Dry ashing of organic rich matrices with palladium for the determination of arsenic using inductively coupled plasma-mass spectrometry.

A dry ashing procedure is developed for the determination of As in organic rich matrices such as wheat flour, lichen and tobacco leaves. The volatility of As during dry ashing is avoided by the addition of palladium nitrate [Pd(NO(3))(2)]. The recovery of both As(III) and As(V) is found to be near quantitative. The residue after dry ashing is dissolved in nitric acid (HNO(3)) and analysed by inductively coupled plasma-mass spectrometry (ICP-MS). The process blank and limit of detection (LOD) are 11 and 6.6 ng g(-1), respectively. The procedure is applied for the determination of As in certified reference materials namely wheat flour NIST SRM 1567a (National Institute of Standards and Technology Standard Reference Material), lichen BCR CRM 482 (Institute for Reference Materials, European Commission) and Virginia tobacco leaves CTA-VTL-2 (Poland Academy of Sciences). The results obtained by the present procedure are in good agreement with the certified values and also determined after complete dissolution of samples using closed microwave digestion.

Determination of trace phosphorus in zirconium-niobium alloy and Zircaloy by UV-vis spectrophotometry.

A spectrophotometric method has been developed for the determination of traces of phosphorus in zirconium based alloys (Zr-2.5Nb and Zircaloy). It is achieved by selective fluoride complexation controlled by boric acid. The samples were dissolved in HF and fluoro-complexes of the matrices were formed by maintaining the concentration of HF while the excess HF was controlled by boric acid. After the formation of phosphomolybdate, extracted into n-butyl acetate, ion-associated with crystal violet and the absorbance was measured at 582 nm. The results obtained by this procedure were in close agreement with the certified reference material (CRM) values and further these values were compared with the values determined by Glow Discharge-Quadrupole Mass Spectrometry (GD-QMS). The potential interferences like fluoride, silicon, arsenic(V), niobium, titanium, tantalum, etc., were tolerable to large level. LOD (3 s) was found to be 0.055 mg kg(-1) with a precision (R.S.D.) of 2-3% and molar absorptivity was 2.7x10(5) L mol(-1) cm(-1).

Determination of traces of rubidium in high purity cesium chloride by electrothermal atomic absorption spectrometry (ETAAS) using boric acid as a modifier.

The use of boric acid as a modifier for the determination of trace amount of rubidium in high purity cesium chloride matrix by electrothermal atomic absorption is described. It was found that the negative influence of the chloride matrix could not be eliminated using stabilized temperature platform (STPF) alone. Due to the high dissociation energy (D(0)=427 kJ mol(-1)) of rubidium chloride, it was difficult to dissociate in the gas phase and hence is lost. Elimination of interferences was achieved by the addition of boric acid as a chemical modifier. Diluted cesium chloride samples (5%, m/v) were analyzed applying the standard addition method. The characteristic mass of 24 pg was obtained. The detection limit of the proposed method is around 26 ng g(-1). The developed method was applied to the determination of traces of rubidium in high purity cesium chloride samples. The data obtained by this method were in good agreement with those obtained by other independent method like FAAS.

Determination of trace impurities in chromium matrices after separation from Cr(III) using the oxalate form of anion exchanger.

A method has been developed for the separation and determination of a set of 11 impurities from chromium matrices using oxalate form of Amberlite IRA 93. Due to slower kinetics of formation of the anionic complex, Cr(III) passed in the effluent while impurities forming strong complexes rapidly are retained on the exchanger. The adsorption of impurities of interest is found to be uniform in pH range 2-6. The adsorbed impurities are eluted with 2 mol l(-1) HNO(3) and determined by inductively coupled plasma-optical emission spectrometer (ICP-OES). The percentage recoveries of Al, Bi, Cd, Co, Cu, Fe, Mn, Ni, Pb, Ga and Zn are in the range 88-101% and separation of matrix is >99.9%. The method has been applied for the analysis of two samples namely CrCl(3).6H(2)O and Cr. The R.S.D. of the method is 5-6% at >10 microg g(-1) level and approximately 15% at <1 microg g(-1) level. The process blank values are in the range sub-microg g(-1) and detection limits are in ng g(-1) range.

Determination of indium in high purity antimony by electrothermal atomic absorption spectrometry (ETAAS) using boric acid as a modifier.

The use of boric acid as a modifier for the determination of trace amount of indium in high purity antimony by electrothermal atomic absorption is described. It was found that the negative influence of the hydrofluoric acid, used for the digestion could not be eliminated by using stabilized temperature platform furnace (STPF) alone. Due to the high dissociation energy (D(0)=506kJmol(-1)) of indium fluoride, it is difficult to dissociate in the gas phase and hence is lost. In presence of HF (used for the dissolution of antimony), the universal Pd-Mg modifier does not work satisfactorily. Additionally, rising corrosion and reduced tube lifetime were observed when the acid digested (HF-HNO(3)) antimony solution was injected in to the platform. Improvement in platform life and elimination of interferences were achieved by the addition of boric acid as a chemical modifier together with ruthenium coating of the platform. Corrosive changes of the transversely heated graphite atomizer (THGA) platform surface were examined by scanning electron microscopy. The standard addition method was applied. A characteristic mass of 36pg was obtained. The detection limit of the proposed method is around 0.04mugg(-1). The developed method was applied to the determination of indium in real samples. The data obtained by this method were in good agreement with those obtained by ICP-MS.

Determination of traces of chloride and fluoride in H2SO4, H3PO4 and H3BO3 by in situ analyte distillation-ion chromatography.

A simple dual vessel in situ analyte distillation (IAD) system has been developed for suppressed ion chromatographic determination of chloride and fluoride ions in complex matrices. In IAD system, water vapours generated from the outer vessel reacts with sulfuric acid generating heat, thus favouring the quantitative distillation of chloride and fluoride within 30 min on water bath temperature (approximately 80 degrees C). The distilled analytes, as their respective acids in water, were directly injected into an ion-chromatograph. This newly developed method has been applied for analysis of trace impurities in H2SO4, H3PO4 and H3BO3. The detection limits for chloride is 8, 80 and 70ppb (w/w) for H2SO4, H3PO4 and H3BO3, respectively. For fluoride the detection limits are 6 and 60 ppb (w/w) for H2SO4 and H3PO4, respectively. The recovery of spikes for both the analytes ranged between 87 and 100%.

In situ matrix evaporation by isothermal distillation of high-purity reagents for the determination of trace impurities by ion chromatography.

In situ matrix evaporation of high-purity acids based on isothermal distillation was achieved in a high-density polyethylene (HDPE) container on a water bath, to avoid contamination from the laboratory environment. The solubility of water and acid vapours in glycerol due to co-association was utilized to achieve complete evaporation. All major sources which contribute to the process blank were taken care of in a simple and effective way. A 50-fold preconcentration with >99.9% matrix removal was achieved for the analysis of low-boiling acids, HCl, HF, HNO3 and H2O2. The non-volatile ions NH4+, Li+, Na+, K+, Mg2+, Ca2+, SO4(2-) and PO4(3-) were determined by ion chromatograph with conductivity detection. The detection limits were 6-130 ng/l with recoveries of 85-110% for all ions studied.

Ion chromatographic determination of trace level phosphorus in purified quartz.

Trace levels of phosphorus in purified quartz are determined by ion chromatography. In situ reagent purification, matrix digestion and oxidation of phosphorus to orthophosphate ion are carried out simultaneously in a vapour phase digestion (VPD) assembly using a mixture of HF, HNO3 and H2O2. A drastic reduction (475 times) in phosphate blank from reagents (HF/H2O2) was achieved in the VPD through in situ purification of the reagent. The residues remaining after volatilisation (solvent/matrix), mostly consisting of insoluble phosphate/fluoride salts of divalent and trivalent cations, were solubilised by ion-exchange dissolution. Phosphate was analysed on the IonPac AS17 column with suppressed conductivity detection. The results of the ion chromatography (IC) method were compared with a spectrophotometric method. Accuracy was evaluated by analysing a certified reference material (silicon, NIST 57a). The method detection limit was 0.05 microg g(-1).

Procedure for determination of trace ions in boric acid by matrix volatilization-ion chromatography.

A method for determination of anions and cations in boric acid is proposed by matrix volatilization. The boric acid matrix was eliminated as trimethyl borate ester in a vapour phase matrix elimination (VPME) system using a mixture of glycerol-methanol. In this VPME system, in situ reagent purification, sample decomposition and digest evaporation were achieved in a single step. Trace anions were separated on anion-exchange column (IonPac AS17) by an isocratic elution with 15 mM sodium hydroxide and the cations on a cation-exchange column (IonPac CS12) by 20 mM hydrochloric acid as eluents. Method detection limits (3sigma) for most ions ranged from 0.3 to 8 ng/g (ppb). Recovery experiments combined with comparison of data obtained by other methods were employed to verify the accuracy of the proposed method. Application of the method to determine trace levels of anions like acetate, oxalate, sulfate, phosphate and cations such as lithium, sodium, potassium, magnesium and calcium in two highly pure grades of boric acid using ion chromatography is demonstrated.

A simple vapour phase decomposition (VPD) of quartz powder in a polypropylene vessel and determination of phosphorus by spectrophotometry.

A simple, low pressure, low temperature vapour phase decomposition (VPD) of quartz powder has been developed for the determination of phosphorus. A platinum dish containing the quartz or silicon powder was placed inside a polypropylene vessel containing 40 ml of 1:1 mixture of HF and HNO(3). After capping the vessel, the entire assembly was heated on a water bath at approximately 90 degrees C for 8 h. The platinum dish was removed from the vessel, the sample solution was treated with 0.5 ml of H(2)SO(4) and 0.5 ml of HClO(4) and was heated on a hot plate till HClO(4) fumed out. The resultant solution was diluted to 40 ml ( approximately 0.4N), analysed for phosphorus by spectrophotometry as an ion-pair of molybdophosphate with crystal violet. Phosphorus contamination by reagents has been drastically reduced (around 250 times) compared to the conventional dissolution procedure. The optimum reaction conditions were [H(+)]=0.42N, [H(+)]/Mo=62 for the formation of molybdophosphate and its extraction into n-butyl acetate. No interferences due to fluoride, silicate (active silica) and arsenic (V) upto 6.7x10(3),2.7x10(3) and 2.0x10(3) times the content of phosphorus, respectively were observed. The LOD was found to be 0.066 mug g(-1) (+/-3 s). RSD is 0.4-2.3% and the molar absorptivity is 2.7x10(5) l mole(-1) cm(-1).

Effect of fungicides on the production of amylase by Rhizopus oryzae.

Seven fungicides (Brassicol), captan, Dithane M-45, Fytolan, Parasan, Sulfex and Thiram) were tested for their effect on the production of amylase enzyme by Rhizopus oryzae. The activity of amylase was determined by cup-plate method. All the fungicides were found inhibitory for the synthesis of amylase. Out of these, Parasan was the most effective causing hundred percent inhibition at 0.025% concentration. No amylase production was recorded when Thiram, Fytolan, Brassicol, Captan and Dithane M-45 were used at 0.5, 1.5, 2.0, 2.0, and 2.0% concentration respectively. Sulfex was found to be less effective, as hundred percent inhibition of amylase production has not been recorded even at 3.0% concentration.