Determination of the pesticide carbaryl by chemical deoxygenation micellar-stabilized room temperature phosphorescence

This paper presents a convenient determination method for carbaryl in polluted water by micellar-stabilized room temperature phosphorescence with Na(2)SO(3) as oxygen scavenger. The effect of various experimental conditions on the determination of carbaryl is discussed in detail. The analytical curve of carbaryl gives a linear dynamic range of 2 x 10(-7)-6 x 10(-5) mol/l., and a detection limit of 2 x 10(-7) mol/l. A recovery of 90-100% was obtained for 0.05-0.1 ppm carbaryl.     

Flow-injection chemiluminometric determination of some thioxanthene derivatives in pharmaceutical formulations and biological fluids using the [Ru(dipy)3(2+)]-Ce(IV) system.

A flow-injection (FI) methodology using tris(2,2'-dipyridyl)ruthenium(II), [Ru(dipy)3(2+)], chemiluminescence (CL) was developed for the rapid and sensitive determination of three thioxanthene derivatives, namely zuclopenthixol hydrochloride, flupentixol hydrochloride and thiothixene. The method is based on the CL reaction of the studied thioxanthenes with [Ru(dipy)3(2+)] and Ce(IV) in a sulfuric acid medium. Under the optimum conditions, calibration graphs were obtained over the concentration ranges 0.002-6 migrograms/ml for zuclopenthixol hydrochloride, 0.5-15 micrograms/ml for flupentixol hydrochloride and 0.05-7.5 micrograms/ml for thiothixene. The limits of detection (s/n = 3) were 4.2 x 10(-9) mol/l zuclopenthixol hydrochloride, 2 x 10(-8) mol/l flupentixol hydrochloride and 4.5 x 10(-8) mol/l thiothixene. The method was successfully applied to the determination of these compounds in dosage forms and biological fluids.     

Large-volume injection electrothermal AAS combined with tungsten-treated pyrolytic graphite furnace: determination of cadmium in tap, snow and river water samples with phosphate modifier.

A large-volume (100 microl) injection-ETAAS with W-treated PG furnace combined with a phosphate modifier was applied to the determination of unpolluted levels of Cd in tap, snow and river-water samples. The limit of detection of 1.1 ng l(-1) was observed for a 4 w/v% NH4H2PO4 modifer. Matrix interference studies were tested for major ion species well found in fresh water. The direct determination of Cd in certified river water (12 +/- 2 ng l(-1)) was carried out and the observed value was in agreement with the certified one. The good recoveries of Cd added to real environmental water samples were also observed. This method was applied to the determination of Cd in unpolluted environmental water samples.     

Atomic fluorescence spectrometric determination of trace amounts of arsenic and antimony in drinking water by continuous hydride generation

A highly sensitive and simple method has been developed for the determination of As(III), total As, Sb(III) and total Sb in drinking water samples by continuous hydride generation and atomic fluorescence spectrometry (HGAFS). For As determination, water samples aspirated in a carrier of 2 mol l(-1) HCl were merged with a reducing NaBH(4) 3%(m/v) solution, with sample and NaBH(4) flow rates of 12.5 and 1.5 ml min(-1) respectively. The hydride generated in a 170 cm reaction coil was transported to the detector with an Ar flow of 400 ml min(-1), and a limit of detection between 5 and 20 ng l(-1) was obtained. For Sb determination, 2.5 mol l(-1) HCl and 2%(m/v) NaBH(4) were employed, with respective flow rates of 9.7 and 2 ml min(-1). The hydride generated in a 50 cm reaction coil was transported to the detector with an Ar flow rate of 300 ml min(-1), and a limit of detection between 6 and 14 ng l(-1) was obtained. Determination of the total concentration of these elements was obtained after a previous reduction with KI. Recovery studies of different added concentrations of these species in natural water samples were between 93 and 104% for As(III), 96-103% for As(V), 93-101% for Sb(III) and 90-119% for Sb(V).     

Determination of diclofenac sodium by capillary zone electrophoresis with electrochemical detection

Capillary zone electrophoresis was employed for the determination of diclofenac sodium using an end-column amperometric detection with a carbon fiber microelectrode, at a constant potential of 0.83 V vs. saturated calomel electrode. The optimum conditions of separation and detection are 4.90 x 10(-3) mol/l Na2HPO4-3.10 x 10(-3) mol/l NaH2PO4 (pH 7.0) for the buffer solution, 10 kV for the separation voltage, 5 kV and 10 s for the injection voltage and the injection time, respectively. The limit of detection is 2.5 x 10(-6) mol/l or 5.2 fmol (S/N=2). The relative standard deviation is 0.8% for the migration time and 4.7% for the electrophoretic peak current. The method was applied to the determination of diclofenac sodium in human urine.     

Stopped-flow spectrophotometric determination of hydrogen peroxide with hemoglobin as catalyst

A rapid and sensitive method was proposed for the determination of hydrogen peroxide based on the catalytic effect of hemoglobin using o-phenylenediamine as the substrate. Stopped-flow spectrophotometric method was used to study the kinetic behavior of the oxidation reaction. The catalytic effectiveness of hemoglobin was compared with other four kinds of catalysts. The initial rate of the formation of the reaction product 2,3-diaminophenazine at the wavelength of 425 nm was monitored, permitting a detection limit of 9.2x10(-9) mol/l H(2)O(2). A linear calibration graph was obtained over the H(2)O(2) concentration range 5.0x10(-8)-3.5x10(-6) mol/l, and the relative standard deviation at a H(2)O(2) concentration of 5.0x10(-7) mol/l was 2.08%. Satisfied results were obtained in the determination of H(2)O(2) in real samples by this method.     

Improvements in the N,N-diethyl-p-phenylenediamine method for the determination of free and combined residual chlorine through the use of FIA

In the determination of free and combined chlorine, the reaction of permanganate standards with N,N-diethyl-p-phenylenediamine (DPD) exhibits nonlinearity presumably because both the colored semiquinoid product and the colorless quinoid product are both formed. The titrimetric DPD method titrates both of the products while the colorimetric method monitors only the colored semiquinoid products. This results in a nonlinear response for the colorimetric method above 1.0 mg/l. as Cl(2). Under FIA conditions, the nonlinearity of the DPD colorimetric method is eliminated in the 0.1-5.0 mg/l. (as Cl(2)) range and the linear range is expanded to 0.1-8.0 mg/l. as Cl(2). Also, relative standard deviations are improved by 0.5-11% relative to the colorimetric method and 1.5-4.0% relative to the titrimetric method. The FIA method was developed further to sequentially determine both free and combined chlorine, since chloramine was found to have a negligible interference in the free chlorine determination.     

Indirect voltammetric determination of trace hydroxylamine using magnetic microspheres

A new indirect voltammetric method for the determination of hydroxylamine is described. It is based on the reduction of an electroactive derivative of hydroxylamine on the surface of a magnetic electrode. The electroactive derivative produced by hydroxylamine reacted with magnetic polymer microspheres containing carbonyl groups on the surface. The experimental conditions are discussed. It was found that the peak potential (Ep) of the derivative was -0.46 V (vs. Ag/AgCl) under optimum conditions. Hydroxylamine could be determined in the range of 5-2,000 microg l(-1) with the detection limit of 2 microg l(-1) and relative standard deviation for the determination of 100 microg l(-1) hydroxylamine was 2.35%. Satisfactory results were obtained for the determination of hydroxylamine in aqueous medium.     

Determination of 8-hydroxy-2'-deoxyguanosine in untreated urine by capillary electrophoresis with UV detection

A capillary electrophoresis method with UV detection was developed for the determination of 8-hydroxy-2'-deoxyguanosine (8-OHdG) in untreated urine samples. The calibration graph for 8-OHdG in urine is linear in the concentration range 10-500 mg/l. and the detection limit is 5 mg/l (17 microM). 8-OHdG was determined in urine from oncological patients treated by radiation therapy. Its concentrations relative to creatinine were found to be in the range 10-47 microg 8-OHdG/l mg creatinine (4-19 micromol 8-OHdG/mmol creatinine). The overall time of the analysis of a urine sample was less than 15 min.     

Flow-injection spectrophotometric determination of cadmium with quinolylazo compound after on-line separation using a silica gel column

2-[2-(4-Methylquinolyl)azo]-5-diethylaminophenol(QADP) reacts with cadmium in aqueous ethanol and the molar absorptivity of the QADP-cadmium complex is the highest (1.51 x 1O(5)M(-1) cm(-1), gamma(max) 569 nm) of the reagents reported previously. A flow-injection spectrophotometric determination of cadmium with QADP after on-line separation using silica gel column was proposed. A 450 mug/l cadmium concentration could be determined in the presence of 13 mg/l zinc, 83 mg/l lead and 11 mg/l iron.     

Determination of tocopherols,tocopherolquinones and tocopherolhydroquinones by gas chromatography-mass spectrometry and preseparation with lipophilic gel chromatography

A method has been developed for the simultaneous determination of a range of aromatic amines using cation-exchange chromatography performed on a standard ion chromatography column using d.c. amperometric detection. The analytes separated were 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA), aniline, o-toluidine, benzidine, p-chloroaniline, 4,4'-diaminodiphenyl (4,4'-DDP), m-nitroaniline and 1-naphthylamine. A Dionex CS12 column was used with gradient elution from an initial eluent of 5% CH3CN+35 mM H2SO4 to 27% CH3CN+35 mM H2SO4 (at 35 min). Detection limits in the range 2.6-22.6 microg/l were observed for all analytes except m-nitroaniline, for which the detection limit was 201 microg/l. Linear calibrations and good precision were observed and the method was applied to the determination of benzidine, p-chloroaniline and 1-naphthylamine in wastewater samples. Further, the separation was also used (after some modification of the eluent conditions) for the determination of 2,4- and 2,6-toluene diisocyanate (2,4- and 2,6-TDI) and 4,4'-methylenediphenyl diisocyanate (4,4'-MDI) after their hydrolysis to 2,4-TDA, 2,6-TDA and 4,4'-DDP. Detection limits for 2,6- and 2,4-TDI and 4,4'-MDI were 3.8, 8.2, and 11.2 microg/l, respectively. The method was applied to the determination of diisocyanates in air.     

Spectrophotometric determination of acid volatile sulfide in river sediments by sequential injection analysis exploiting the methylene blue reaction

This paper demonstrates the application of sequential injection analysis to perform sulfide determination using the methylene blue chemistry, based on two reagents: 3.63 mmol l(-1)N,N dimethyl-p-phenylene diamine hydrochloride in 1.1 mol l(-1) HCl solution and 19 mmol l(-1) FeCl(3), also in 1.1 mol l(-1) HCl. These solutions are aspirated inside the holding coil of the sequential injection system as two reagent zones sandwiching the sample zone. Under optimized conditions, the detection limit was calculated at 40 mug l(-1) S(2-), with a linear dynamic range from 0.05 to 2 mg l(-1) S(2-). This linear range can be extended up to 32 mg l(-1) using in-line dilution for sulfide concentrations greater than 2 mg l(-1). The robust characteristic of the SI system with syringe pump leads to very stable analytical curves (precision of 4%), minimizing the laborious preparation of sulfide standards. The method was applied in the determination of acid volatile sulfide in river sediments.     

Application of a contactless conductometric detector for the simultaneous determination of small anions and cations by capillary electrophoresis with dual-opposite end injection

A contactless conductometric detection (CCD) system for capillary electrophoresis (CE) with a flexible detection cell was applied for the simultaneous determination of small anions and/or cations in rain, surface and drainage water samples. The applied frequency, the amplitude of the input signal, the electrolyte conductivity and electrode distance were found to be the most significant factors affecting the detection sensitivity. 2-(N-Morpholino)ethanesulfonic acid/histidine-based (MES/His) electrolytes were used for direct conductivity detection of anions and cations, while ammonium acetate was selected for indirect conductivity determination of alkylammonium salts. For the simultaneous separation procedure, involving dual-opposite end injection, an electrolyte consisting of 20 mM MES/His, 1.5 mM 18-crown-6 and 20 microM cetyltrimethylammonium bromide provided baseline separation of 13 anions and cations in less than 6 min. The detection limits achieved were 7-30 micrograms/l for direct conductometric detection of various common inorganic cations and anions, excluding F- (62 micrograms/l) and H2PO4- (250 micrograms/l), and 35-178 micrograms/l for indirect conductometric detection of alkyl ammonium cations. The developed electrophoretic method with conductometric detection was compared to ion chromatography.     

液相色谱测定糙米中烯虫酯残留量

研究了液相色谱测定糙米中烯虫酯残留量的方法。试样用丙酮提取，经活性炭，中性氧化铝层析柱一步净化，用液相色谱测定。线性范围０．２－１０．０ｍｇ／Ｌ，检出限为０．０５ｍｇ／Ｌ，当添加浓度０．５－１０．０ｍｇ／ｋｇ时，回收率为８４．２％－１００．７％之间。用于糙米中烯虫酯残留量检验，结果满意。     

Simultaneous determination of beryllium and aluminium in mixtures using derivative spectrophotometry

The spectrophotometric determination of beryllium and aluminium with 5,8-dihydroxy-1,4-naphthoquinone in the presence of a non-ionic surfactant is reported. Absorption maxima, molar absorptivity and Sandell's Sensitivity of 1:2 (M:L) beryllium and aluminium complexes are, 585 nm and 598 nm, 1.63 x 10(4) l.mole(-1).cm(-1) and 2.04 x 10(4) l.mole(-1).cm(-1), and 0.55 ng/cm(2) and 1.32 ng/cm(2) respectively. Beer's law is obeyed between 7.20-3.96 x 10(2) ng/ml beryllium and 1.08 x 10(1)-1.08 x 10(3) ng/ml aluminium. A method for simultaneous determination of beryllium and aluminium in their mixture using derivative spectra is described. The range 3.6 x 10(1)-3.6 x 10(2) ng/ml beryllium could be determined in the presence of 1.08 x 10(2)-1.08 x 10(3) ng/ml aluminium, and vice versa.     

Synthesis of a novel chemiluminescent reagent for the determination of hydrogen peroxide in snow waters

7-(4,6-Dichloro-1,3,5-triazinylamino)-4-methylcoumarin (DTMC) was synthesized as a completely new chemiluminescent reagent, and with it a novel chemiluminescence method was developed for the determination of hydrogen peroxide in the absence of any added catalyst or co-oxidant. The chemiluminescence intensity of the DTMC-H(2)O(2) system could be enhanced by the addition of cation surfactants. The chemiluminescence intensity was directly proportional to the concentration of H(2)O(2) in the range 1.0 x 10(-7)-4.0x10(-4) mol l(-1), and the detection limit was 4.0 x 10(-8) mol l(-1). The relative S.D. was 4.9% for 1.0 x 10(-6) mol l(-1) of H(2)O(2) (n=10). The selectivity of this method was high, and most of the transition metal ions have no effect on the determination. The proposed method has been applied to the determination of trace amounts of hydrogen peroxide in snow water. A possible mechanism of the chemiluminescence reaction is also discussed.     

Kinetic methods for the determination of cadmium(II) based on a flow-through bulk optode

Three kinetic methods based on flow injection, flow, and stopped-flow injection were applied for the determination of Cd(II) using a flow-through bulk optode membrane that incorporates 1-(2-pyridylazo)-2-naphtol (PAN) in a plasticized poly(vinyl) chloride membrane entrapped in a cellulose support. The calibration graphs plotting the reflectance at 560 nm versus [Cd(II)](1/2) for the first two methods and versus [Cd(II)] for the third were linear up to 56.2 mg l(-1). The detection limits of the methods were 0.01, 0.06 and 0.8 mg l(-1), respectively. The FI method was selected for application purposes. The variation coefficient of the sensor response for 11.2 mg l(-1) of Cd(II) was +/-0.31 and +/-0.65% between different membranes. The sensor can be readily regenerated with a carrier (acetic-acetate) buffer of pH 4. The FI method was applied to the determination of cadmium in an alloy and in water.     

Gas chromatographic-mass spectrometric method for quantification of 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone in chlorinated water samples

A method for the determination of 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone (MX), in drinking water by GC-MS with a limit of detection of 3.0 microg/l and a limit of quantification of 7.0 microg/l is presented. Clean-up by SPE and extraction of water samples with dichloromethane were carried out before the preconcentration of MX, which was derivatized directly in the injector of the GC, and the MX trimethylsilyl derivative was identified and quantitatively determined by MS.     

Spectrophotometric determination of zinc in copper-base alloys with TAN

TAN reacts with zinc(II) forming a red complex with composition 1:2 Zn(II)-TAN and absorption maximum at 582 nm. Zinc can be determined with this reagent in the presence of Triton X-100, in the pH range 6.20-8.00 with a molar absorptivity of 4.5×10⁴ l/mol/cm Beer's Law was obeyed up to least 1.55 g/ml. Copper interference was eliminated with a mixture of thiosulfate and ascorbic acid and nickel separated by precipitation with dimethylglyoxime. The proposed method was used for zinc determination in several copper-base alloys and the results of analysis in comparison with certified values indicated that the procedure was accurate and precise. A derivative procedure is also proposed, allowing zinc determination with high sensitivity (5-400 ng/ml).     

Solid phase extraction and spectrophotometric determination of silver with 2-(2-quinolylazo)-5-diethylaminophenol as chromogenic reagent.

A new chromogenic reagent, 2-(2-quinolylazo)-5-diethylaminophenol (QADEAP), was synthesized. A sensitive, selective and rapid method has been developed for the determination of microg/L level silver ion based on the rapid reaction of silver(l) with QADEAP and the solid phase extraction of the colored chelate with C18 cartridge. The QADEAP reacts with Ag(l) to form a violet chelate of a molar ratio 1:2 (silver to QADEAP) in pH 3.5-8.0. This chelate was prconcentrated by solid phase extraction with C18 cartridge. An enrichment factor of 100 was achieved. The molar absorptivity of the chelate is 1.30 x 10(5) L mol(-1) cm(-1) at 590 nm in measured solution. Beer's law is obeyed in the range of 0.01-0.6 microg/ml. The relative standard deviation for eleven replicate samples of 0.01 microg/ml is 1.15%. The detection limit is 0.02 microg/L in the original samples. This method was applied to the determination of microg/L level silver ion in water with good results.