a 20-fold improvement over those with conventional continuously aspirated systems for Ba, Be, Cd, Co, Cu, Mn, Ni and Pb. The sampling rate is 30 h-1.
Ion exchange Spectrophotometry Chelex Multielement Nebulizer Resin Preconcentration

"Automated Online Ion-exchange Trace Enrichment System With Flame Atomic Absorption Detection"
Anal. Chem. 1989 Volume 61, Issue 6 Pages 520-524
Yan Liu and James D. Ingle

Abstract: Chelex-100 chelating resin is used for enrichment of transition metals at trace concentrations In an automated flow system. The effects of column dimensions, resin particle size, and sample loading and eluting flow rates are studied. To avoid the problems of using a strong acid as the stripping reagent, complexing reagents like cysteine and ethylenedlaminetetraacetic acid are successfully employed to elute transition metals such as Cu, Cd, Mn, Zn, and Pb from small columns packed with Chelex-100 resin. To improve detection limits, the system can be configured for multiple injections of a given sample solution before the column is eluted. A stop-flow technique is developed to allow complete elution from Chelex-100 resin of transition metals that react more slowly with the stripping complexing ligands. The detection limits of the system with flame atomic absorption spectrophotometry are 0.09 pg/L for Cu and Cd and 0.08 pg/L for Mn with a 10 mL sample loop.
Ion exchange Spectrophotometry Stopped-flow Preconcentration Chelex

"Determination Of Manganese In Seawater Using Flow Injection Analysis With Online Preconcentration And Spectrophotometric Detection"
Anal. Chem. 1992 Volume 64, Issue 22 Pages 2682-2687
Joseph A. Resing and Michael J. Mottl

Abstract: The method was based on measurement of the absorbance of a solution of malachite green (I) formed by the Mn(II)-catalyzed reaction of KIO4 with leucomalachite green (II). The sample was was pre-concentrated on a column (7 cm x 3.2 mm) containing quinolin-8-ol immobilized on a vinyl polymer gel (Landing et al., Ibid., 1986, 58, 3031) which was rinsed with Tris buffer at pH 7.8 before elution of the Mn with 36 mM HCl which was then mixed in a 1-m coil with a stream of a solution containing 6 M HCl and II. Streams of 10 mM KIO4 and 2 M NH4+ acetate buffer at pH 4.15 were mixed in a 1-m coil and then mixed with the Mn-containing mixed streams in a 10 m coil at 50°C before measurement of the I solution absorbance at 620 nm. The mixing coils were constructed from knitted Teflon tubing (0.5 mm i.d.). The system also contained a second resin column which was loaded while the first column was eluted. Calibration graphs were rectilinear and parabolic for 25 pM to 0.5 nM and 0.5 to 20 nM of Mn(II), respectively; the detection limit was 36 pM-Mn(II). In the determination of 404 pmol kg-1 of Mn(II) in NASS-2 seawater the coefficient of variation were 5.4%. There was no significant interference from Co, Cu, Ni, Zn, Fe and I- at concentration. twenty-fold higher than their oceanic values. A method for the rapid determination of dissolved Mn in seawater uses online concentration of Mn(II) onto 8-hydroxyquinoline immobilized on a vinyl polymer gel. The Mn(II) is then eluted from the gel by acid and its concentration. determined by spectrophotometric detection of the malachite green formed from the reaction of leucomalachite green and KIO4 with Mn(II) acting as a catalyst. The limit of detection is 36 pmol/L when concentrating 15 mL of seawater. The accuracy of the method was tested using NASS-2 standard seawater. The method has a precision of ~5% for Mn(II) concentrations of ~400 pmol/L. Analysis time is ~5.5 min/sample.
Sea NRCC NASS-2 Spectrophotometry Knotted reactor Reference material 8-Hydroxyquinoline Interferences Resin Preconcentration

"Metal Speciation By Supercritical-fluid Extraction With Online Detection By Atomic Absorption Spectrometry"
Anal. Chem. 1994 Volume 66, Issue 22 Pages 3900-3907
Jin Wang and William D. Marshall

Abstract: A silica flame-in-tube interface is described for the AAS detection of As, Cd, Cu, Mn, Pb, Se or Zn in the eluate from a SFE apparatus. It consisted of a heated optical tube placed within the optical beam of the spectrometer, a flame tube fitted with H2 and O2 gas entry ports and a sample introduction tube. The analyte metal in an aqueous medium was complexed in situ with tetrabutylammonium dibutyldithiocarbamate and the derivative was mobilized into supercritical CO2. The superheated extractor eluate was nebulized into the upper region of a diffuse flame in the interface flame tube and introduced into the optical tube for analysis. The optimal flame conditions were slightly reducing for aqueous and CO2 mobile phases but slightly oxidizing for a methanolic mobile phase. The detection limits of the metals were in the sub ng to low pg range when a standard was flow-injected into the mobile phase. The recoveries of 5 or 10 µg/ml of Cu, Mn and Pb were 92-94.4% with RSD of 0.1%; the RSD for the cumulative area under the AAS response curve was appreciably more variable. The differences in the rates of mobilization of analyte metal from different matrices was studied using fresh and freeze-dried bovine liver.
Liver Sample preparation Spectrophotometry Speciation Solvent extraction

"Flow Injection Analysis In The Teaching Laboratory"
Fresenius J. Anal. Chem. 1982 Volume 312, Issue 5 Pages 441-443
D. Betteridge

Abstract: Experiences in the teaching laboratory with a very simple form of flow injection analysis, in which a constant head is used to propel the carrier stream and the detector is made by a combination of light emitting diode and phototransistor, are described and discussed.
Education Review

"Comparison Of Ion Chromatography And Atomic Absorption Spectrometry For Metal-ion Analysis In Wine And Fruit Juices"
Fresenius J. Anal. Chem. 1985 Volume 322, Issue 5 Pages 474-479
Da-ren Yan, E. Stumpp und G. Schwedt Contact Information

Abstract: Copper, Zn, Fe, Mn, Ca and Mg were determined in wines and fruit juices by ion chromatography and AAS; the results were compared. The chromatographic separation was optimized for a Nucleosil SA-10 column (25 cm x 4 mm) with a mobile phase (2 mL min-1) of 1.5 mM oxalic acid - 2 mM ethylenediamine at pH 3.5. Post-column derivatization was carried out with 0.25 mM 4-(2-pyridylazo)resorcinol containing Zn and EDTA; detection was at 490 nm. Results were comparable with those obtained by AAS between 213.86 and 422.67 nm.
Fruit Wine HPIC Spectrophotometry Spectrophotometry Method comparison Post-column derivatization

"Optimization Of Ion-chromatographic Trace Analysis For Heavy And Alkaline-earth Metals By Post-chromatographic Derivatization"
Fresenius J. Anal. Chem. 1987 Volume 327, Issue 5-6 Pages 503-508
Da -ren Yan, und Georg Schwedt

Abstract: Six metal ions (Fe(III), Cu, Zn, Co, Fe(II) and Mn in elution order) can be separated in 2.5 min by HPLC on a glass column (10 cm x 3 mm) packed with the strong-acid silica gel cation exchanger BT V TM (10 µm; Biotronik) and operated with a mobile phase (2 mL min-1) of 0.25 M tartrate (pH 2.45). A mixture containing 11 ions (additionally Pb, Ni, Cd, Ca and Mg) was separated in 24 min by HPLC on a glass column (20 cm x 4 mm) packed with BT V TM and operated with a mobile phase (1.3 mL min-1) of 0.1 M tartrate (pH 3.05). Detection (at 490 nm) followed post-column derivatization (60°C, 0.25 mL min-1) with a reagent containing 1 mM 4-(2-pyridylazo)resorcinol, 2 M NH3 (pH 11) and, for the 11-elements separation, 0.25 mM ZnEDTA. Detection limits were 1 to 2 ppb although, with pre-concentration. of water samples on a column (5 cm x 3 mm) packed with BT V TM, metals in concentration. 1 part in 1012 could be determined.
Water HPIC Spectrophotometry Heated reaction Post-column derivatization Preconcentration Speciation Optimization

"Microanalytical Determination Of Metallic Constituents Of River Sediments"
Fresenius J. Anal. Chem. 1991 Volume 340, Issue 4 Pages 223-229
E. Ruiz, A. Echeand&iacute;a and F. Romero

Abstract: The distribution of metallic constituents in torrential rivers as a function of the size particle cannot be frequently achieved by conventional analytical procedures, because of the lack of sufficient amounts of the fine fractions. For the study of river sediments in the Basque Country, microanalytical methods have been developed both for major (Na, K, Ca, Mg, Fe, Al, Si) and trace (Cu, Zn, Mn, Cr, Pb, Ni, Cd) components. Wet digestion in PTFE vessels at 140°C was done with 0.05 g sample using HNO-3-HClO-4-HF-H-3BO-3 or HNO-3-HClO-4, respectively. Further determinations were made by i) emission spectrometry (Na, K), ii) visible spectrophotometry (A1), iii) FIA (Fe, Si) and iv) AAS with flow spoiler (Ca, Mg, Cu, Zn, Mn) or graphite furnace (Cr, Pb, Ni, Cd). The proposed method has been checked with a standard sample obtaining mean values almost coincident with the certified ones and variation coefficients lower than 2% for major and 8% for trace components. Then it was applied to total samples and the fine fractions (<63 µm) of 26 samples of sediments from three torrential rivers. Replicated values with analogous variation coefficients were obtained. Some considerations on distribution of major and trace constituents as a function of particle size are also included.
River Spectrophotometry Spectrophotometry Spectrophotometry Spectrophotometry Sample preparation Reference material

"Analysis Of Standard Reference Materials After Microwave-oven Digestion In Open Vessels Using Graphite Furnace Atomic Absorption Spectrophotometry And Zeeman-effect Background Correction"
Fresenius J. Anal. Chem. 1993 Volume 347, Issue 6-7 Pages 233-237
D. Chakraborti, M. Burguera and J. L. Burguera

Abstract: Heating-covered teflon digestion vials located inside a reheatable container in the presence of different acid mixtures with microwave oven dissolve the metals from biological and environmental certified reference materials. Pb, Cd, Cu, Mn and Fe from the dissolved samples are determined by graphite furnace atomic absorption spectrophotometry and Zeeman-effect background correction. The method allows the treatment of about 100 samples per operation. [References: 10]
Biological Environmental Sample preparation Spectrophotometry Reference material

"Flow Injection Flame Atomic Absorption Analysis Of Iron And Manganese In Cement Samples"
Fresenius J. Anal. Chem. 1993 Volume 347, Issue 8-9 Pages 356-360
A. Salvador, R. Martinez-Avila, V. Carbonell and M. de la Guardia

Abstract: Cement (50 mg) was ultrasonically dispersed in 25 mL of 0.12 M HCl/0.15 M HNO3 and the resulting suspension was digested for 10 min at 50°C. In the determination of Fe, a 100 µL portion of the suspension was injected into a water carrier stream (4 ml/min) and this was passed into a magnetically-stirred mixing chamber (1 mL capacity) before aspiration into an air-acetylene flame for determination by AAS at 248.7 nm. The analytical range was 1-125 µg/ml of Fe. For Mn, a 200 µL portion was injected into a water carrier stream (4 ml/min) and this was passed through a PTFE mixing coil (55 cm x 0.8 mm i.d.) before introducing it into an air-acetylene flame for AAS at 279.5 nm. The analytical range was 0.03-6 µg/ml of Mn. Results for a standard cement and four actual cement samples agreed with certificate values or those obtained by independent analytical procedures.
Commercial product Sample preparation Spectrophotometry Reference material Method comparison Well stirred mixing chamber

"Flow Injection Flame Atomic Absorption Spectrometry For Slurry Atomization: Determination Of Manganese, Lead, Zinc, Calcium, Magnesium, Iron, Sodium And Potassium In Cements"
Fresenius J. Anal. Chem. 1994 Volume 350, Issue 6 Pages 359-364
M. A. Bautista, C. P&eacute;rez Sirvent, I. L&oacute;pez Garc&iacute;a and M. Hern&aacute;ndez C&oacute;rdoba

Abstract: Cements of varying silica content (details given) were made in to a slurry in the 0.05-0.25% (m/v) range, by weighing appropriate amounts and adding 50 mL of a 30% glycerol/2% HNO3/2% HF solution. The suspensions were submitted to ultrasound for 10 min and stirred for a further 50 min. Portions (50-200 µL) were taken for analysis, while the suspension was being stirred, and fed straight into one of the two flow injection manifolds, (i) for direct injection and (ii) for on line dilution of the slurries (details given). The carrier was water (5 ml/min). For those instances where the online device was used, 0.1% suspensions were prepared in a similar way, but the suspension medium also contained 0.5 g solid lanthanum nitrate. The carrier was 5% glycerol and 1% lanthanum nitrate solution (4 ml/min). Calibration was performed using aqueous standard solutions under the same experimental conditions. Results are tabulated and agreed with those obtained by conventional procedures.
Commercial product Sample preparation Spectrophotometry Slurry Suspension Method comparison

"Limitations Of A Laboratory Robot For Extracting Available Nutrients From Soil"
Fresenius J. Anal. Chem. 1996 Volume 354, Issue 1 Pages 77-80
N. Brenes, A.M. Bunnell, P.A. Langan, M.N. Quigley, W.S. Reid

Abstract: Soil (2 ml) and 0.2 mL of activated charcoal were transferred to borosilicate glass test tubes (15 cm x 2.5 cm i.d.) by hand, placed in one of four racks of 40. The Zymate II weighed the samples, added 10 mL of acetate buffer of pH 4.8 (Morgan's reagent), vortex-mixed the tubes for 30 s at a setting of 100 units and centrifuged the mixtures. The supernatant liquids were analyzed for phosphate and nitrate by continuous-flow colorimetry and for Al, Ca, Fe, Mg, Mn, K and Zn by the sample volume to 3, 4, 5 and 6 ml, while maintaining the same sample/reagent ratio, were studied. The vortexing step was unchanged, but, for comparison, in another set, the solutions were mixed by hand with a glass rod during a pause. These procedures were applied to a reference soil sample. For all analytes, the maximum extraction by vortexing was obtained with the standard 2 mL sampling; with larger volumes, the amount extracted dropped to half or less. In theory, hand mixing should give results independent of sample volume and this was approximately the case for some analytes (nitrate, phosphate, Ca, K, Mg) but not all. The implications of these findings are discussed briefly.
Environmental Spectrophotometry Sample preparation Extraction Robot

"Simultaneous Determination Of Metal-ion Concentrations In Binary-mixtures With A Multi-LED Photometer"
Fresenius J. Anal. Chem. 1997 Volume 357, Issue 8 Pages 1056-1060
P. C. Hauser and Thusitha W. T. Rupasinghe

Abstract: A compact photometer is based on up to seven different light-emitting diodes whose light is guided into a photometric cell by means of a fiber-optic coupler. The wavelength is selected by switching on the appropriate light source. The application of this multiwavelength photometer to the determination of binary metal ion samples is demonstrated using model mixtures. Solutions of Fe, Co, Cu, Ni, Cr and Mn were used in combination with several photometric reagents. It was found that the instrument yielded concentration measurements which were usually within a few percent of the correct concentration. These results are comparable to reported data obtained with conventional instruments for similar measurements. The application of the instrument for simultaneous determination in flow injection analysis employing rapid computer controlled switching of the light-emitting diodes is also demonstrated. A limitation in the use of light-emitting diodes for the simultaneous determination was found to arise from the fact that in some instances non-linear calibration curves are obtained when employing light-emitting diodes as light sources. This occurs when the absorptivity of the measured compound changes over the emission band of the diodes. Multiple regression analysis is then not easily possible. A compact photometer is used based on up to seven different LED (from blue to near-IR); the light is guided into a photometric cell via a fiber-optic coupler. Wavelength is selected by switching on the appropriate light source. The photometer was applied to the analysis of several model metal ion mixtures in combination with several photometric reagents (details given). Results obtained were comparable to those reported using conventional instruments. This instrument was also applied to simultaneous determination in flow injection analysis using rapid computer-controlled switching of the LED. 19 References
Spectrophotometry Chemometrics Light emitting diode Multicomponent Optical fiber Computer

"Application Of An Online Preconcentration System In Simultaneous ICP-AES"
Microchim. Acta 1992 Volume 106, Issue 3-6 Pages 191-201
Peter Schramel, Li -Qiang Xu, G&uuml;nter Knapp and Markus Michaelis

Abstract: A PC-controlled online pre-concentration system (TRACECON) was connected to a JY-70 Plus simultaneous inductively coupled plasma (ICP) spectrometer to pre-concentrate online seven trace elements (Cu, Fe, Zn, Cr, Ni, Mn, V) in biological and environmental samples. EDTrA-cellulose was used as column material. The elemental concentrations were determined by simultaneous ICP-AES. The effect of pH of the sample solution on the enrichment was studied. It was found that the recoveries of chromium and iron depend strongly on the pH of the sample solution. All the elements mentioned were recovered quantitatively at pH 4.0. The flow rates of sample solution and element solution were optimized. The enrichment factors for seven elements at 5 mL loading volume range from 3.9 for Cu to 7.9 for Zn. The detection limits of all seven elements were improved. The accuracy of the method was tested by the analysis of a number of CRMs of NIST, BCR and NIES. Most results are in good agreement with the certified values.
Biological Environmental Spectrophotometry Computer Reference material Preconcentration Column Optimization pH

"Some Observations On The Sensitivity Of Flow Injection Techniques For Atomic Absorption Spectrophotometry"
Microchem. J. 1989 Volume 40, Issue 2 Pages 233-241
Carbonell, V.;De La Guardia, M.;Salvador, A.;Burguera, J.L.;Burguera, M.

Abstract: Means of improving sensitivity of flow injection AAS systems are discussed, including use of T-connector interfaces, different carriers and flow compensation solvents. The optimized system was applied in the determination of Mn and Cu in sewage sludge.
Sludge Spectrophotometry Optimization Sensitivity Interface Nebulizer

"Determination Of Cadmium, Cobalt, Copper, Manganese, Nickel, Lead And Zinc By Inductively Coupled Plasma Mass Spectroscopy Or Flame Atomic Absorption Spectrometry After Online Preconcentration And Solvent Extraction By Flow Injection System"
Microchem. J. 1996 Volume 54, Issue 4 Pages 402-411
A. Bortoli a, M. Gerottoa, M. Marchioria, F. Maricontib, M. Palontaa and A. Troncona

Abstract: A flow injection manifold and sequence of operations for online separation and pre-concentration of Cd, Co, Cu, Mn, Ni, Pb and Zn are diagramatically presented. Bonded silica with octadecyl functional group C18, packed in a microcolumn of 100 µL capacity, was used to collect diethyldithiocarbamate complexes of the heavy metals in aqueous solution. The metals were complexed with a chelating agent, adsorbed on the C18 column and eluted with methanol directly in the flow injection system. The metals were then determined by GF AAS or ICP-MS (details given). Calibration graphs and detection limits are presented.
Environmental Environmental Spectrophotometry Mass spectrometry Sample preparation Spectrophotometry Preconcentration Solvent extraction C18 Chelation

"Soluble And Particulate Metals In The Adige River"
Microchem. J. 1998 Volume 59, Issue 1 Pages 19-31
A. Bortoli, E. Dell'Andrea, M. Gerotto, M. Marchiori, M. Palonta and A. Troncon

Abstract: The concentrations of 10 metals (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) were monitored over a one-year period in the waters of the lower Adige River, Italy. Concentrations in the dissolved and particulate phases were measured, thus constructing a database on metal variability. The concentrations. of Cd, Cr, Cu, Mn, Ni, and Pb in these water samples are too low to be directly determined by flame atomic absorption spectrometry or graphite furnace atomic absorption spectrometry. In this work, Cd, Co, Cu, Mn, Ni, Pb, and Zn were determined by inductively coupled plasma mass spectrometry (ICP-MS) or GFAAS after online pre-concentration. and following solvent elution with a flow injection analysis system (FIAS). The eluted samples were also dried in a vacuum container and restored to a small volume with concentrated HNO3 and Milli-Q water for anal. by ICP-MS or GFAAS. The concentrations of soluble Cd, Fe, and Mn and particulate As, Cr, Cu, Pb, and Zn are well correlated with seasonal variability (P < 0.01). Dissolved As and Fe are well correlated (P < 0.01), and with respect to the particulate phase, good correlations are observed between Pb, Cd, and Cu.
River Mass spectrometry Spectrophotometry Sample preparation Preconcentration Solvent extraction

"Determination Of Trace Elements In Power Plant Emissions By Inductively Coupled Plasma Mass Spectrometry: Comparison With Other Spectrometric Techniques"
Microchem. J. 1998 Volume 59, Issue 2 Pages 203-218
M. Bettinelli, S. Spezia, U. Baroni and G. Bizzarri

Abstract: Particulate matter in stack effluents of coal-fired plants was collected with an isokinetic probe nozzle suitable for (a) total particulate samplings on membrane filters and (b) sampling with a low volume 10-stage single orifice cascade impactor plus a backup filter. A microwave digestion method using an acid mixture of HNO3-HCl-HF in a closed vessel was developed for the determination of major, minor, and trace elements in very small amounts of sample. Analyses were carried out by inductively coupled plasma mass spectrometry (ICP-MS). A recovery study was conducted using multielemental standard solutions, NIST1633a Trace Elements in Coal Fly Ash and NIST 1648 Urban Particulate Matter, to examine the capabilities of the method. The results for real samples dissolved by this procedure were compared with results obtained by instrumental neutron activation anal., graphite furnace atomic absorption spectrometry, and flow injection hydride generation atomic absorption spectrometry. The anal. capabilities of ICP-MS make it one of the techniques of choice for the determination of trace elements in emission particulate matter collected in different granulometric particle sizes.
Industrial NIST 1633 NIST 1648 Mass spectrometry Sample preparation Method comparison Reference material

"Indirect Potentiometric Determination Of Metal Ions By Flow Injection Analysis With A Copper Electrode"
Anal. Lett. 1984 Volume 17, Issue 4 Pages 309-320
P. W. Alexander; M. Trojanowicz; P. R. Haddad

Abstract: Injections of Mg, Ca, Pb, Co, Cu, Ni, Mn, Ba and Zn (60 µM to 1 mM) into a stream of phosphate buffer solution containing EDTA and a copper wire (0.8 mm diameter), as an indicator sensitive to ligands that bind Cu ions, give peak heights dependent on both the metal ion and EDTA concentration. The theory of the method is presented; it is based on the partial complexation of EDTA present in the carrier stream. Block diagrams are given of the flow cell and the manifold of the flow system. Flow rates (ml min-1) of 4.2 (H2O) and 2.1 (EDTA) were used, with 75 µL injections of samples into the carrier stream by means of a rotary injection valve.
Electrode Electrode Potentiometry EDTA Complexation Indirect

"Flow Injection Analysis - Inductively Coupled Plasma Mass Spectrometry: Study Of Inter-element Effects"
Anal. Lett. 1989 Volume 22, Issue 11&12 Pages 2653-2663
Al Swaidan, H.M.;Lacy, N.;Christian, G.D.

Abstract: A Sciex Elan model 250 ICP-MS instrument was coupled to a flow injection system with water or HNO3 as the carrier stream. In most instances, the addition of HNO3 enhanced and stabilized the signals, particularly for Ag, Mn, Ni, Cu, Pb and Co; most signals became nearly constant above 2% of HNO3.
Mass spectrometry Multielement Interferences

"Extractable Sulfate-sulfur, Total Sulfur And Trace-element Determinations In Plant Material By Flow Injection Analysis. 2. Total Sulfur And Copper, Zinc, Manganese And Iron In Plant Material"
Anal. Lett. 1990 Volume 23, Issue 4 Pages 675-702
D. L. Heanes

Abstract: Oven-dried samples (200 to 500 mg) were digested (at 100 samples per day) with HNO3 containing HClO, NH4NO3 and CaCl2 in a Pyrex tube at 60°C to 220°C (details given). The cooled digest was diluted to 15 mL with water and a flow injection analysis (FIA) system was used for the turbidimetric determination of total S in the supernatant solution, with the use of aqueous 0.01% Brij 35 as carrier solution, aqueous 1% Na ascorbate as sample diluent, and 0.25% of Na2EDTA in 0.1 M NaOH and 11% of BaCl2.2H2O in 1% gum arabic as reagent solution (valve switch timing sequence given). The throughput rate was 120 samples h-1. Calibration graphs were rectilinear for 1 to 200 mg mL-1 of sulfate-S in 0.25 M HClO4. The detection limit was 8 mg kg-1 in plant material. In the determination of 100 mg L-1 of sulfate-S in 0.254HClO4 and the analysis of kale, lucerne hay and oat grain, the coefficient of variation was 0.7% (n = 10). The recovery of 0.2% of S in plants was 97 to 104%. There was no interference from 6% of Ca, 5% of Mg, Na or K, 2.5% of Si, or 0.5% of P or N. A procedure for the FIA of Zn, Mn, Cu and Fe with AAS detection was also described.
Vegetable Oat Lucerne Sample preparation Spectrophotometry Turbidimetry Dilution Calibration Detection limit Interferences

"Simultaneous Measurements Of Trace Metals By Adsorptive Stripping Voltammetry"
Electroanalysis 1989 Volume 1, Issue 3 Pages 229-234
Joseph Wang*, Jawad Mahmoud, Javad Zadeii

Abstract: Simultaneous measurements of trace metals, based on adsorptive stripping voltammetry of their chelates with dihydroxyazo dyes, are demonstrated. Variables affecting the resolution between neighboring chelate peaks, including the ligand and its concentration, pH, adsorption time and potential, concentration ratio, and scan rate, are assessed. Adequate resolution is demonstrated for more than 10 pairs of metals, present at the ppb level. Possible changes in peak heights, associated with competition for the complexing ligand and/or coadsorption effects, are explored. Different concentration ratios of the mixture components can be tolerated. Applicability to seawater analysis is illustrated.
Water Voltammetry

"Reversed-phase High Performance Liquid Chromatographic Separation Of Some Trace Impurities In Oxygen-free Electronic Copper By Post-column Chelation With 4-(2-pyridylazo)resorcinol And Arsenazo-III"
J. Chromatogr. A 1992 Volume 605, Issue 1 Pages 63-68
Rajananda Saraswati and T. H. Rao

Abstract: Cu samples were dissolved in HNO3, boiled, then diluted with water. The solution was subjected to electrolysis at 0.6 A with Pt electrodes to remove the Cu, heated, diluted with water, then portions were subjected to HPLC on a column (30 cm x 3.9 mm) of Spherisorb S-5 ODSI, with a mobile phase (1 mL min-1) of 1 mM octane-1-sulfonate - 0.023 M tartaric acid at pH 5.5 (for Mn, Fe, Co, Ni, Zn, Bi; Group A) or pH 6.0 (for Al, Cr, Zn, Pb; Group B). Post-column derivatization was carried out with 0.25 mM 4-(2-pyridylazo)resorcinol - 23 mM tartrate and detection at 533 nm for Group A metals; or with 1 mM 2,2'-arsenazo III - 0.3% NH3 solution and detection at 600 nm for Group B metals. Absolute detection limits ranged from 0.1 to 2.4 ng.
Metal HPLC Sample preparation Post-column derivatization Chelation

"Improved Method For The Determination Of Manganese In Nuclear Power Plant Waters"
J. Chromatogr. A 1993 Volume 640, Issue 1-2 Pages 371-378
Archava Siriraks and John Stillian, Dennis Bostic

Abstract: Manganese was determined in nuclear power plant water by ion chromatography in a Dionex DX-300 system with pre-concentration. on a MetPac CC-1 column, separation on an IonPac CS12 column with 10 mM HCl/8 mM H3PO4 as eluent (1 ml/min) and cation micro-membrane suppression and conductivity detection with post-column derivatization with 0.4 mM pyridylazoresorcinol/1 M dimethylethanolamine/0.3 M NaHCO3 and detection at 530 nm. The detection limit was 90 pg of Mn (1-3 pg/ml); no calibration ranges or RSD are given.
Waste Waste HPIC Preconcentration Post-column derivatization Metpac

"Determination Of Copper, Nickel, Zinc, Cobalt And Manganese In Seawater By Chelation Ion Chromatography"
J. Chromatogr. A 1993 Volume 640, Issue 1-2 Pages 365-369
Raffaela Caprioli and Sandro Torcini

Abstract: Seawater (100 ml) was mixed with 10^-20 mL of 2 M ammonium acetate of pH 5.4 and pre-concentration of the cited metals was carried out by passing the sample through a MetPac CC-1 column and a TMC-1 column. The metals were eluted from the TMC-1 column with 0.35 M HNO3, after washing with with 0.1 M ammonium nitrate (pH 3.5). Analysis was on a CS5 separation column of mixed ion-exchange resin, equipped with a similar pre-column, with pyridine-2,6-dicarboxylic acid as eluent (1 ml/min) and spectrophotometric detection after post-column derivatization with 4-(2-pyridylazo)resorcinol. Calibration graphs were rectilinear from 0.1 ng (detection limit) to 250 ng of the cited metals; RSD were 0.3-16.2%.
Sea HPIC Spectrophotometry Chelation Preconcentration Metpac Post-column derivatization

"Determination Of Trace Metals In Seawater By Graphite-furnace Atomic Absorption Following Online Separation And Preconcentration"
Spectrochim. Acta B 1993 Volume 48, Issue 1 Pages 91-98
Laerte C. Azeredo, Ralph E. Sturgeon and Adilson J. Curtius

Abstract: The elements Cd, Cu, Fe, Mn, Ni, Pb and Zn were pre-concentrated as their chelates in a flow injection manifold (diagrams given) on a column of silica-immobilized quinolin-8-ol (20 µL) and eluted with 2 M HCl - 0.8 M HNO3 followed by AAS. The recoveries from reference materials were between 92 and 100% with coefficient of variation (n = 4 to 7) from 2 to 12%. The results were close to certified values. Detection limits were from 0.36 to 2.04 ng L-1 for a 5 mL sample.
Sea Spectrophotometry Preconcentration Chelation Reference material Silica 8-Hydroxyquinoline

"Online Precipitation/dissolution System For The Preconcentration And Determination Of Manganese Traces By Atomic Absorption Spectrometry"
Spectrochim. Acta B 1996 Volume 51, Issue 14 Pages 1935-1941
Carola Dittfurth, Evaristo Ballesteros, Mercedes Gallego and Miguel Valc&aacute;rcel*

Abstract: Sample solution (8 or 24 ml; pH 3), containing 40-720 ng of Mn, was injected into a carrier stream of 0.5% H2O2 (at 4 ml/min) and merged with a reagent stream of ammoniacal buffer solution of pH 9 (4 ml/min). The combined streams were heated at 40°C, and the resulting hydrated Mn(IV) oxide was collected on a stainless-steel filter (3 cm2; pore size 0.5 µm). The Mn collected on the filter was dissolved by a stream of 2 M HNO3 (1 ml/min) and carried to a fuel-lean air-acetylene flame. Enrichment factors of up to 55 were obtained. For 8 and 24 mL samples the calibration graphs of peak heights were linear for 5-90 and 1.3-30 ng/ml of Mn and the detection limits were 2 and 1 ng/ml, respectively. Results for digests of biological reference materials agreed with the certified values.
Biological material Sample preparation Spectrophotometry Reference material Preconcentration Precipitation Heated reaction

"Flow Injection Thermospray Sample Deposition For Electrothermal-atomization Atomic Absorption Spectrometry"
Spectrochim. Acta B 1989 Volume 44, Issue 6 Pages 571-579
P. C. Bank, M. T. C. de Loos-Vollebregt and L. de Galan

Abstract: The flow injection thermospray introduction system described previously (Ibid., 1988, 43B, 983) has been modified to obtain more reproducible sample deposition on to the wall of a graphite-tube atomizer. Under optimum conditions, viz, a sample flow rate of 0.7 mL min-1, a thermospray vaporizer temperature of 300°C and a deposition temperature of 120°C in the graphite tube, the sensitivities for Ag, Al, As, Au, Cd, Co, Mn, Pb, Ru and V were identical with those obtained by conventional graphite-furnace AAS. The area of spray-deposited material formed on the wall of the graphite tube is independent of sample volume (unlike conventional manual injection), and thus the flow injection thermospray system can be used over wide analytical ranges. Solutions containing up to 2% of NaCl could be injected without plugging of the thermospray vaporizer capillary.
Spectrophotometry Optimization Interface

"Determination Of Manganese At Trace Levels In Natural Waters With Continuous-flow System Utilizing Online Cation-exchange Separation And Catalytic Detection"
Anal. Sci. 1986 Volume 2, Issue 2 Pages 191-195
T. YAMANE

Abstract: The filtered (0.45 µm, Millipore) sample is made ~0.06 M in HCl and passed through a column of Hitachi Custom Resin No. 2611 (15.5 µm; strong cation exchanger), from which Mn is eluted with 0.2 M Na tartrate - 6 mM tartaric acid - 0.32 M NaCl (pH 5.1). Streams of 52 mM 3,4-dihydroxybenzoic acid (I), 1.5% H2O2 solution and 1.0 M Na2CO3 are pre-mixed in a coil, then mixed in a reaction coil (5 m long) with the Mn-containing eluate. The increase in absorbance at 480 nm, due to the Mn-catalyzed oxidation of I, is recorded. The detection limit with use of a 906 µL sample loop is 0.2 ng mL-1. For river and lake waters containing 1.4 to 11.2 ng mL-1 of Mn, the coefficient of variation was <2.5% (n = 5 or 6). The method shows good selectivity.
Lake River Ion exchange Spectrophotometry Catalysis Column Resin Optimization

"Spectrophotometric Flow Injection Analysis Of Silicates For Manganese"
Anal. Sci. 1987 Volume 3, Issue 3 Pages 251-255
K. OGUMA, K. NISHIYAMA and R. KURODA

Abstract: Powdered silicate rock (100 mg) was fused with anhydrous Li2CO3 - H3BO3 (1:1) at ~1000°C for 15 min. The melt was dissolved in 1 M HCl and diluted. Aliquots of sample solution were treated with HF and HClO4, the mixture was evaporated, the residue was moistened with HClO4 and the acid was evaporated. The residue was dissolved in 1 M HCl, the solution was applied to a column (7 cm x 8 mm) of cellulose phosphate (Whatman P-11) and Mn was eluted with 1 M HCl. An aliquot of the eluate and 1% aminoethanethiol hydrochloride were injected into 1 M HCl and water (carrier solution), respectively, and after mixing, the combined solution was mixed with 0.36 M formaldoxime in NH3 buffer solution (pH 10.5) and passed through a reaction coil in a water bath at 80°C. The absorbance was monitored at 452 nm. The flow injection manifold used is described (with diagram). The coefficient of variation (n = 10) were 0.8 and 0.33%, respectively, for 0.5 and 2 ppm of Mn. The sampling rate was 45 h-1.
Silicate Spectrophotometry Heated reaction

"Determination Of Manganese By Flow Injection Analysis Based On Its Catalytic Effect On The Oxidative Coupling Reaction Of 3-methyl-2-benzothiazolinone Hydrazone With NN-dimethylaniline"
Anal. Sci. 1991 Volume 7, Issue 1 Pages 97-101
Y. MIYATA, T. HIRANO, S. NAKANO and T. KAWASHIMA

Abstract: Sample solution was injected into a carrier stream of aqueous 1.2% H2O2 and reacted at 50°C in a reaction coil (3 m) with 0.1 M citrate - 0.2 M Tris buffer solution (pH 11), 30 mM NN-dimethylaniline - 3 mM 3-methyl-2-benzothiazolinone hydrazone - 3 mM 1,10-phenanthroline. The mixture was cooled to 25°C in a 1-m reaction coil and the absorbance was measured at 590 nm. The calibration graph was rectilinear for 4 to 30 ng mL-1 of Mn and the coefficient of variation were 1.9 to 4.2%. The method was applied in the analysis of standard reference materials, the results obtained compared well with certified values.
NIES 1 NIES 3 NIES 7 Spectrophotometry Buffer Catalysis Heated reaction Reference material

"Determination Of Major And Trace-elements For Certified Reference Material Of Riverine Water JAC-0031 And JAC-0032 By ICP-MS"
Anal. Sci. 1997 Volume 13, Issue 2 Pages 177-182
T. SHIMAMURA and M. IWASHITA

Abstract: Element concentrations were determined by ICP-MS for certified reference materials of riverine water JAC 0031 and JAC 0032 which were recently distributed for a collaborative study to determine certified values. Concentrations were determined of nine elements (Mg, Al, Mn, Ni, Cu, Zn, As, Cd and Pb) out of sixteen elements, which were intended to be certified. An additional eleven trace elements (Li, V, Co, Rb, Sr, Mo, Sb, Cs, Pa, W and U) were also determined. The results obtained for the former nine elements generally agreed well with the values from other laboratories and with certified values. The results obtained for the latter eleven elements were consistent with our previous data, which were obtained from our monitoring project for the same river at a nearby sampling point. 39 References
JAC 31 JAC 32 River Mass spectrometry Reference material Method comparison

"Multielement Determination Of Ultratrace Impurities In High Purity Tantalum Metals By Flow Injection/inductively Coupled Plasma Mass Spectrometry"
Anal. Sci. 1998 Volume 14, Issue 4 Pages 757-762
Shuji KOZONO), Hiromu SAKAMOTO), Ryuma TAKASHI) and Hiroki HARAGUCHI

Abstract: A rapid and sensitive method for the determination of impurity elements in high purity tantalum metals is proposed. Tantalum metals were digested with nitric acid (HNO3) and hydrofluoric acid (HF). The digested sample solutions were injected into a flow injection system with a cation exchange column. Impurity elements adsorbed were eluted with the mixture of HNO3 and HF, and then the effluent was introduced into an ICP plasma with conventional pneumatic nebulization. In the present flow injection/ICP-MS system, the detection limits, based on 3 times the standard deviation of the blank, were in the range 0.03-6 ng/g for the 16 impurity elements (Li, Na, Mg, Mn, Co, Cu, Zn, Ga, Rb, Sr, Cd, In, Ba, Tl, Pb, and Bi).
High purity Mass spectrometry Sample preparation Ion exchange Preconcentration

"Flow Injection Techniques. Analytical Chemistry At The Interface"
Anal. Proc. 1981 Volume 18, Issue 1 Pages 26-31
D. Betteridge, E. L. Dagless, B. Fields, P. Sweet and D. R. Deans

Abstract: In our work we have been concerned exclusively with exploiting the chemical and physical changes that take place across the interfacial region. Insofar as we are dealing with fast reactions in flow systems, two practical problems arise in pursuing this investigation. The first is an instrumental one, resulting from the need to measure concentration profiles across the sample and to process the data obtained. This problem requires the development of sensitive flow detectors that are compatible with digital computers. The second problem is in sorting out and taking advantage of the chemistry that occurs in the few seconds which elapse between the points of injection and detection. This paper presents a progress report of this long-term study.
Refractometry Diffusion coefficients Gradient technique Theory

"Ion-pairing Flow Injection Extraction"
Anal. Proc. 1989 Volume 26, Issue 9 Pages 315-317
M. Harriott, D. Thorburn Burns

Abstract: A flow injection system for automated ion-pairing solvent extraction methods is described and illustrated. The essential components of the system are: (i) a mixing chamber to converge and mix incoming streams; (ii) a segmenter to produce identical alternative segments in the stream; (iii) a phase separator to split the segmented stream into aqueous and organic phases and (iv) a flow cell and detector. The system was applied in the determination of ClO4- in potassium chlorate, Mn and Co in steel and Bi in pharmaceutical preparations (conditions described). Results compared well with stated values.
Inorganic compound Pharmaceutical Alloy Sample preparation Ion pair extraction Mixing chamber Phase separator Segmented flow

"Simultaneous Determination Of Hydride And Non-hydride Forming Elements By Inductively Coupled Plasma Atomic-emission Spectrometry"
Anal. Proc. 1992 Volume 29, Issue 10 Pages 438-439
Zhang Li, Susan McIntosh and Walter Slavin

Abstract: Arsenic, Se, Sb, Bi, Cd, Cr, Cu, Fe, Mn, Ni and Pb were determined in the NIST environmental standard reference materials steel, coal fly ash, urban particulated and 1643b water by ICP-AES. A Perkin-Elmer FIAS-2000 flow injection system was used for hydride generation (experimental conditions tabulated). The sample solution was split into two streams, one being pumped directly to the nebulizer, the other mixed with HCl and NaBH4 solution in the mixing tubes of the chemifold. After separation, the hydride was swept into the spray chamber through a slightly modified cross-flow nebulizer cap. The hydride was then carried into the plasma together with sample aerosol. Recoveries of 20 µg L-1 of As, Sb and Se and 50 µg L-1 of non-hydride forming elements in river- and seawater standards were >80%.
NIST 1643 NIST 1633 NIST 1648 Particulates Alloy Environmental Coal Fly ash River Sea Spectrophotometry Spectrophotometry Reference material FIAS-200 Nebulizer Volatile generation Volatile generation

"Effect Of Anesthesia With Halothane On The Serum Concentration Of Iron, Copper, Manganese, Zinc And Cobalt In Humans Determined By Flow Injection Analysis And Atomic Absorption Spectrophotometry"
Acta Cient. Venez. 1988 Volume 39, Issue 2 Pages 130-134
Alarcon OM, Cuicas H, Rivas E, Burguera JL, Burguera M.

Abstract: n this study serum concentrations of Zn, Cu, Fe, Mn and Co were evaluated in 40 patients 15 to 70 years old: 25 men (62.5%) and 15 women (37.5%), who underwent surgical treatment and were anesthetized with halothane. The flow injection analysis-atomic absorption spectrophotometry technique was used for each element determination. The concentration of these elements in the preoperative samples were within the "normal" range when compared with previously published values. 60 minutes and 24 hours after exposure to halothane, a remarkable trend to increase serum Zn and Cu concentrations was observed. Theses increases in the concentrations of serum Zn and Cu could be attributed to an hepatotoxic effect of halothane and to surgical trauma, respectively.
Serum Human Clinical analysis Spectrophotometry

"Use Of A Flow Injection Ion Exchange-atomic Absorption System For Determination Of Manganese, Lead And Copper"
An. Quim. 1985 Volume 81, Issue 1B Pages 117-121
Hernandez, P.;Hernandez, L.;Vicente, J.;Sevilla, M.T.

Abstract: The method involved use of a micro-column of Dowex A-1 (50 to 100 mesh) for pre-concentration of the elements before AAS; concentration. of <1 ppm could be determined semi-automatically with use of a flow injection system. To analyze welding fumes, the samples, collected on cellulose ester filters, were digested with HNO3 - HClO4, the digests were evaporated to dryness, and solution of the residues were applied to the column. The Mn, Pb and Cu were eluted with 0.3 M HCl, 1 M HCl and 16.3 M NH3 - NH4Cl buffer solution, respectively, and the eluates were analyzed by AAS
Industrial Ion exchange Sample preparation Spectrophotometry Cellulose ester Dowex Preconcentration

"Speciation Of Calcium By Flame Atomic Absorption Spectrometry Using Slurries"
Analusis 1991 Volume 19, Issue 7 Pages 213-217
Martinez Avila, R.;Salvador, A.;De La Guardia, M.

Abstract: Divalent calcium ion and solid Ca3(PO4)2 (I) are determined simultaneously in a single slurry sample (dispersed solid size of 6.3 to 20.5 m) by flame AAS at 422.7 nm with use of an air - acetylene or N2O - acetylene flame and La as an interference buffer. Results are interpreted from two separate calibration plots for dissolved Ca2+ and I, and an equation relating measured absorbance to the intercept and slope of the individual calibration plots and the concentration. of both forms of Ca is presented. Lower limits of detection were obtained with the N2O - acetylene flame, e.g., 0.02 and 0.03 mg L-1 for Ca2+ and I, respectively; the air - acetylene flame was more sensitive (0.048 and 0.028 absorbance units (mg mL-1)-1 for Ca2+ and I. For both flames, the coefficient of variation was 1% for Ca2+ and 3% for I. Results for synthetic samples are reported.
Sludge Spectrophotometry Slurry Speciation

"Online FIA Atomic Spectrometry For The Analysis Of Metal Traces"
Ann. Chim. 1995 Volume 85, Issue 7-8 Pages 443-454
MENTASTI E

Abstract: A review is presented, with 28 references. It is concluded that the practical blank-limited detection limit obtainable by flow injection pre-concentration online with atomic spectrometry has nearly been reached, and that the only further possibility (apart from the impractical use of a larger sample volume) is the development of flow injection ICP-MS. Sensitivity of the pre-concentration to the chemical state of the metal indicates the possibility of using flow injection atomic spectrometry for speciation. Online flow injection analysis (online FIA) for the determination of metal traces by atomic spectrometry is reviewed and discussed with reference to environmental applications. The FIA manifold comprises a microcolumn packed with XAD-2 resin which retains the analytes in form of metal complexes. Successive elution enables the achievement of an enrichment step with which very low detection limits can be reached. (28 references)
Sea Mass spectrometry Sample preparation 8-Hydroxyquinoline Chelex Preconcentration Review Solid phase extraction Speciation

"Catalytic Determination Of Trace Amounts Of Manganese With A Flow Injection System"
Bunseki Kagaku 1984 Volume 33, Issue 12 Pages 652-656
Yamane, T.;Nozawa, Y.

Abstract: A 75 µL portion of the sample solution is injected into a carrier stream of water, which then meets mixed streams of 0.052 M 3,4-dihydroxybenzoic acid(I), aqueous 1.5% H2O2 and 1 M Na2CO3. All four streams are pumped at 0.48 mL min-1. The Mn-catalyzed oxidation of I takes place in a reaction coil (5 m x 0.5 mm), and the absorbance is monitored at 480 nm. The calibration graph (peak heights) is rectilinear up to 40 ng mL-1 of Mn, and the limit of detection is 1 ng mL-1. About 60 determinations can be carried out in 1 h. The coefficient of variation (n = 15) for 10 ng mL-1 of Mn was 2.0%. There is serious catalytic interference from Co, and Fe(III) and Cr(III) also interfere in twenty- and ten-fold excess, respectively.
Water Spectrophotometry Catalysis Interferences

"Simultaneous Determination Of Trace Amounts Of Cobalt And Manganese In High Purity Aluminum By Flow Injection Analysis With Catalytic Method"
Bunseki Kagaku 1988 Volume 37, Issue 7 Pages 360-364
Kitamura, T.;Yamane, T.

Abstract: High purity aluminum was dissolved in HCl and HNO3, the acids were removed by heating and the solution was adjusted to pH 3 with 0.2 M Na tartrate and diluted to 100 mL with water. The solution was injected into the flow system (described) where, after online cation-exchange separation in tartrate - NaCl medium of pH 5.1, Co and Mn catalyzed the oxidation of 3,4-dihydroxybenzoic acid by H2O2 in weakly alkaline medium (Na2CO3). The absorbance was measured at 480 nm. Detection limits were 0.02 and 0.1 µg g-1 in 243 µL of injected solution for Co and Mn, respectively. Interference by other metals was studied. Results agreed well with those obtained by graphite-furnace AAS.
High purity Ion exchange Spectrophotometry Catalysis Indirect Interferences Merging zones Method comparison

"Determination Of Seven Trace Elements In Environmental Water Samples By Inductively Coupled Plasma Mass Spectrometry With Online Preconcentration"
Bunseki Kagaku 1993 Volume 42, Issue 7 Pages 423-428
Akatsuka, K.;McLaren, J.W.;Berman, S.S.

Abstract: An online pre-concentration method was studied to allow the simultaneous determination of Mn, Co, Ni, Cu, Zn, Cd and Pb in 5 mL environmental water samples by inductively coupled plasma mass spectrometry. A semiautomated system with a microprocessor-controlled high performance quaternary gradient pump and valves was used to lead and transport the mobile phase. The system includes a column containing silica-immobilized 8-hydroxyquinoline. The pH of the samples was adjusted to 8 to improve the retention of several elements, in particular manganese. Quantitative elution from the column took 3.5 min with a 1.5 M HCl/0.6 M HNO3 mixture at a flow rate of 2.0 mL min-1. Mn and Co were determined by a standard additions technique, and stable isotope dilution was applied for Ni, Cu, Zn, Cd and Pb. The good precision and accuracy of this method are demonstrated by analyzing standard samples of riverine water (SLRS-2), estuarine water (SLEW-1) and coastal seawater (CASS-2). The detection limits of the method range from 7 ng L-1 for Cd to 130 ng L-1 for Zn. [References: 18]
NRCC SLRS-2 NRCC SLEW-1 NRCC CASS-2 Sea River Mass spectrometry Preconcentration Computer Column Immobilized reagent Silica 8-Hydroxyquinoline Reference material Standard additions calibration

"Rapid Analysis Of Steel By ICP-AES With Electrolytic Dissolution"
Bunseki Kagaku 1996 Volume 45, Issue 8 Pages 777-782
Kondo, H.;Ono, A.;Uemura, T.;Minami, T.

Abstract: In the PC-controlled continuous-flow system described, the sample is dissolved in HCl (1:1) at constant current and the solution is passed to the ICP automatically; a sample can be analyzed in ~e;1 min. Diagrams of the flow system and electrolysis cell are presented, and operating conditions for both the multichannel and sequential determinations of Fe, Si, Mn, Ni, Cu, Al, Ti and Cr are tabulated. The results for standard steels agreed with the certified values. To determine Ti present in inclusions, the samples were best dissolved at constant potential (0.8-1 V) in HCl/HNO3/H2O (1:1:2). Good agreement with certified values was again obtained.
Alloy Spectrophotometry Computer Reference material Multielement

"Integrated FIA - HPLC Method For Preconcentration And Determination Of Transition Metal Ions"
Chromatographia 1992 Volume 34, Issue 9-10 Pages 445-449
P. Richter, J. M. Fern&aacute;ndez-Romero, M. D. Luque de Castro and M. Valc&aacute;rcel

Abstract: Transition and heavy metals (Cd, Co, Cu, Mn, Ni, Pb and Zn) in water were determined by pre-concentration. within a flow injection manifold (details given) comprising two injection valves in series, the loop of valve 1 containing 0.1 M HNO3 and the loop of valve 2 containing a Chelex-100 (ammonium form) micro-column through which a portion of the sample was passed. The loop of valve 1 was opened into valve 2, the concentrated metals were eluted quantitatively onto an HPLC column (25 cm x 4.6 mm) of Ultrabase C18 (5 µm) and were then eluted with aqueous 50 mM tartaric acid and 2 mM sodium octanesulfonate (pH 3.5). Post-column derivatization was with 0.1 mM 4-(2-pyridylazo)-resorcinol monosodium salt in 0.4 M ammonia - 0.2 M ammonium acetate buffer and detection at 500 nm. Calibration graphs were rectilinear from 2 to 200 ng mL-1 with detection limits of 2 to 6.6 ng mL-1 (transition metals) and 24.4 ng mL-1 (Pb). Recoveries were 97.1 to 108.5% and coefficient of variation (n = 11) were 1.6 to 5.1%. An automatic method based on the combination of a flow injection (FI) manifold with a liquid chromatograph has been developed for the enrichment and determination of transition metal ions in water samples. Alternatively, the FI configuration can be used as a screening system for the determination of the total concentration of heavy metals. Two-parameter expressions for calibration graphs involving pre-concentration time and concentration. of the analytes were established for both the FIA and the integrated FIA/HPLC methods. The pre-concentration time depends on the concentration. level of the analytes in the samples. The method is linear in the range 2-200 ng/mL, with RSD values between 1.5 and 5.0. It has been applied to the determination of copper, lead, zinc, nickel, cobalt, cadmium, and manganese in synthetic water samples.
Environmental HPLC Spectrophotometry Chelex Post-column derivatization Preconcentration

"Manganese And Iron In Hydrothermal Plumes Resulting From The 1996 Gorda Ridge Event"
Deep Sea Res. II 1998 Volume 45, Issue 12 Pages 2683-2712
Gary J. Massoth, Edward T. Baker, Richard A. Feely, John E. Lupton, Robert W. Collier, James F. Gendron, Kevin K. Roe, Stacy M. Maenner and Joseph A. Resing

Abstract: We sampled hydrothermal plumes over the N. Gorda Ridge four times between March and August 1996 to document Mn and Fe discharge resulting from a magmatic intrusion/seafloor eruption. Two separate event plumes, EP96A and B, and chronic hydrothermal emissions lasting similar to 6 months were characterized. Shipboard time-series measurements of an event plume sample were used to calibrate an Fe phase clock useful for estimating sample age up to similar to 6 days after fluid discharge. Samples collected from EP96A. and B had Mn/heat (< 0.15 nmol J-1) and Fe/Mn (> 2 mol mol-1) ratios similar to historical event plume observations. We suggest these 'signature' ratio values are generally characteristic of event plumes and hypothesize that Mn and Fe may be supplied to event plumes by different processes: Mn by entrainment of fluids from an extant shallow subseafloor reservoir, and Fe by short-lived, high-temperature water-rock reaction coincident with dike emplacement. Calculations based on the Fe phase clock indicate that the two event plumes were released more than a month apart. The largest event plume, EP96A (similar to 2.3 x 10(6) M Mn and 13 x 10(6) M Fe), formed similar to 7 March soon after seismic activity began. The smaller EP96B (similar to 0.49 x 10(6) M Mn and 3.5 x 10(6) M Fe) was not discharged until similar to 11 April, 3 weeks after the cessation of seismic activity detectable by SOSUS T-phase monitoring. We hypothesize that the subseafloor disturbance that triggered EP96B also resulted in the episodic flushing of a reservoir of chronic-plume-like fluids. Total event plume inventories of Mn and Fe at N. Gorda Ridge are much smaller than those associated with the 1986 event at N. Cleft segment of the Juan de Fuca Ridge, but comparable to event plume inventories at N. Cleft segment in 1987 and CoAxial segment in 1993, Mn/heat values for chronic plumes over the eruption site underlying EP96A evolved from moderate (similar to 0.25 oon-mol J-1, reflecting probable admixture with event plume formation fluids) to high (similar to 0.7 nmol J-1, typical of chronic plumes) to low (similar to 0.1 nmol J-(1,) similar to diffuse vent fluid values), marking a complete episode of intrusion/eruption-induced hydrothermal discharge.
Hydrothermal Sea Spectrophotometry Remote instrument Process monitoring

"Stop-flow Reverse Flow Injection Analysis For Trace Manganese The Manganese(II)-sodium Phosphinate (NaH2PO2)-potassium Periodate NTA System"
Fenxi Huaxue 1988 Volume 16, Issue 4 Pages 315-319
Yuan, Y.;Wang, Y.;Qu, K.

Abstract: The water sample (tap water after removal of Cl by boiling, or polluted or well water after removal of bacteria by filtration) was merged with separate reagents of 1.1 mM KIO4 (40 µL) and 16% hexamine - HCl - NaOH buffer (pH 6.6), containing 0.15 mM NaH2PO2 and 0.3 mM nitrilotriacetic acid, in the stopped-flow apparatus (diagram given), and reacted in a 70-cm tube for 5 min followed by elution and absorbance measurement of Mn(II) at 236 nm. Both sample matrix and the hexamine reagent act as carriers. A rectilinear calibration graph is obtained for up to 5 µg L-1 of Mn(II) and the detection limit is 0.05 µg l-1. For determination of 3 µg L-1 of Mn(II), the coefficient of variation is 3% (n = 10). Most foreign ions, e.g., Al(III), Ba(II) (2 µg mL-1), Cr(VI) (6) and Pb(II) (1.6) do not interfere but Co(II) (>4 ng mL-1) produces a negative interference.
Well Water Spectrophotometry Interferences Reverse Stopped-flow

"Stopped-flow Catalytic Spectrophotometric Determination Of Trace Manganese"
Fenxi Huaxue 1990 Volume 18, Issue 11 Pages 1041-1043
Li, K.;Ren, Y.

Abstract: A flow injection analysis method is proposed (diagram given). Natural water, containing 180 ng of Mn, is mixed with 2 mL of 9 mM nitrilotriacetic acid solution (pH 3.8; I), 5 mL of 0.2 M Na acetate - acetic acid buffer (pH 3.8) and diluted with water to 25 mL. Three reagent streams of viz, 20 µM-Malachite green (C.I. Basic Green 4), 10 mM KIO4 and 10 mM I solution in buffer solution (pH 3.8), are pumped (2 mL min-1) into a reactor for 1 to 2 min with a stopped-flow time of 10 min. The mixture is mixed with a carrier stream of test solution (2 mL min-1) at 52°C in a 2-m coil with detection at 615 nm. The calibration graph was rectilinear for up to 7.2 ng mL-1 of Mn2+ and the detection limit was 0.07 ng mL-1. The coefficient of variation was 3.9%.
Environmental Spectrophotometry pH Buffer Dilution Stopped-flow Calibration Detection limit Heated reaction

"Online Column Preconcentration And Determination Of Trace Elements By Flow Injection Inductively Coupled Plasma - Atomic-emission Spectrometry"
Fenxi Huaxue 1993 Volume 21, Issue 12 Pages 1410-1413
Peng, X.J.;Jiang, Z.C.;Zeng, Y.N.

Abstract: Sample solution was treated with 13.4 µM-meso-tetrakis-(4-sulfophenyl)porphyrin and ammoniacal buffer of pH 9.24 before dilution with water and heating at 100°C for 30 min. The mixture was applied at 1 ml/min to a column of silica gel (10-40 µm) and elution was effected with 2 M HCl. The eluate was sprayed directly into the spectrograph for ICP-AES analysis for Cu, Mn, Ni, Fe, Pd and Cd. The detection limits for these elements were 0.32-26.8 ng/ml and the RSD (n = 6) were 1.3-3%. No interference was observed from co-existing ions. The enrichment factor was 9.3-11.3 and the sampling rate was 12 runs/h. The method was employed in analysis of bovine liver and tomato leaves reference materials.
Liver Leaves Spectrophotometry Preconcentration Reference material Silica gel Column Interferences

"Flow Injection Online Preconcentration With Active Carbon Fibre For Multi-element Determination In Water Samples Using ICP-AES"
Fenxi Kexue Xuebao 1995 Volume 11, Issue 2 Pages 16-20
Lin Yongjing; Gong Zhenbin; Zhuang Zhixia; Deng Zhiwei; Wang Xiaoru

Abstract: The FIA manifold systems for online column flows are shown schematically for pre-concentration and elution regimes. For the determination of Zn, Pb, Ni, Cd and Mn in mineral and seawater, an appropriate amount of the sample was mixed with 1 mL acetic acid/NH4 acetate buffer solution of pH 7 and 3 mL 0.05% quinolin-8-ol. Portions of the solution were injected at 3.1 ml/min on to columns (11-20 mm x 2.2-3.6 mm) of active carbon fiber and the analyte metals were eluted with 3 M HNO3 at 2.7 ml/min. Portions of eluate were injected into the ICP operating with an RF frequency of 27.15 MHz, an RF power of 1.2 kW, carrier gas of 1 l/min and observation height of 15 mm. The recoveries were 97.5-107.2% and the detection limits were 0.2-4 ng/ml.
Mineral Sea Spectrophotometry Preconcentration 8-Hydroxyquinoline Column Carbon fiber

"The Effects Of Organic Carrier Stream On Sensitivities In Flow Injection - Atomic Absorption Spectrometry"
Fenxi Shiyanshi 1986 Volume 5, Issue 10 Pages 16-18
Xuan Weikang and Wang weiping

Abstract: The behavior of twelve elements was studied in flow injection - AAS with eight types of organic solvents as carrier stream and a hydrodynamic conduit in place of an injection valve. Enhanced sensitivity of detection was observed for K, Na, Co, Mn, Fe, Zn, Pb and Ni with isobutyl methyl ketone, n-butyl acetate or TBP as carrier stream and, less markedly, for, Ca, Mg and Cr with Na dodecyl sulfate, hexadecyltrimethylammonium bromide, OP emulsifier or quinolin-8-ol.
Spectrophotometry Sample preparation Chelation Extraction Hydrodynamic injection Optimization Sensitivity

"Preconcentration Of Trace Metals For Their Determination With ICP-AES"
Fortschr. Atomspektrom. Spurenanal. 1984 Volume 1, Issue 1 Pages 491-499
Vos, Gerrit; Van Dordrecht, Peter; Ten Bras, Petrus W. (SFS)

Abstract: Trace metals were determined in natural waters by inductively coupled plasma atomic emission spectroscopy (ICP-AES) after pre-concentration by ion exchange or solvent extraction Chelex 100 [11139-85-8] gave better recoveries of Mn, Co, Ni, Cu, Zn, Cd, and Pb than Amberlite IR 120 [9002-23-7] or 8-hydroxyquinoline [148-24-3] immobilized on SiO2. However, CHCl3 extraction with 4-ethyl-1,2,4-triazole [43183-55-7]/Na diethyldithiocarbamate (I) [148-18-5] or ammonium pyrrolidinedithiocarbamate [5108-96-3]/I gave better results. (SFS)
Environmental Ion exchange Spectrophotometry Sample preparation Preconcentration Solvent extraction Chelex Amberlite 8-Hydroxyquinoline Diethyldithiocarbamate Pyrrolidine dithiocarbamate

"Elimination Of Interferences In ICP-AES By Flow Injection Gradient Technique-generalized Standard Addition Method"
Gaodeng Xuexiao Huaxue Xuebao 1989 Volume 10, Issue 12 Pages 1185-1188
Luo Jianbo, Zhang Zhanxia, Qian Haowen, Cai Mingxiang

Abstract: A method based on a flow injection gradient technique (FIGT) and generalized standard addition method (GSAM) is developed for the elimination of matrix and/or spectral interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). Only one standard for an analyte is used to obtain the signals required for the evaluation in the GSAM. Operating parameters, including the carrier flow rates and residence times, are discussed in detail. To assess the proposed method, two synthetic samples, two types of Cu alloys and steel were analyzed for Zn, Mn, and As respectively. The relative standard deviations are 0.5-1.9%.
Alloy Alloy Spectrophotometry Gradient technique Interferences Standard additions calibration

"Determination Of Copper, Zinc, Iron, Manganese, Sodium, Potassium, Calcium, And Magnesium In Plants And Soil By Flow Injection Atomic Absorption Spectrometry"
Guangpuxue Yu Guangpu Fenxi 1984 Volume 4, Issue 3 Pages 42-47
Zhang Sucun, Sun Lijing, Jiang Hengchun, Fang Zhaolun

Abstract: A FIA Method for the determination of Cu, Zn, Fe, Mn, Na, K, Ca and Mg by AAS was described. When determination of Cu, Zn, Fe, Mn, Na, and K, the water carrier stream was aspirated by nebulizer of AAS. The mono-channel manual rotary valve was used for sampling. The relative standard deviation was 1% at the sampling rate of 514 samples/hr. The merging zone technique was adapted for determination of Ca and Mg. The sample and lanthanum reagent were injected simultaneously into water carrier stream using dual channel manual rotary valve and peristatic pump, After the merging the stream was directed to burner. Consumption of lanthanum reagent was about 1% of that of manual method (0.4 mg/sample). The results obtained agreed well with those obtained by conventional AAS.
Plant Environmental Spectrophotometry Method comparison

"Simultaneous Multi-element Analysis And Matrix Effect Of Sodium Chloride By Flow Injection ICP-AES"
Guangpuxue Yu Guangpu Fenxi 1991 Volume 11, Issue 5 Pages 32-37
Zhang, Z.;Zeng, X.

Abstract: The determination of Cd, Cr, Fe, Mn, Ni, V, Ca, Co, Cu, Mg and Zn by ICP-AES combined with flow injection analysis. The best coefficient of variation and detection limits were obtained with 5- or 10-s integral times. The effects of a NaCl matrix on the elements were studied. The results show that the flow injection technique could reduce analytical signal drift and improve determination reproducibility. The matrix effects of NaCl varied with different r.f. power and the matrix effect of NaCl existed mainly in the evaporation - atomization - excitation process in the ICP.
Inorganic compound Spectrophotometry Multielement Signal drift Interferences

"Study Of The Effects Of Matrix And Acid In Flow Injection ICP-AES"
Guangpuxue Yu Guangpu Fenxi 1992 Volume 12, Issue 3 Pages 49-54
Chen, H.;Jiang, Z.C.;Zeng, Y.N.;Kong, L.Y.

Abstract: To study matrix and acid effects in flow injection ICP-AES, a PGS-2 plane-grating spectrograph was used (working conditions tabulated). Results showed that the introduction of 5 mg mL-1 of matrices (viz. Na, Ca, Fe and Zn) and acids (viz. HCl, HNO3 and H2SO4) caused a decrease in emission intensity of Cr, Mn, Ni, Cu, V, Cd and Zn, but no significant change in excitation temperature and electron density was observed. The matrix interference could be eliminated by adding an appropriate amount of the matrix elements into the carrier.
Spectrophotometry Interferences

"Studies On The FIA-ICP-AES Method. 3. Simultaneous Determination Of Calcium, Sodium, Magnesium, Aluminum, Iron, Copper, Chromium, Manganese And Zinc In Biological And Clinical Samples"
Huanjing Huaxue 1989 Volume 8, Issue 1 Pages 68-73
Chen, Hao; Kong, Lingying; Jiang, Zucheng; Zen, Yune; Cheng, Zhujun; Hu, Hongxing

Abstract: A method has been developed for the determination of Ca, Na, Mg, Al, Fe, Cu, Cr, Mn, and Zn in biological and clinical samples by using the FIA-ICP-AES technique. Several factors including volume of sample introduced, exposure time, and ICP operating conditions influencing the analysis were investigated. Under optimum experimental conditions, the detection limits for the analytes were 0.032-6.5 mg/mL, the relative standard deviations are in the range 0.58-2.8% (n = 10), and the recoveries of the method are higher than 90%. The results obtained show that the FIA-ICP-AES technique is superior to the method of continuous nebulization ICP-AES in analysis efficiency, precision, matrix effect, and introducing the amount of sample. This method has been applied to the analysis of a variety of biological and clinical samples.
Biological material Spectrophotometry Clinical analysis Optimization Method comparison

"Flame Atomic Absorption Spectrometric Determination Of Copper, Lead, Cadmium, And Manganese In Natural Waters Using A Flow Injection System With Online Ion Exchange Preconcentration"
Huanjing Kexue 1995 Volume 16, Issue 5 Pages 54-56
Wang Peng

Abstract: The title method was developed, and some practical considerations in the design of online column pre-concentration FIA system for FAAS were studied. The relative standard deviation was about 2.0% (n=11) at a sampling frequency of 45 h-1 with an enrichment of around 20 times. The advantages, such as high-efficiency, online, accuracy, precision, micro-amount of sample, automation et al., made it possible to be applied to the routine analysis of natural waters.
Environmental Spectrophotometry Speciation Preconcentration Precision

"Determination Of Manganese In Vegetables And Medicinal Plants Using Flow Injection System"
Indian J. Technol. 1990 Volume 28, Issue 2 Pages 78-80
Devi, S.

Abstract: Sample solution (20 µL) was injected into a flowing stream (1 mL min-1) of methanolic 1 mM 2-acetylpyridine thiosemicarbazone (I) and buffer solution (pH 9.0), and the Mn(II) - I complex was extracted into CHCl3 by passage along a 50-cm coil. The phases were separated in a PTFE separator, and the absorbance of the organic phase was measured at 410 nm. The calibration graph was rectilinear for 50 to 150 µM-Mn, and the detection limit was 0.5 µM. The sampling rate was 60 h-1. The method was applied to plant material after dry ashing and acid dissolution. Results showed good agreement with those of AAS.
Vegetable Plant Sample preparation Spectrophotometry Sample preparation Buffer Calibration Extraction Method comparison Phase separator Organic phase detection

"Slurries Introduction In Flow Injection Atomic Absorption Spectroscopic Analysis Of Sewage Sludges"
J. AOAC Int. 1990 Volume 73, Issue 3 Pages 389-393
Martinez-Avila, R.; Carbonell, V.; Guardia, M. de la; Salvador, A

Abstract: The effects were studied of flow injection parameters on the determination of Cu, Mn and Pb in sewage sludge, by injection of a sample into a carrier stream and detection by air - acetylene flame AAS. Samples were pre-digested with HNO3 with heating in a microwave oven. AAS instrumental parameters are given for each metal. The limits of detection were 0.06, 0.05 and 0.3 ppm, respectively, which are adequate for analysis of real samples. The method was applied to two reference materials; accuracy was better than that obtained by continuous aspiration.
Sludge Spectrophotometry Sample preparation Slurry Detection limit Reference material

"Autocatalysis In The Spectrophotometric Flow Injection Determination Of Manganese As Permanganate. Soil, Plant And Rock Analysis"
J. Braz. Chem. Soc. 1990 Volume 1, Issue 1 Pages 28-34
M. Mesquita, A O Jacintho, E. A G. Zagatto and R. F. Antonio

Abstract: Periodate oxidation was carried out under acidic conditions at ~95°C. The reaction rate was accelerated by exploiting the autocatalytic effect which was enhanced with addition of a permanganate confluent stream. Reagent concentration, permanganate addition, level, acidity, flow rates, color stability and interference effects were studied. Hydrochloric acid was tolerated up to 0.5M. Detection limit was ~0.3 mg L-1 Mn. Analysis time was 60 h-1. Results agreed well with those obtained by AES.
Plant Environmental Geological Spectrophotometry Catalysis Interferences Detection limit Method comparison Heated reaction

"Measurement Of Trace Metallic Contaminants On Silicon Wafer Surfaces In Native And Dielectric Silicon Oxides By Vapor Phase Decomposition Flow Injection Inductively Coupled Plasma Mass Spectrometry"
J. Electrochem. Soc. 1993 Volume 140, Issue 4 Pages 1105-1109
J. Fucsko, S. S. Tan, M. K. Balazs

Abstract: The concentration of trace metals on silicon wafer surfaces was measured using a novel highly sensitive multi-element analytical method, called vapor phase decomposition flow injection inductively coupled plasma-mass spectrometry (ICP-MS). Metallic contaminants result in a deterioration in the performance and yield of semiconductor devices. ICP-MS uses hydrogen fluoride vapor to decompose and release metal contaminants from surface oxides. The metals are collected by scanning a small drop of dilute acid solution throughout the surface of the wafer and are measured by ICP-MS using flow injection sample introduction. As many as 60 elements can be determined with detection limits ranging from 108 to 1011 atom/cm2. ICP-MS has the potential to serve as a reference technique for the calibration of surface analytical methods, as well as offering an improved technique for measuring trace metals. One or more Si wafers were loaded into a specially constructed vapor-phase decomposition box containing a reservoir of HF solution The exposure time depends on the thickness of the oxide layer, 20 min for 15-30 .angstrom., 3-12 h for 2000-10 000 .angstrom.. A single drop of HF was then placed on the wafer surface and carefully rolled over the surface to extract the trace metals. The drop was transferred to a small sample tube and injected into the Ar ICP torch assembley with a cross-flow pneumatic nebulizer. Calibration was performed using multi-element standard solution For solution containing either 0.8 or 4.0 ppb of Mg, Cu, and Ni, and Cu the precision (n = 10) was ± 15% and ± 8%, respectively. The recovery of trace metals spiked on to bare Si wafers varied from 90-110% for Al, Cr, Fe, Ni and Na at surface concentration. of 5.67 x 1010-63.5 x 1010 atom/cm2. The recovery of Cu was 8.3% with the experimental conditions used. The detection limits were 108-109 atom/cm2 for Cr, Co, Fe, Pb, Mg, Mn, Ni, K, V, Zr, 2 x 1010 for Al and Fe and 1 x 1010 for Na. The procedure was applied to the determination of metal contaminants on bare Si wafers from different sources. Aluminum, Fe and Na are the most common metal contaminants.
Metal Inorganic compound Mass spectrometry Multielement

"Flow Injection Determination Of Manganese Using Malachite Green-periodate Catalytic Reaction"
J. Flow Injection Anal. 1988 Volume 5, Issue 1 Pages 14-22
Susumu Kawakubo, Tsugio Fukasawa, Masaaki Iwatsuki and Tsutomu Fukasawa*

Abstract: A flow injection system is described (with diagram); sample solution (20 µL) is injected into a carrier stream of 0.44 µM-malachite green (C. I. Basic Green 4) and 1.7 mM IO4- in 2 M Na acetate - 10 M acetic acid (pH 4.4; 5:2) and the mixture is passed through a reaction coil in a water bath at 50°C ± 1°C. The decrease in absorbance is measured at 615 nm. The calibration graph is rectilinear up to 2 ng of Mn. With use of a 2-m reaction coil the determination limit was 0.04 ng of Mn and the coefficient of variation (n = 5) at 1 ng of Mn was 1.8%; corresponding values obtained with use of a 4-m coil were 0.03 ng and 1.3%.
Spectrophotometry Heated reaction Indirect

"Catalytic Determination Of Trace Elements By Flow Injection Analysis"
J. Flow Injection Anal. 1994 Volume 11, Issue 1 Pages 7-23
Teshima, N.;Nakano, S.;Kawashima, T.

Abstract: A review is presented of the use of catalytic reactions in FIA methods for trace analysis. Catalytic reactions are easily controlled in FIA by fixing the flow rate of the solution and the length of the reaction coil. Diagrams of the flow manifolds for Mn and V determinations are also presented. (56 references).
NIST 1643 Catalysis Review

"Simple, Rapid, And Precise Determination Of Manganese In Iron And Steel By Flow Injection Analysis"
J. Iron Steel Inst. Jpn. 1993 Volume 79, Issue 4 Pages 492-496
Takeshi YAMANE, Masae SAITO

Abstract: In order to improve the simplicity, rapidity, accuracy and precision in the chemical analysis of iron and steel, a flow-injection analysis (FIA) has been studied for manganese determination with photometric detection. The FIA system consists of a direct on-line coupling of coloring reaction and absorbance measurement in a continuous now mode ; manganese is oxidized by ammonium peroxodisulfate to MnO4- and the absorbances of the resultant solution are measured before and after the addition of sodium nitrite. The FIA manifold and the optimum reaction conditions were established for allowing this simultaneous measurements of analytical and blank signals by single sample injection with single detector. The analytical results by the proposed method for four Japanese standards of steel (The Iron and Steel Institute of Japan) agreed well with the certified values for manganese and showed high precision of relative standard deviations of 0.25-0.50% which are much smaller than those usually observed in manually operated spectrophotometric methods. An injection rate of 12 sample solutions/h can be achieved. The most appealing feature of the proposed method is that the analysis is achieved in a continuous and nearly closed system without complicated manual operations, which can afford simpler and rapid as well I as accurate and precise determination of manganese.
Metal Alloy

"Manganese Levels In Serum Of Healthy Venezuelan Infants Living In Merida"
J. Trace Elem. Med. Biol. 1996 Volume 10, Issue 4 Pages 210-213
Alarcon OM, Reinosa-Fuller JA, Silva T, Ramirez de Fernandez M, Gamboa J

Abstract: Taking up where a previous paper had left off (10) the purpose of this study was to examine in further detail the serum concentration of manganese of 180 apparently healthy Venezuelan infants (96 boys and 84 girls) ranging from 5 days to 12 months old, all residents of Merida. The flow injection analysis atomic absorption spectrophotometric technique was used for the determination of manganese. The mean values of serum manganese were 0.42±0.12, 0.41±0.11, 0.39±0.13, 0.39±0.1, 0.38±0.09, 0.37±0.11, 0.36±0.12 and 0.29±0.10µg/L in infants 5 days and 1,3,5,7,10,11 and 12 months old, respectively. These values indicate that the average concentration of manganese in serum decreases with age, but the mechanism involved is not yet known, nor are the consequences of the decrease. The statistical analysis did not show any significant influence of sex on the serum value of the metal in the age range of 5 days to 12 months.
Serum Human Spectrophotometry

"Catalytic Determination Of Manganese By A Micro Ion Exchange Separation - Flow Injection Method"
Kenkyo Hokoku 1987 Volume 50, Issue 11 Pages 211-216
Zhang, C.L.;Kawakubo, S.;Fukasawa, T.;Iwatsuki, M.;Fukasawa, T.

Abstract: A combined ion-exchange separation and flow-injection anal. method was proposed for the determination of 0.2 to 7 ng of manganese, and applied to Mn determination in HF, HNO3, HCl, hydrochloric acids, Si, and Ti samples. A silicon or titanium sample was decomposed by the above acids, adjusted to be 1.5 M in HF and 0.2 M in HCl and followed by a cation-exchange separation using a microcolumn. The adsorbed manganese was eluted with 0.2 mL of 6 M HCl. Any acid samples described above and the eluate containing manganese were evapd. to dryness. The residue was dissolved and made to 300 µL (or more) of a 0.1 M acetate buffer solution (pH 4.4). A 100 µL aliquot was analyzed by the flow injection analysis based on the Malachite Green-periodate catalytic reaction. (SFS)
Metal Metal Ion exchange Catalysis

"Determination Of Manganese By Malachite Green-periodate Catalytic Reaction With Concentrated Reagents And Its Application To Flow Injection Analysis"
Kenkyu Hokoku 1986 Volume 49, Issue 2 Pages 147-152
Kawakubo, S.;Fukasawa, T.;Iwatsuki, M.;Fukasawa, T.

Abstract: Mn was determined by its catalytic action on the redox reaction in malachite green-IO4- system at pH 3.3. The induction period could be eliminated with concentrated solutions of the reagents at higher temperature (48°C). From the decrease in absorbance at 615 nm, 2-200 ng Mn was determined by the batchwise method, whereas 0.03-2 ng Mn/20 µL by flow-injection analysis. (SFS)
Water Spectrophotometry Catalysis Heated reaction Indirect

"Flow Injection Spectrophotometric Determination Of Manganese In Electroplating Solutions"
Lihua Jianyan, Huaxue Fence 1989 Volume 25, Issue 4 Pages 207-208
Tao, S.;Hu, X.;Wang, H.;Lin, S.

Abstract: A 2 mL sample, obtained by tenfold dilution of the electroplating solution, is mixed with 3 mL of aqueous NH3 and 3 drops of 3% H2O2 solution and then heated in a water bath (at 80°C) for 2 min before addition of 3 drops of 0.2% Na2OsO4 solution. After being cooled, the mixture is centrifuged at 4000 rpm, and the ppt. is dissolved in 3 mL of 2 M H3PO4 and 0.5 mL of 1 M KI. The solution is diluted with water to 25 mL. The I3- produced (stable for 24 h) is determined by flow injection spectrophotometry, with water as carrier stream and detection at 400 nm. Beer's law is obeyed for 0 to 1.6 mg mL-1 of Mn. Recovery was 100 to 103%. Results agreed well with those by ICP-AES. For determination of 0.4 mg of Mn, NaCl (200 mg), Ni (100 mg), Co or BO33- (10), Cu (5), and Fe(III), Cr(III), Cd or Sn(II) (1) did not interfere.
Industrial Spectrophotometry Interferences Indirect Method comparison

"Flow Injection Catalytic Spectrophotometric Determination Of Trace Manganese By Use Of The Reaction System Nitrilotriacetic Acid-manganese(II)-fuchsine-potassium Periodate"
Lihua Jianyan, Huaxue Fence 1994 Volume 30, Issue 2 Pages 86-88
Zi, Y.Q.;Chen, L.G.;Zeng, Q.G.

Abstract: Mn(II) solution (0.1 ml) was injected into the flow injection analyzer. to mix with a stream of 0.12 mM basic fuschine before further mixing and reaction with streams of 0.2 M acetic acid/0.2 M sodium acetate buffer of pH 4.5, 3 mM nitrilotriacetic acid and 15 µM-KIO4 (all streams at 2.52 ml/min) in a 130 cm reaction tube in a constant-temp. bath of 75°C, cooling in a 40 cm tube with running water as coolant and measurement of the decreased absorbance at 540 nm. The response was linear for up to 0.35 µg/ml, and the detection limit was 0.3 ng/ml. There was no interference in the determination of 0.1 µg/ml of Mn. The sampling frequency was 24 per h. The method was applied to environmental water, soil and cereals, including wheat and beans, with RSD of 1.3%.
Environmental Environmental Wheat Vegetable Spectrophotometry Catalysis Heated reaction Interferences

"Determination Of Dissolved Manganese In Seawater By Flow Injection Analysis With Colorimetric Detection"
Limnol. Oceanogr. 1993 Volume 38, Issue 6 Pages 1290-1295
MALLINI, LEANNE J., AND ALAN M. SHILLER

Abstract: A flow injection technique for the determination of dissolved Mn in seawater and other natural waters has been developed. The technique utilizes the Mn-catalyzed oxidation of tiron by peroxide. The reaction product is determined colorimetrically. Sensitivity is enhanced and salt effects minimized through on-line pre-concentration of Mn. For a 3 mL sample, a detection limit of 40 pmol kg-1 is possible. Use of a lab-built colorimetric detector can provide an inexpensive alternative to a commercial flow-through spectrophotometer.
Sea River Spectrophotometry Preconcentration Indirect Interferences

"Simultaneous Measurement Of Oxide, Manganese, Iron, Iodide, And Sulfide In Marine Pore Waters With A Solid-state Voltammetric Microelectrode"
Limnol. Oceanogr. 1998 Volume 43, Issue 2 Pages 325-333
Luther, George W., III, Paul J. Brendel, Brent L. Lewis, Bj&oslash;rn Sundby, Lucie Lefran&ccedil;ois, Norman Silverberg, and Donald B. Nuzzio

Abstract: A solid-state Au/Hg voltammetric microelectrode was used to measure, simultaneously and with millimeter spatial resolution, the vertical distributions of O2, Mn2+, Fe2+, HS-, and I- in the pore water of sediments from the Canadian continental shelf and slope. The electrode was used shipboard to analyze undisturbed sediment cores and in a sediment mesocosm to determine the three-dimensional distribution of redox species in the sediment surrounding an actively irrigated worm burrow. In cores from Emerald Basin and Cabot Strait, O2 disappeared and Mn2+, Fe2+, and HS- appeared in the vertical sequence predicted on the basis of thermodynamics. In a core from the Scotian slope, O2 disappeared at ~14-mm depth but Mn2+ was not detected over the 50-mm depth examined with the probe. In all three cores, I- was detected in the pore water below the oxygen-penetration depth. In none of the cores did the distributions of O2 and Mn2+ overlap. The thickness of the layer within which neither O2 nor Mn2+ could be detected ranged from 8 to 40 mm; we suggest that nitrate, not oxygen, is used to oxidize Mn2+. The upwarddirected Mn2+ gradients of 3.5 and 10 mol mm4 in the Emerald Basin and Cabot Strait sediments, respectively, drive manganese fluxes that are more than one order of magnitude lower than the O2 fluxes, which are estimated at 4-S mmol mm 2 d-1. The three-dimensional distributions of solutes in the pore water in the sediment surrounding an irrigated worm burrow demonstrate that both the O2-penetration depth and the depth where Mn2+ is first detected are deeper in the vicinity of the worm burrow than away from it. This is consistent with the notion that irrigation brings oxygenated water into the worm tube, allowing oxygen to diffuse across the burrow wall into the sediment and react with Mn2+ and other reduced porewater constituents. Three-dimensional heterogeneity in porewater composition cannot be detected by conventional one-dimensional coring and slicing techniques. Because these latter techniques average the porewater composition in a large volume of sediment, they may indicate that the distributions of individual species overlap when in fact they do not.
Sea Environmental Voltammetry Electrode Simultaneous analysis

"Spectrophotometric Determination Of Dissolved Manganese In Natural Waters With 1-(2-pyridylazo)-2-naphthol: Application To Analysis In Situ In Hydrothermal Plumes"
Mar. Chem. 1992 Volume 37, Issue 1-2 Pages 65-82
Carol S. Chin, Kenneth S. Johnson and Kenneth H. Coale

Abstract: In the described flow injection system, the seawater sample (300 µL) is injected into the carrier stream (low-Mn seawater; 0.8 mL min-1), which then merges with a stream of 1-(2-pyridylazo)-2-naphthol - Triton X-100 - borate buffer solution (pH 9.7 to 10.0) containing desferrioxamine to mask Fe (0.15 mL min-1). The combined streams pass to a glass bead mixing column (50 cm) and the absorbance of the resulting solution is measured in a flow-through cell at 560 nm. Temperature and pressure did not adversely affect the sensitivity. The method was tested by application in situ to hydrothermal plumes with use of a submersible chemical analyzer.; the detection limit was ~22 nM.
Sea Spectrophotometry Triton X Glass beads Single bead string reactor Remote instrument Surfactant

"Flow Injection Determination Of Trace Manganese With Catalytic Photometric Detection"
Mem. Fac. Arts Sci. Yamanashi Univ. 1980 Volume 31, Issue 1 Pages 47-52
Yamane, Takeshi

Abstract: NA
Spectrophotometry Catalysis

"Microscale Ion-exchange Separation And Flow Injection Catalytic Determination Of Manganese In High-purity Sodium Chloride"
Nippon Kaisui Gakkaishi 1989 Volume 43, Issue 1 Pages 48-53
Susumu KAWAKUBO, Masaaki IWATSUKI, Tsutomu FUKASAWA

Abstract: A technique for microscale ion-exchange separation of manganese at 0.1 ng levels was developed and combined with flow-injection spectrophotometry based on manganese-catalyzed oxidation of malachite green with periodate. A sample (0.2 to 1.5g) was dissolved in less than 4.5 ml of a 0.04 M ammonia - 0.16 M ammonium chloride buffer solution (pH 9). The solution was then passed through a chelate resin µcolumn of 20 µl capacity (Dowex A-1, 50 to 100 mesh) to adsorb manganese and to remove the interfering matrix salt. The adsorbed manganese was eluted with 0.3 ml of 2 M nitric acid. A column of 10 µL capacity could be used for less than 1 ml of the sample solution. After evaporation of the effluent, the residue was dissolved with 0.1 M acetate buffer solution (pH 4.4), and a 100 µL aliquot was injected into a flowinjection system. The reduction of absorbance of malachite green was measured at 615 nm after reaction for 6.5 min at 50°C. Manganese of ppb levels in high purity salt is determined within a standard deviation of about 0.1 ppb.
High purity Ion exchange Spectrophotometry Catalysis Preconcentration Interferences

"Selective Accumulation Of Elements By Plants Synthesizing Saponin"
Appl. Biochem. Microbiol. 1997 Volume 33, Issue 6 Pages 641-642
LOVKOVA M.JA., PONOMAREVA S.M., SOKOLOVA S.M., SHELEPOVA O.V., BUSUK G.N.

Abstract: Elemental compositions (including 4 macroelements and 16 microelements) of 15 medicinal plant species synthesizing saponin were determined by atomic absorption spectrometry of wet-ashed and dry-ashed samples on a Z-6000 spectrophotometer (Hitachi, Japan) and a FIA-Star flow injection analyzer (Tecator, Sweden), the. These species were shown to selectively accumulate nine elements (Fe, Cr, Zn, Mn, Co, Al, Cu, Ba, and V) whose levels were considerably (more than 30-fold) higher than the respective average levels for plants growing in the same climatic zones. The ability of saponin-synthesizing species to accumulate certain elements, as well as low variance of the concentrations of the majority of such elements combined with high coefficients of correlation between them, suggest that these species have a specific elemental composition.
Plant Spectrophotometry Tecator

"Pneumatic Nebulizer As A Dilution Chamber In A Flow Injection System For Multielement Analysis By ICP-MS"
Quim. Nova 1998 Volume 21, Issue 4 Pages 405-409
Gomes Neto, Jos&eacute; Anchieta; Silva, Jos&eacute; Bento B.; Rodrigues Neto, Renato; Curtius, Adilson Jos&eacute;; Souza, Ivan G.

Abstract: An automatic dispenser based on a flow injection system used to introduce sample and anal. solution into an inductively coupled plasma mass spectrometer through a spray chamber is proposed. Anal. curves were constructed after the injection of 20 to 750 µL aliquots of a multielement standard solution (20.0 µg L-1 in Li, Be, Al, V, Cr, Mn, Ni, Co, Cu, Zn, As, Se, Sr, Ag, Cd, Ba, Tl, Pb) and the acquisition of the integrated transient signals. The linear concentration. range could be extended to ~five decades. The performance of the system was checked by analyzing a NiST 1643d reference material. Accuracy could be improved by the proper selection of the injected volume Besides good precision (relative standard deviation <2%), the results obtained with the proposed procedure were closer to the certified values of the reference material than those obtained by direct aspiration or by injecting 125 µL of several anal. solutions and samples.
NIST 1643 Mass spectrometry Dilution Nebulizer Reference material

"Note. Determination Of Mineral Elements In Honey From Different Floral Origins By Flow Injection Analysis Coupled To Atomic Spectroscopy"
Rev. Espan. Cienc. Tecnol. Aliment. 1994 Volume 34, Issue 4 Pages 441-449
Mercedes Lozano Ruiz, E. Osorio, F. Salinas, Vicente Montero de Espinosa

Abstract: A flow injection analysis coupled to atomic spectroscopy was developed to determine Ca, Mg, Mn, K, Na and Zn in honey. The method involved a 30 cm dispersion tube length, 6 ml/min carrier solution flow-rate and 430 µL sample volume. Detection limits (in µg/g) were: Ca, 1.6; Mg, 4.8; Mn, 0.8; K, 27.0; Na, 3.6 and Zn, 0.4. Levels of these minerals in 19 Eucalyptus, 11 Helianthus annuus, 18 honeydew, 3 heather and 23 multifloral honeys are reported.
Nectar Nectar Nectar Spectrophotometry

"Determination Of Cobalt And Manganese In Blood Serum By Flow Injection Analysis And Atomic Absorption Spectroscopy"
Rev. Roum. Chim. 1986 Volume 31, Issue 3 Pages 353-360
Leon, N.;Burguera, J.L.;Burguera, M.;Alarcon, O.M.

Abstract: In the flow injection system described, the serum was manually injected, by means of a micro-syringe, into the sample-injection unit (Rocks et al., Anal. Abstr., 1984, 46, 8D21) and thence into a continuously aspirated carrier stream, which was fed to the nebulizer of an AAS instrument (air - acetylene flame). Absorption measurements were effected at 240.7 nm (Co) and 279.5 nm (Mn), and the working range of the method was 0.001 to 0.18 µg mL-1 of Co and 0.008 to 0.1 µg mL-1 of Mn. The sample throughput was ~120 h-1, and the within- and between-batch coefficient of variation (n = 12) were ~3.5 and 2.9% for Co and ~3.2 and 3.4% for Mn. Samples were sufficiently small to allow the method to be used for the analysis of paediatric serum.
Serum Human Clinical analysis Spectrophotometry

"The Semi-automated Determination Of Manganese In Seawater With Leuco-malachite Green"
Sci. Total Environ. 1986 Volume 49, Issue 1 Pages 101-113
J&oacute;n &Oacute;lafsson

Abstract: The determination of manganese in sea water by the leuco-malachite green method of Strickland and Parsons (1968) has been automated and the reaction conditions modified and optimized. The sensitivity is 0.024 µg Mn l-1, and the coefficient of variation is 1.3% at 0.9 µgMn L-1 and 13% at 0.06 µgMn l-1. The method is not suitable for samples from estuaries, but can give valuable information on the continental shelf distribution of manganese and on geothermal signatures.
Sea

"Ion-chromatographic Determination Of Total Metals In Soils"
Soil Sci. Soc. Am. J. 1990 Volume 54, Issue 5 Pages 1289-1297
N. T. Basta and M. A. Tabatabai*

Abstract: Surface soil samples (2 g) were digested sequentially with concentrated HNO3, HClO4 and HF. The HF treatment was repeated until dissolution was complete. An aliquot (25 ml) of the resulting solution was treated with ammonium citrate buffer (5 ml), hydroxylammonium chloride solution (2 ml) and pyridine (2.5 ml). The solution, pH adjusted to 9.5 with 10 M NaOH, was extracted with 0.2% of dithizone in CHCl3 (2 x 15 ml). The combined extracts were evaporated to dryness and the residue was treated with concentrated HNO3 (3 ml) and again heated to dryness. The residue was dissolved in 0.1 M HCl and analyzed on a HPIC-CS 5 column equipped with a HPIC-CG 5 guard column with buffered 4 mM 2,6-pyridinedicarboxylic acid (pH 4.8) or 40 mM oxalic acid (pH 4.8) as mobile phase (1 mL min-1). Post-column derivatization was achieved by mixing the column effluent with a stream of 0.01% ammoniacal solution of 4-(2-pyridylazo)resorcinol and 0.02% NN-dimethylethanolamine; the absorbance of the metal complexes was measured at 520 nm. Results obtained for Cu, Ni and Zn agreed with those obtained by AAS; low results were obtained for Cd, Mn and Pb. With oxalic acid as eluent, the detection limits were 5 µg L-1 for Cu and Zn and 20 µg L-1 for Ni; the coefficient of variation were 4.9% (n = 6).
Environmental HPIC Sample preparation Spectrophotometry Buffer Column Post-column derivatization Detection limit Method comparison Complexation Dithizone

"Automated Analyzer ADM300 With Microcomputer-controlled Evaluator AE2-2"
Wasserwirtsch. Wassertech. 1985 Volume 35, Issue 5 Pages 98-99
Mueller, Albrecht; Eulenberg, Horst; Kopprasch, Wolfgang

Abstract: The ADM 300 analyzer for flow-injection anal. of water has a AE2-2 microcomputer-controlled evaluator and can process ~160 samples/day. The flow injection analysis app. can be used for determination of Fe, Mn, NH4+, NO2-, and NO3- in drinking water; P and N determinations in water monitoring; and Fe and P determination in optimization of the use of pptg. agents in wastewater treatment. (SFS)
Waste Water Computer Precipitation

"Flame Atomic Absorption Spectrometry With Flow Injection Sample Introduction For The Determination Of Heavy Metals In Biological Materials"
Wiss. Z. Univ. Halle 1987 Volume 36, Issue 1 Pages 3-15
Friese, K.;Matschiner, H.

Abstract: The cited method was applied in the determination of Mn in hair, Cr in biological tissues and Pb in blood. The coefficient of variation were 5.8, 8.1 and 1.7% for 1.9 ppm of Mn, 0.07 ppm of Cr and 4.6 µM-Pb, respectively.
Biological tissue Blood Hair Spectrophotometry Theory

"Single-standard FIA Gradient Calibration Technique In Catalytic Kinetic Spectrometric Determination"
Yingyong Huaxue 1991 Volume 8, Issue 2 Pages 75-77
Yang Jiannan, Zang Shuliang, Jiang Yufen, Liu Gang

Abstract: In combination with microprocessor, by using FIA stopped-flow technique and gradient calibration, a single standard catalytic kinetic spectrophotometric method is described. The method is simply operated and good reproducible. It has been used in determination of trace Mn(II) in natural water. The results were in accordance with those obtained using Otto-Rentsch-Werner method in literature.
Environmental Spectrophotometry Calibration Catalysis Gradient technique Kinetic Stopped-flow

"Ion Chromatography Of Cations And Anions In Mineral Waters"
Z. Lebensm. Unters. Forsch. 1990 Volume 190, Issue 3 Pages 205-211
Georg Schwedt und Hans -Heinrich Schaper

Abstract: Various procedures are examined for the separation of Li, Na, K, Ca, Mg, Mn, HCO3-, Cl-, SO42- and NO3- by using silica gel, polymer-based and reversed-phase ion exchangers, with conductivity or spectrophotometric detection [after post-column derivatization with 4-(2-pyridylazo)resorcinol - Zn - EDTA for Ca, Mg and Mn]. Three injections with two separation systems are sufficient to determine nine ions in 30 min. Thus, Ca, Mg and Mn can be determined simultaneously in 16 min on a Partisil SCX column, with a mobile phase containing 2.5 mM oxalic acid and 2 mM ethylenediamine. Lithium, Na, K, Ca and Mg are determined simultaneously on a column consisting of a butadiene - maleic acid polymer on Nucleosil 5, with 10 mM tartaric acid as mobile phase. Calcium Mg and the anions are determined simultaneously on a Nucleosil 10 SB or PRP X-100 column, with EDTA solution as mobile phase. Results for fifteen samples are reported and agree well with those obtained by AAS.
Mineral Ion exchange Spectrophotometry Spectrophotometry Silica gel Post-column derivatization EDTA Column Method comparison

"Automated System For Rapid Flow Injection Extraction - Atomic Absorption Spectrometric Analysis Of Heavy Metals In Solutions"
Zavod. Lab. 1996 Volume 62, Issue 12 Pages 26-28
Kirko, E.V.;Sorokina, N.M.;Galdina, N.N.;Tsizin, G.I.;Zolotov, Y.A.

Abstract: The apparatus consisted of a peristaltic pump, two injection valves, an extraction column and an AAS instrument controlled by a computer. Samples were applied to the extraction column, the heavy metals were eluted with 2 M HNO3 and the eluate was analyzed by AAS. The column was regenerated periodically with 1 M ammonium acetate buffer. The extraction column, of ~0.1 mL capacity, contained a weak cross-linked polystyrene resin with diethylenetriaminetetra-acetate groups. The flow-through the column was 2-10 ml/min. The limits of detection of Cd, Co, Cu, Mn, Ni, Pb and Zn using the system described were 20-50 times lower than the limits obtained by direct AAS determination. The RSD were Up to 40 samples/h could be analyzed.
Spectrophotometry Sample preparation Column Resin Solid phase extraction

"Determination Of Chromium And Manganese Traces In Biological Material By Flame AAS With Flow Injection Sample Introduction"
Zentralbl. Pharm., Pharmakother. Lab. Diagn. 1988 Volume 127, Issue 6 Pages 420-421
Friese, K.

Abstract: The combination of flow injection analysis and flame AAS is briefly discussed. For the cited application, samples were digested in closed PTFE vessels to give a final volume of 0.5 to 2 mL. Human hair samples (25 to 50 mg) were analyzed for Mn and gave day-to-day coefficient of variation of 20% (at 0.2 ppm) and 5% (at 2 ppm). Various biological tissues were analyzed for Cr. The accuracy of the procedure was demonstrated by analysis of four IAEA standard reference materials.
Biological tissue Hair Spectrophotometry Reference material

"Flow Injection System For Catalytic Spectrophotometric Determination Of Manganese In Seawater"
J. Anal. Chem. 1988 Volume 43, Issue 2 Pages 284-288
Kolotyrkina, I.Y.;Shpigun, L.K.;Zolotov, Y.A.

Abstract: A Tecator FIAStar automated instrument is used for kinetic determination of 0.02 to 10 ng mL-1 of Mn(II) in seawater by flow injection analysis. The method is based on the catalytic effect of Mn on the oxidation of NN-diethylaniline(I) by KIO4. Seawater (2 mL min-1) is mixed successively with a stream of 1 mM I (0.6 mL min-1) in a 60-cm mixing coil and with a stream of phosphate buffer of pH 7.0 (1.2 mL min-1) (into which 20 µL portions of 10 mM KIO4 are injected) in another 60-cm coil. The reaction zone proceeds through a 180-cm coil and then it is stopped in the 1-cm detector cell for 99 s. The increase in absorbance of the oxidation product is measured at 475 nm. The flow-line tubes have i.d. of 0.7 mm and the max. sample throughput is 25 h-1. The coefficient of variation are 19% (n = 20 to 42) for 0.1 to 0.4 ng mL-1 of Mn.
Sea Spectrophotometry Catalysis Kinetic Tecator

"Flow Injection Systems For Indirect Potentiometric Determination Of Metal Ions"
J. Anal. Chem. 1992 Volume 47, Issue 9 Pages 1588-1595
Shpigun, L.K.;Bazanova, O.V.

Abstract: Sample solution (0.2 ml) containing Co, Mn, Ni or Zn is introduced into an water carrier stream (0.8 mL min-1) that then merges in a 60-cm coil with a stream (0.8 mL min-1) of a complexing reagent solution that also contains a certain amount of active ion for detection by an Ag+-, Cu2+-, Pb2+- or Cd2+-selective electrode vs. Ag - AgCl. Equations have been derived that describe approximately the electrode response as a function of the metal-ion and reagent concentration. as well as the ratio of conditional stability constants of the complexes formed. The best results were obtained with a Cu2+-selective electrode in the presence of Na citrate and with Ag+- and Cd2+-selective electrodes in the presence of ammonium nitrilotriacetate. The determination range is 0.1 to 10 mM. The possibility has been shown of indirect potentiometric determination of heavy metal ions in a two-channel FIA system with Ag-, Cu-, Pb-, Cd-selective electrodes using a complexing organic reagent solution as carrier stream. Equations have been derived which approximately describe the electrode response height as a function of metal ion and reagent concentrations. as well as the ratio of conditional stability constants for the complexes formed. The best results were obtained in systems with a Cu-electrode in the use of sodium citrate, with Ag- and Cd-electrodes in the use of ammonium nitrilotriacetate. The determination range for the metal ions is between 1 x 10^-4 and 1 x 10^-2 mol/L. Sixty samples per h can be analyzed.
Potentiometry Electrode Electrode Electrode Electrode Complexation Interferences Indirect

"Application Of Flowing Stream Techniques To Water Analysis: Part III. Metal Ions: Alkaline And Alkaline-earth Metals, Elemental And Harmful Transition Metals, And Multielemental Analysis"
Talanta 2004 Volume 63, Issue 2 Pages 201-223
Manuel Mir&oacute;, Jos&eacute; Manuel Estela and V&iacute;ctor Cerd&agrave;

Abstract: In the earlier parts of this series of reviews [1 and 2], the most relevant flowing stream techniques (namely, segmented flow analysis, continuous flow analysis, flow injection (FI) analysis, sequential injection (SI) analysis, multicommuted flow injection analysis and multisyringe flow injection analysis) applied to the determination of several core inorganic parameters for water quality assessment, such as nutrients and anionic species including nitrogen, sulfur and halogen compounds, were described.In the present paper, flow techniques are presented as powerful analytical tools for the environmental monitoring of metal ions (alkaline and alkaline-earth metals, and elemental and harmful transition metals) as well as to perform both multielemental and speciation analysis in water samples. The potentials of flow techniques for automated sample treatment involving on-line analyte separation and/or pre-concentration are also discussed in the body of the text, and demonstrated for each individual ion with a variety of strategies successfully applied to trace analysis. In this context, the coupling of flow methodologies with atomic spectrometric techniques such as flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma mass spectrometry (ICPMS) or hydride-generation (HG)/cold-vapor (CV) approaches, launching the so-called hyphenated techniques, is specially worth mentioning.
Environmental Review

"On-line Preconcentration And ICP Determination For Trace Metal Analysis"
Microchim. Acta 1989 Volume 99, Issue 3-6 Pages 247-255
Valerio Porta, Corrado Sarzanini and Edoardo Mentasti

Abstract: The use of a closed-loop on-line enrichment procedure in combination with an ICP plasma emission spectrometer has been developed for the analysis of trace metal ions, such as Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn. The procedure utilizes a pre-concentration column filled with an anion exchange resin and 8-hydroxy-7-iodoquinoline-5-sulphonic acid is added to the sample prior to pre-concentration. Details on the optimization of pretreatment and instrumental conditions are described. Results obtained for the analysis of river water and antarctic seawater are reported.
Sea River Spectrophotometry Preconcentration Column Resin Closed loop

"Solid Phase Retention With Reversed Elution In A SIA System With Detection By Flame Atomic Absorption Spectrometry"
Can. J. Anal. Sci. Spectrosc. 2003 Volume 48, Issue 5 Pages 320-324
COSTA Rui C. C. ; ARAUJO Alberto N. ; MONTENEGRO M. Conceicao B. S. M. ; PIMENTEL M. Fernanda ; SILVA Valdinete L.

Abstract: The development of a pre-concentration procedure based on sequential injection analysis with flame atomic absorption spectrometry (SIA/FAAS) for the determination of Mn in water samples presenting a concentration between 4.50 and 200.0 ?g L-1 is described. Mn is retained on-line on a strong cationic resin (AG 50W-X8) and eluted under stopped-flow conditions with a chelating solution. Accuracy of the results attained was assessed by comparison with electro thermal atomic absorption spectrometry providing the relationship [SIA] ?g/L = 1.00 (±0.07)*[ETAAS]?g/L - 0.3 (± 7.6) after analysis of 10 samples. Evaluation of repeatability give a relative standard deviation of 2.9 and 1.8 % after ten replicate of two samples containing 108 and 166 ?g L-1 of Mn, respectively.
Water Spectrophotometry