Tin determination in marine sediment, soil, coal fly ash and coal slurried samples by hydride generation-electrothermal atomic absorption spectrometry

Different procedures of tin hydride generation from aqueous and acidified slurries of marine sediment, soil, coal fly ash and coal samples, coupled to electrothermal atomic absorption spectrometry were optimised by using factorial designs. A batch mode generation system and Ir-treated graphite tubes were used for the hydride generation and atomisation, respectively. Eight variables, affecting the hydride generation and hydride transport efficiency (hydrochloric acid and sodium tetrahydroborate concentrations, particle size, acid volume and argon flow rate), the hydride trapping efficiency (trapping temperature and trapping time) and the atomisation efficiency (atomisation temperature) were studied and optimised. In addition, acid pre-treatment procedures assisted by ultrasonic energy were used for soil and coal matrices, to obtain acidified slurries and acid leachates. The involved variables were hydrochloric and nitric acid concentrations, exposure time to ultrasound, particle size and leaching solution volume. Adequate accuracy (41.5±0.8 and 1.4±0.2 mg kg⁻¹, for PACS-1 (sediment marine) and NIST-1633b (coal fly ash), respectively) were obtained by using aqueous slurry reference materials. In addition, values of 6.2±0.6 and 1.2±0.1 mg kg⁻¹ were assessed by analysing GBW-07401 (soil) and NIST-1632c (coal) certified reference materials.     

Bismuth determination in environmental samples by hydride generation-electrothermal atomic absorption spectrometry

A hydride generation procedure, via flow injection, coupled to electrothermal atomic absorption spectrometry was optimised for Bi determination in sea water and hot-spring water and acid extracts from coal, coal fly ash and slag samples. The effects of several variables such as hydrochloric acid and sodium tetrahydroborate concentrations, hydrochloric acid and sodium tetrahydroborate flow rates, reaction coil length, trapping and atomisation temperatures, trapping time and the Ar flow rate have been investigated by using a 2⁹*3/128 Plackett-Burman design. From these studies, certain variables (sodium tetrahydroborate concentration and trapping time) showed up as significant, and they were optimised by a 2²+star central composite design. In addition, a study of the bismuthine trapping and atomisation efficiency from graphite tubes (GTs) permanently treated with uranium, tantalum, lanthanum oxide, niobium, beryllium oxide, chromium oxide and tantalum carbide were investigated. The results obtained were compared with those achieved by iridium and zirconium-treated GTs. The best analytical performances, with characteristic mass of 35 pg and detection limit of 70 ng l⁻¹, were achieved by using U-treated GTs. Accuracy were checked using several reference materials: 1643d (Trace Elements in Water), TM-24 (Reference Water), GBW-07401 (Soil) and 1632c (Trace Elements in Coal).     

Determination of inorganic oxyanions of As and Se by HPLC-ICPMS

A liquid chromatographic separation of inorganic oxyanions of As (As(V) and As(III)) and Se (Se(VI) and Se(IV)) using mixed ion-pairing reagents followed by ICPMS detection is described. The separation was accomplished in less than 4 min on Capcell C18 RP column using mixed ion-pairing modifier containing 5 mM of butane sulfonic acid (BSA), 2 mM malonic acid, 0.30 mM hexane sulfonic acid (HSA) and 0.5% methanol of pH 2.5. All four species were resolved with retention times of 2.4, 2.6, 3.0, and 3.1 min for Se(VI), As(V), As(III), and Se(IV), respectively. The detection limits were less than 0.08 and 0.77 μg l⁻¹ for arsenic and selenium species, respectively. The relative standard deviation of the proposed method for arsenic (at 2.5 μg l⁻¹) and selenium (at 10 μg l⁻¹) was less than 3.7 and 4.8%, respectively. The technique was used to determine inorganic oxyanions of As and Se in water samples (tap, well, and river) and extracts of coal fly ash and sediment. Low power microwave digestion was employed for extraction from fly ash and sediment samples.     

Direct As,Bi, Ge,Hg and Se(IV) cold vapor/hydride generation from coal fly ash slurry samples and determination by electrothermal atomic absorption spectrometry

Direct cold vapor and hydride generation procedures for As, Bi, Ge, Hg and Se(IV) from aqueous slurry of coal fly ash samples have been developed by using a batch mode generation system. Ir-treated graphite tubes have been used as a preconcentration and atomization medium of the vapors generated. A Plackett–Burman experimental design has been used as a strategy for evaluation of the effects of several parameters affecting the vapor generation efficiency from solid particles, vapor trapping and atomization efficiency from Ir-treated graphite tubes. The effects of parameters such as hydrochloric acid and sodium tetrahydroborate, argon flow rate, trapping and atomization temperatures, trapping time, acid solution volume and mean particle size have been investigated. The significant parameters obtained (trapping and atomization temperatures for As and Ge; trapping temperature and trapping time for Bi; argon flow rate and atomization temperature for Se) have been optimized by 2²+star central composite design. For Hg, the trapping temperature has been also significant. Optimum values of the parameters have been selected for the development of direct cold vapor/hydride generation methods from slurry particles. The accuracy of methods have been verified by using NIST-1633a coal fly ash certified reference material. Absolute detection limits of 11.5, 48.0, 600, 55.0 and 11.0 ng l⁻¹ for As, Bi, Ge, Hg and Se have been achieved, respectively. A particle size less than 50 μm has shown to be adequate to obtain total cold vapor/hydride generation of metals content in the aqueous slurry particles.     

Direct mercury determination in aqueous slurries of environmental and biological samples by cold vapour generation-electrothermal atomic absorption spectrometry

Direct cold vapour generation from aqueous slurries of environmental (marine sediment, soil, coal) and biological (human hair, seafood) samples have been developed using a batch mode generation system coupled with electrothermal atomic absorption spectroscopy. The effects of several variables affecting the cold vapour generation efficiency from solid particles (hydrochloric acid and sodium tetrahydroborate concentrations, argon flow rate, acid solution volume and mean particle size) have been evaluated using a Plackett-Burman experimental design. In addition, variables affecting cold vapour trapping and atomisation efficiency on Ir-treated graphite tubes (trapping and atomisation temperatures and trapping time) have been also investigated. Atomisation and trapping temperatures, trapping time and hydrochloric acid concentration were the significant variables. The 2²+star and 2³+star central composite designs have been used to obtain optimum values of the variables selected. The accuracy of methods have been verified by using several certified reference materials (PACS-1, GBW-07410, NIST-1632c, CRM-397 and DORM-2). A characteristic mass of 390 pg were achieved. The detection limits of methods were in the range of 40-600 ng g⁻¹. A particle size less than 50 μm is adequate to obtain total cold vapour generation of Hg content in the aqueous slurry particles.     

Evaluation of non-chromatographic approaches for speciation of extractable As(III) and As(V) in environmental solid samples by FI-HGAAS

Non-chromatographic speciation approaches have been developed for determination of water-soluble and phosphate-exchangeable As(III) and As(V) in certified reference materials of coal fly ash and sediments by FI-HGAAS. A 2_IV^6-2 fractional factorial design was employed for screening optimisation of the flow injection manifold. A simple two-stage sequential extraction protocol involving deionized water and a phosphate buffer as extractants was employed. Determination of both oxidation states of As in the extracts could be accomplished following arsine generation under different reaction conditions, namely, (i) selective determination of As(III) in citric acid medium or using soft generation conditions (i.e. low HCl and NaBH₄ concentrations); (ii) determination of total As in each extract using thioglycollic acid as reaction medium or after pre-reduction of As(V) to As(III) with a KI+ascorbic acid mixture. The As(V) content was estimated by difference between both measurements. Reaction conditions were previously optimised and analytical parameters in each reaction medium were established. Overall, the extractable As content was less than 5% in sediment and fly ash CRMs. The LOD of As was around 0.07 μg l⁻¹ for As(III) determination, and 0.06 μg l⁻¹ for total As determination after prereduction. Liquid chromatography coupled to atomic fluorescence spectrometry with post-column hydride generation was used for comparison.     

Optimization and comparison of chemical and electrochemical hydride generation for optical emission spectrometric determination of arsenic and antimony using a novel miniaturized microwave induced argon plasma exiting the microstrip wafer

Continuous flow (CF) chemical hydride generation (CHG) and electrochemical hydride generation (ECHG) directly coupled to a novel 40 W, atmospheric pressure, 2.45 GHz microwave microstrip Ar plasma exiting a microstrip wafer has been developed for the emission spectrometric determination of As and Sb using a miniaturized optical fiber spectrometer and a CCD-array detector. The experimental conditions for both procedures were optimized with respect to the relative net intensities of the As I 228.8 nm and Sb I 252.8 nm lines and their signal-to-background intensity ratios. Additionally, the susceptibility to interferences from Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn and other hydride-forming elements in the determination of As and Sb using the CHG and ECHG techniques was investigated in detail. Under the optimized conditions, it was found that ECHG is more prone to interferences compared to CHG. The detection limits (3σ) of As (6 ng mL⁻¹) and Sb (7 ng mL⁻¹) obtained for the ECHG-MSP-OES method are about three times lower than in the case of the CHG-MSP-OES method due to a two-fold lower amount of H₂ introduced into the MSP in case of the ECHG, resulting in a better plasma stability and reduced background level. The linearity ranges for both calibration curves to a concentration of up to 5 μg mL⁻¹ and a precision between 2% and 7% (2 μg mL⁻¹ and 0.050 μg mL⁻¹ of As and Sb, respectively) were found for both methods. The developed ECHG-MSP-OES method was validated for As through the analysis of a certified coal fly ash standard reference material (NIST SRM 1633a) after sample dissolution. The derived concentration (140 ± 8 μg g⁻¹) was found to agree well with the certified data (145 ± 15 μg g⁻¹). The method was also successfully applied to the analysis of both a galvanic bath sample, which contained Sb and was spiked with As, and a tap water sample spiked with both analytes. Recovery rates of 99-101% and a Sb concentration of 6.6 μg mL⁻¹ in the galvanic bath sample were revealed. The latter value showed a good agreement with the data obtained from ICP-OES analysis, which was also used for validation purpose.     

Development of a class selective immunoassay for the type II pyrethroid insecticides

A general and broad class selective enzyme-linked immunosorbent assay was developed for the type II pyrethroid insecticides, such as cypermethrin, deltamethrin, cyhalothrin, cyfluthrin, fenvalerate, esfenvalerate and fluvalinate. Polyclonal antibodies were generated by immunizing with a type II pyrethroid immunogen ((RS)-α-cyano-3-phenoxybenzyl (RS)-cis,trans-2,2-dimethyl-3-carboxyl-cyclopropanecarboxylate) conjugated with thyroglobulin. Antisera were screened against nine different coating antigens. The antibody-antigen combination with the most selectivity for type II pyrethroids such as cypermethrin was further optimized and tested for tolerance to co-solvent, pH and ionic strength changes. The IC₅₀s of the optimized immunoassay were 78 μg l⁻¹ for cypermethrin, 205 μg l⁻¹ for cyfluthrin, 120 μg l⁻¹ for cyhalothrin, 13 μg l⁻¹ for deltamethrin, 6 μg l⁻¹ for esfenvalerate, 8 μg l⁻¹ for fenvalerate and 123 μg l⁻¹ for fluvalinate. No cross-reactivity was measured for the type I pyrethroids such as permethrin, bifenthrin, phenothrin, resmethrin and bioresmethrin. This assay can be used in monitoring studies to distinguish between type I and II pyrethroids.     

Determination and interference studies of bismuth by tungsten trap hydride generation atomic absorption spectrometry

The determination of bismuth requires sufficiently sensitive procedures for detection at the μg L⁻¹ level or lower. W-coil was used for on-line trapping of volatile bismuth species using HGAAS (hydride generation atomic absorption spectrometry); atom trapping using a W-coil consists of three steps. Initially BiH₃ gas is formed by hydride generation procedure. The analyte species in vapor form are transported through the W-coil trap held at 289 °C where trapping takes place. Following the preconcentration step, the W-coil is heated to 1348 °C; analyte species are released and transported to flame-heated quartz atom cell where the atomic signal is formed. In our study, interferences have been investigated in detail during Bi determination by hydride generation, both with and without trap in the same HGAAS system. Interferent/analyte (mass/mass) ratio was kept at 1, 10 and 100. Experiments were designed for carrier solutions having 1.0 M HNO₃. Interferents such as Fe, Mn, Zn, Ni, Cu, As, Se, Cd, Pb, Au, Na, Mg, Ca, chloride, sulfate and phosphate were examined. The calibration plot for an 8.0 mL sampling volume was linear between 0.10 μg L⁻¹ and 10.0 μg L⁻¹ of Bi. The detection limit (3 s/m) was 25 ng L⁻¹. The enhancement factor for the characteristic concentration (C_o) was found to be 21 when compared with the regular system without trap, by using peak height values. The validation of the procedure was performed by the analysis of the certified water reference material and the result was found to be in good agreement with the certified values at the 95% confidence level.     

Liquid chromatography-hydride generation-atomic fluorescence spectrometry hybridation for antimony speciation in environmental samples

Atomic fluorescence spectrometry was used as an element-specific detector in hybridation with liquid chromatography (LC) and hydride generation for the speciation of Sb(III), Sb(V) and trimethylantimony dichloride (TMSbCl₂). The three species were poorly resolved in a single chromatogram but good results were obtained by anion-exchange chromatography, using a mobile phase with 20 mM EDTA and 8 mM hydrogenphthalate to separate Sb(III) and Sb(V) and 1 mM carbonate at pH 10 to separate Sb(V) and TMSbCl₂. Calibration graphs were linear between 2 and 100 μg l⁻¹. Detection limits were 0.9, 0.5 and 0.7 μg l⁻¹ for Sb(III), Sb(V) and TMSbCl₂, respectively. The method was applied to the speciation of antimony in environmental samples.     

Enhancement reagents for simultaneous vapor generation of zinc and cadmium with intermittent flow system coupled to atomic fluorescence spectrometry

Simultaneous vapor generation of zinc (Zn) and cadmium (Cd) was evaluated by atomic fluorescence spectrometry coupled with an intermittent flow vapor generation system. Some complexing reagents, surfactant and transition metal ions were respectively tested as enhancement reagents. Experiments showed that an appropriate amount of 8-hydroxyquinoline or phenanthroline and nickel ion simultaneously, effectively improved the vapor generation efficiency of Zn and Cd. The volatile species generation was presumed to be a hydrogenation process interpreting how the enhancement reagents played an important role in vapor generation. Additionally, due to the instability of volatile species, reaction temperature, rapid and sufficient mixing of reagents and rapid separation of the volatile species from liquid phase were also crucial. The method of simultaneous determination of Zn and Cd by intermittent flow vapor generation led to the development of atomic fluorescence spectrometry. The detection limits (3σ_b) were 1.6 μg l⁻¹ for Zn and 0.01 μg l⁻¹ for Cd and the relative standard deviations were 3.6% for Zn (50 μg l⁻¹, n=11) and 1.7% for Cd (2 μg l⁻¹, n=11) respectively. Results for the determination of Zn and Cd have been confirmed by the analysis of CRMs with good agreement between the certified and found values.     

Determination of arsenic(III) and total inorganic arsenic in water samples using an on-line sequential insertion system and hydride generation atomic absorption spectrometry

A simple and robust on-line sequential insertion system coupled with hydride generation atomic absorption spectrometry (HG-AAS) was developed, for selective As(III) and total inorganic arsenic determination without pre-reduction step. The proposed manifold, which is employing an integrated reaction chamber/gas-liquid separator (RC-GLS), is characterized by the ability of the successful managing of variable sample volumes (up to 25 ml), in order to achieve high sensitivity. Arsine is able to be selectively generated either from inorganic As(III) or from total arsenic, using different concentrations of HCl and NaBH₄ solutions. For 8 ml sample volume consumption, the sampling frequency is 40 h⁻¹. The detection limit is c_L = 0.1 and 0.06 μg l⁻¹ for As(III) and total arsenic, respectively. The precision (relative standard deviation) at 2.0 μg l⁻¹ (n = 10) level is s_r = 2.9 and 3.1% for As(III) and total arsenic, respectively. The performance of the proposed method was evaluated by analyzing the certified reference material NIST CRM 1643d and spiked water samples with various concentration ratios of As(III) to As(V). The method was applied for arsenic speciation in natural waters samples.     

Determination of bismuth in solid samples by hydride generation atomic fluorescence spectrometry with a dielectric barrier discharge atomizer

An atmospheric pressure dielectric barrier discharge (DBD) atomizer was investigated for bismuth (Bi) determination with hydride generation (HG) atomic fluorescence spectrometry (AFS). The characteristics of the atomizer and the effects of experimental parameters, including observation height, discharge power, flow rate of discharge gas and AFS carrier gas were optimized. The linear range of present method for Bi determination is 0.5-300.0 μg L⁻¹ with a detection limit of 0.07 μg L⁻¹ (3σ). The method was validated by the analysis of reference materials (GBW08517 and GSB-14) and the results agreed well with the reference values. The established method was applied to the determination of Bi in ore, soil and ash samples.     

Simultaneous determination of fluorophores with overlapped spectra by sequential injection analysis coupled to variable angle scanning fluorescence spectrometry and multivariate linear regression algorithms

An automated and versatile sequential injection spectrofluorimetric procedure for the simultaneous determination of multicomponent mixtures in micellar medium without prior separation processes is reported. The methodology is based upon the segmentation of a sample slug between two different buffer zones in order to attain both an improvement of sensitivity and residual minimization for the whole species. Resolution of overlapping fluorescence profiles is achieved using a variable angle scanning technique coupled to multivariate least-squares regression (MLR) algorithms at both sample edges.The potentialities of the described methodology are illustrated with the spectrofluorimetric determination of four widespread pesticides with different acid-base properties; viz. carbaryl (CBL) (1-naphthyl-N-methylcarbamate), fuberidazole (FBZ) (2-(2′-furyl)benzimidazole), thiabendazole (TBZ) (2-(4′-thiazolyl)benzimidazole) and warfarin (W) (3-α-acetonylbenzyl)-4-hydroxycoumarin). Detection limits at the 3σ level were 3.9, 0.02, 0.03 and 10 μg l⁻¹ for CBL, FBZ, TBZ and W, respectively at the maximum sensitivity pH. Dynamic ranges of 13-720 μg l⁻¹ CBL, 0.10-14 μg l⁻¹ FBZ, 0.19-60 μg l⁻¹ TBZ and 0.05-5 mg l⁻¹ W were achieved. Relative standard deviations (n=10) were 0.2% for 100 μg l⁻¹ CBL and 2.4 μg l⁻¹ FBZ, 0.7% for 8 μg l⁻¹ TBZ and 1.0% for 1 mg l⁻¹ W. The proposed automated methodology, which handles 17 samples/h, was validated and applied to spiked real water samples with very satisfactory results.     

Development of a new electrochemical hydride generator with tungsten wire cathode for the determination of As and Sb by atomic fluorescence spectrometry

A novel electrochemical hydride generator has been developed for the determination of As and Sb. This newly devised hydride generator is constructed from a flowing electrolytic cell, in which the tungsten wire is selected as cathode. Compared with some cathode material usually used in electrochemical hydride generator, the tungsten cathode is of better interference tolerance, corrosion-resistant and longer working time. The characteristics of the cathode material, hydride generating efficiency and interferences of concomitant have been studied in detail. The detection limits (3σ) of As and Sb in sample solution were 0.10 μg L⁻¹ and 0.15 μg L⁻¹, the precisions for 11 replicate measurements of 20 μg L⁻¹ As and Sb were 1.3% and 1.7%. The electrochemical hydride generator coupled with atomic fluorescence spectrometry has been applied to the determination of total As and Sb in tobacco samples.     

Speciation and preconcentration of inorganic antimony in waters by Duolite GT-73 microcolumn and determination by segmented flow injection-hydride generation atomic absorption spectrometry (SFI-HGAAS)

A selective matrix removal/separation/enrichment method, utilizing a microcolumn of a chelating resin with SH functional groups (Duolite GT-73), was proposed for the determination of Sb(III) in waters by segmented flow injection-hydride generation atomic absorption spectrometry (SFI-HGAAS). The resin was selective to Sb(III) at almost all pH and acidity values employed, whereas Sb(V) was not retained at all and could be determined after a pre-reduction step with l-cysteine. Spike recoveries were tested at various concentration levels in different water types and were found to vary between 85 and 118%. Accuracy of the proposed methodology was checked by analyzing a standard reference material and a good correlation was found between the determined (13.3 ± 1.1 μg l⁻¹) and the certified value (13.79 ± 0.42 μg l⁻¹). The method was applied to several bottled drinking water samples for antimony determination with and without preconcentration and none of the samples were found to contain antimony above the permissible level (5 μg l⁻¹). The characteristic concentration (the concentration of the analyte corresponding to an absorbance of 0.0044) was 0.55 μg l⁻¹ and the 3 s limit of detection (LOD) based on five times preconcentration was 0.06 μg l⁻¹. The applicability of the microcolumn separation/preconcentration/matrix removal method for flow injection systems was also demonstrated.     

Automatic flow procedure based on multicommutation exploiting liquid-liquid extraction for spectrophotometric lead determination in plant material

A not expensive automatic flow system based on multicommutation and exploiting the liquid-liquid extraction methodology for the determination of lead in plant material is described. The spectrophotometric procedure for lead determination was based on the reaction with dithizone followed by extraction using an organic solvent. The facilities afforded by the multicommutation approach allowed the use of an air stream as carrier, thus contributing to reduce the overall waste generation. The results obtained analysing plant materials compare very well with those obtained employing inductive coupled plasma optical emission spectrometry (ICP OES) at 90% confidence level. Others profitable features such as a linear response range between 50 and 200 μg l⁻¹ Pb (r = 0.999); a sampling rate of 15 determination per hour; a relative standard deviation of 1.8% (n = 12) for a typical sample containing 163 μg l⁻¹ Pb; a detection limit of 12 μg l⁻¹; a reagent consumption of 4.5 mg dithizone; and a waste generation of 225 μl organic solvent per determination were also achieved.     

Ochratoxin A in wines-assessing global uncertainty associated with the results

Ochratoxin A (OTA) is a mycotoxin (potentially carcinogenic secondary metabolite derived from fungal contamination), produced by some Aspergillus and Penicillium strains. Although present and legislated in different food sources in the human diet, the regulation for wine intake is still under discussion. The Office International de la Vigne et du Vin (OIV) recommended maximum levels in wine of 2 μg l⁻¹. Some reports refer to OTA contamination in wines up to 15 μg l⁻¹ and a special incidence in red wines from the southern regions of Europe and the north of Africa, but the majority of the data available are below 1 μg l⁻¹. When working at such low concentrations, the problem of the uncertainty of the results becomes decisive towards the implementation of legal limits. In order to assess the global uncertainty associated with OTA determination in wines and widen the data set and knowledge of the situation in Portugal, 340 wines were analysed (189 Port Wine, 85 Vinho Verde and 66 wines from other regions in the country) by a high performance liquid chromatography (HPLC)-fluorescence detection (FD) method using immunoaffinity columns for clean up. OTA was detected in 69 wines by the method used, but in concentrations below 0.5 μg l⁻¹, except for two which showed levels up to a maximum of 2.1 μg l⁻¹. However, the global uncertainty for OTA is close to 37% for concentrations above 0.5 μg l⁻¹, and therefore, such value can be below or exceed the OIV limit. In the vicinity of the limit of detection, 0.084 μg l⁻¹, the global uncertainty rises exponentially to a maximum of about 70%. This can be an obstacle when discussing safety intake limits. Ethanol and glucose content did not interfere in the clean up of OTA by immunoaffinity columns.     

On-line organoselenium interference removal for inorganic selenium species by flow injection coprecipitation preconcentration coupled with hydride generation atomic fluorescence spectrometry

The existence of dimethylselenium (DMSe) and dimethyldiselenium (DMDSe) in some environmental samples can cause serious interference on Se(IV) determination by hydride generation atomic fluorescence spectrometry (HG-AFS) due to their contribution on HG-response. A flow injection separation and preconcentration system coupled to HG-AFS was therefore developed by on-line coprecipitation in a knotted reactor (KR) for eliminating interference subjected from organoselenium. The sample, spiked with lanthanum nitrate, was merged with an ammonium buffer solution (pH 8.8), which promoted coprecipitation of Se(IV) and quantitative collection by 150 cm PTFE KR. DMSe and DMDSe, however, were unretained and expelled from the KR. An air flow was introduced to remove the residual solution from the KR, then a 1.2 mol l⁻¹ HCl was pumped to dissolve the precipitates and merge with KBH₄ solution for HG-AFS detection. The interference of DMSe and DMDSe on the Se(IV) determination by conventional HG-AFS and its elimination by the developed separation and preconcentration system were evaluated. With optimal experimental conditions and with a sample consumption of 12.0 ml, an enhancement factor of 18 was obtained at a sample frequency of 24 h⁻¹. The limit of detection was 0.014 μg l⁻¹ and the precision (R.S.D.) for 11 replicate measurements of 1.0 μg l⁻¹ Se(IV) was 2.5%. The developed method was successfully applied to the determination of inorganic selenium species in a variety of natural water samples.     

Part-per-trillion determination of chlorobenzenes in water using dispersive liquid-liquid microextraction combined gas chromatography-electron capture detection

In this study, a simple, rapid and efficient method, dispersive liquid-liquid microextraction (DLLME) combined gas chromatography-electron capture detection (GC-ECD), for the determination of chlorobenzenes (CBs) in water samples, has been described. This method involves the use of an appropriate mixture of extraction solvent (9.5 μl chlorobenzene) and disperser solvent (0.50 ml acetone) for the formation of cloudy solution in 5.00 ml aqueous sample containing analytes. After extraction, phase separation was performed by centrifugation and the enriched analytes in sedimented phase were determined by gas chromatography-electron capture detection (GC-ECD). Our simple conditions were conducted at room temperature with no stiring and no salt addition in order to minimize sample preparation steps. Parameters such as the kind and volume of extraction solvent, the kind and volume of disperser solvent, extraction time and salt effect, were studied and optimized. The method exhibited enrichment factors and recoveries ranging from 711 to 813 and 71.1 to 81.3%, respectively, within very short extraction time. The linearity of the method ranged from 0.05 to 100 μg l⁻¹ for dichlorobenzene isomers (DCB), 0.002-20 μg l⁻¹ for trichlorobenzene (TCB) and tetrachlorobenzene (TeCB) isomers and from 0.001 to 4 μg l⁻¹ for pentachlorobenzene (PeCB) and hexachlorobenzene (HCB). The limit of detection was in the low μg l⁻¹ level, ranging between 0.0005 and 0.05 μg l⁻¹. The relative standard deviations (R.S.D.s) for the concentration of DCB isomers, 5.00 μg l⁻¹, TCB and TeCB isomers, 0.500 μg l⁻¹, PeCB and HCB 0.100 μg l⁻¹ in water by using the internal standard were in the range of 0.52-2.8% (n = 5) and without the internal standard were in the range of 4.6-6.0% (n = 5). The relative recoveries of spiked CBs at different levels of chlorobenzene isomers in tap, well and river water samples were 109-121%, 105-113% and 87-120%, respectively. It is concluded that this method can be successfully applied for the determination of CBs in tap, river and well water samples.