Ultra-trace determination of arsenic species in environmental waters,food and biological samples using a modified aluminum oxide nanoparticle sorbent and AAS detection after multivariate optimization

We describe a simple and efficient method for solid phase extraction and speciation of trace quantities of arsenic. It is based on the use of functionalized aluminum oxide nanoparticles and does not require any oxidation or reduction steps. The experimental parameters affecting extraction and quantitation were optimized using fractional factorial design methods. Adsorbed arsenic was eluted from the sorbent with 1 M hydrochloric acid and determined by graphite furnace atomic absorption spectrometry. Preconcentration factors up to 750 were achieved depending on the sample volume. Studies on potential interferences by various anions and cations showed the method to be highly selective. Under optimum conditions, the calibration plots are linear in the 5.0 to 280 ng L⁻¹ and 8.0 to 260 ng L⁻¹ concentration ranges for As(III) and total arsenic, respectively. The detection limits (calculated for S/N ratios of 3) are 1.81 and 1.97 ng L⁻¹ for As(III) and total arsenic, respectively. The method was successfully applied to the determination and speciation of arsenic in (spiked) environmental, food and biological samples and gave good recoveries. The method was validated using a certified geological reference material.

Novel functionalized Al₂O₃ nanoparticles were synthesized and used for speciation and determination of arsenic in different samples. The experimental variables were optimized using fractional factorial design that can save time and operational costs.

     

Multivariate optimization of a procedure for Cr and Co ultratrace determination in vegetal samples using GF AAS after cloud-point extraction

Abstract

Sediment cores were collected at the MOLAR (MOuntain LAke Research) site Jörisee. The goal of the analysis was to date the sediment cores in order to correlate actual input conditions of nutrients and pollutants at this high-alpine, remote site, to historical situations. The sediment cores were dated by determining gamma rays of Pb-210 and Cs-137. The calculated sedimentation rate is 0.1 cm/year. Leaching techniques were used to investigate redox sensitive species. The results give evidence for post depositional recycling in case of Fe and Mn. In contrast, the heavy metals Pb, Zn, Cr and Ni are not affected by existing redox gradients. Sediment samples were leached with diluted nitric acid to determine anthropogenic input of Pb, Zn, Cr and Ni. Concentrations of these heavy metals reflect changes in the input conditions since the beginning of industrialization, which is the examined time period.     

Simultaneous determination of inorganic arsenic,antimony, selenium and tellurium by ICP-MS in environmental waters using SPE preconcentration on modified silica

This paper deals with a simplified multi-element profiling of inorganic arsenic, antimony, selenium and tellurium in the form of ⁷⁵As, ⁸²Se, ¹²¹Sb and ¹²⁵Te by ICP-MS for amounts less than 10?µg?L^?1. Internal standards such as ⁷²Ge and ²⁰⁹Bi were successfully used for the suppression of both influence of macro elements Na⁺, K⁺, Ca²⁺, Mg²⁺ or Al³⁺, and interference of limited concentrations of heavy metal ions. Modified silica sorbents Separon? SGX C18, C8, CN, NH₂, RPS and Phenyl were tested for the preconcentration of As, Sb, Se and Te (0.25–5?µg?L^?1) in the form of ion associates with cationic surfactants from 50–250?mL sample volume. 1-etoxycarbonyl-pentadecyltrimethylammonium bromide (Septonex®, 0.005?mol?L^?1) was suitable for this purpose in the presence of 4-(2-pyridylazo) resorcinol, 2-pyrrolidinecarbodithioate and 8-hydroxyquinoline-5-sulphonic acid. The quantitative retention occurred at pH 7?±?0.2 and the mixture of acetone with ethanol in ratio 1?:?1 in the presence of 0.1?mol?L^?1 HCl was used for the quantitative elution. Organic solvents and the excess of acid were removed by evaporation prior to the determination by ICP-MS. The determination of the above trace metalloids in various kinds of water with enrichment factor till 50 times on silica Separon? SGX C18 and the above reagents were compared with the standard addition method.     

Selective preconcentration and determination of iodine species in milk samples using polymer inclusion sorbent

A method to determine low levels of iodine species namely I⁻ and IO₃⁻ in aqueous samples was developed and applied to milk and milk powder samples. It is based on selective preconcentration of I⁻ in polymer inclusion sorbent (PIS) and neutron activation analysis (NAA) of I⁻ sorbed in PIS. The PIS was found to be highly selective for I⁻ in presence of IO₃⁻ and other anions commonly present in the milk samples. In order to preconcentrate total I⁻ + IO₃⁻ content in the PIS, IO₃⁻ was reduced to I⁻ using a mixture of acetic acid and ascorbic acid. It was found that total iodine content in milk could be determined with epithermal neutron activation analysis (ENAA). A scheme was developed to determine I⁻, IO₃⁻ and total iodine. The developed method was applied to milk reference materials (NIST SRM-1549 and IAEA-RM-153 milk powder) and a commercially available milk powder. The scheme for estimation of iodine in different forms was validated by using reference material NIST SRM-1549.     

Simplex optimization of conditions for the determination of arsenic in environmental samples by using electrothermal atomic absorption spectrometry

Simplex optimization was used to efficiently delineate the optimum experimental conditions to be used for the electrothermal atomic absorption spectrometric analysis of arsenic in a standard reference material of marine origin. Four experimental variables, were considered: ashing temperature, atomization temperature, modifier concentration, and atomization ramping time. This combination of methods and materials provides a powerful means of rapidly improving the experimental conditions used for analysis of arsenic in a wide variety of samples of environmental origin. Excellent recoveries of arsenic were obtained when using the optimum electrothermal atomic absorption spectrometry conditions to analyze standard solutions of arsenobetaine, arsenocholine and tetramethylarsonium iodide.     

Non-destructive determination of aluminum in biological reference samples using neutron activation analysis

The non-destructive methods of thermal and epithermal neutron activation analysis have been employed to determine the aluminum concentration of seven National Institute of Standards and Technology certified biological reference materials. Through the judicious use of both thermal and epithermal neutron activation analysis using bare and boron-lined irradiation carriers, the major and minor contributions of the³¹P/n, /²⁸Al and of the²⁸Si/n, p/²⁸Al reactions, respectively, to the²⁷Al/n, /²⁸Al reaction could be corrected for explicitly. Based on replicate determinations precision of the analysis ranged from 2.5% for citrus leaves determined at the 75 ppm level to 18% for bovine liver measured at the 1 ppm level. Accuracy was demonstrated whenever possible by comparison to existing published data.     

Nonextractive spectrofluorimetric determination of aluminium in real, environmental and biological samples using chromotropic acid

An ultra-sensitive and highly selective nonextractive fluorimetric method is presented for the rapid determination of aluminium at nano-trace levels using chromotropic acid as a fluorimetric reagent [lambda(ex) = 360 nm and lambda(em) = 390 nm] in the pH range of 4.1-4.7. The fluorescence intensity of the metal chelate (2:3 complex) reaches a constant value within 1/2 hr and remains unchanged for over 48 hr. The fluorescence intensity aluminium concentration calibration curve is collinear between 1 and 300 ng/ml of Al. A constant fluorescence intensity is obtained over a wide range (1:50-1:1500) of Al:reagent molar concentrations. Large excesses of over 60 cations, anions and complexing agents (like tartrate, oxalate, phosphate, thio-urea, SCN(-), etc.) do not interfere in the Al determination. The developed method was successfully used in assaying aluminium in several standard reference materials (Al-bronze, brass, stainless steel) as well as in some environmental and biological samples. The method is very precise and accurate (S.D = +/-0.001 on 10 ng/ml; 11 determinations).     

Modified nanoalumina sorbent for sensitive trace cobalt determination in environmental and food samples by flame atomic absorption spectrometry

1-(2-pryidylazo)-2-naphthol (PAN) immobilized on sodium dodecyl sulfate-coated nano alumina was developed for the preconcentration and determination of metal cations Co (II) from environmental and food samples. The research results displayed that adsorbent has the highest adsorption capacity for Co (II) in this system. Desorption by elution of the adsorbent with 2.0?ml of a mixture of nitric acid and ethanol was carried out. After phase separation, the enriched analyte in the final solution is determined by flame atomic absorption spectrometry (FAAS) by using a micro sample introduction system. Analytical influencing parameters including pH value, amount of sorbent, equilibrium time, sample volume, volume and concentration of eluent were examined. The effect of common matrix ions has also been investigated and it was found that they had no influence on cobalt preconcentration. Under the optimum experimental conditions, the maximum capacity of sorbent was obtained as 20?mg?g^?1. The preconcentration factor and limit of detection were found to be 250 and 0.15?µg?L^?1, respectively. This method showed good precision with the relative standard deviation (RSD) of 2.4% and 2.1% in concentrations of 20 and 50?µg?L^?1, respectively. The accuracy of the method was evaluated by comparison of results with those obtained by electrothermal atomic absorption spectrometry. This method was successfully applied for preconcentration and determination of Co (II) in environmental and food samples.     

Analytical methodology for speciation of arsenic in environmental and biological samples

A literature search on the speciation of arsenic in environmental and biological samples shows an increasing interest of many researchers in the subject. Because of the low level of arsenic species in real samples, many problems related with its speciation remain unresolved: species instability during sampling, storage and sample treatment, incomplete recovery of all species, matrix interferences, lack of appropriate certified reference materials and of sensitive analytical methods, etc. These aspects are underlined in this paper. The continued development of new analytical procedures pretending to solve some of these problems claim for an up-to-date knowledge of the recent publications. Therefore, this paper pretends to review the latest publications on the chemical speciation of arsenic, emphasizing the increasing activity in the development of accurate and precise analytical methods. In most of the cases, separation and preconcentration is necessary, followed by element-specific detection for sensitivity improvement. Hydride generation following separation procedures (e.g., ion-exchange or high performance liquid chromatography) coupled to atomic absorption or atomic emission detectors proved to have sufficient sensitivity to monitor arsenic exposure, although restricts the analysis to hydride-forming species. Modified procedures including some kind of heating in the presence of highly oxidizing agents have proved successful to completely decompose the arsenic containing compounds to arsenate and so to extend the range of compounds which can be determined by these methods. On-line arrangements have the additional advantage of avoiding excessive sample handling, although some of them involve numerous steps and others are too costly to be recommended for routine use. The analytical figures of merits, specially detection limits are given for most of the methods in order to afford comparison and judge possible applicability. These studies, which have been approached in many different ways, would lead to knowledge that are determinant in the understanding of the cycle of this element in environment and of its physiological and toxicological behavior in the living organisms.     

Simultaneous determination of arsenic and selenium in biological samples by HG-AFS

A new method is proposed for simultaneous determination of traces of arsenic (As) and selenium (Se) in biological samples by hydride-generation double-channel non-dispersive atomic-fluorescence spectrometry (HG-AFS) from tartaric acid media. The effects of analytical conditions on fluorescence signal intensity were investigated and optimized. Interferences from coexisting ions were evaluated. Under optimum conditions linear response ranges above 20 g L^–1 for As and 32 g L^–1 for Se were obtained with detection limits of 0.13 and 0.12 g L^–1, respectively. The precision for elevenfold determination of As at the 4 g L^–1 level and of Se at the 8 g L^–1 level were 2.7 and 1.9% (RSD), respectively. Recoveries of 92.5–95.5% for As and 101.2–108.4% for Se were obtained for four biological samples and two certified biological reference materials. The proposed method has the advantages of simple operation, high sensitivity, and high efficiency; it was successfully used for simultaneous determination of As and Se in biological samples.     

Spectrophotometric determination of isoproturon using p-aminoacetophenone and its application in environmental and biological samples

A simple and sensitive method for the determination of isoproturon, a widely used herbicide is described here which is based on alkaline hydrolysis of isoproturon to its corresponding primary amine followed by diazotization and coupling with p-aminoacetophenone in alkaline medium. The absorption maxima of the coloured compound formed is measured at 525 nm. Beer's law is obeyed over the concentration range of 0.5-5.0 mug in a final solution volume of 25 ml (0.02-0.2 ppm). The molar absorptivity and Sandell's sensitivity were found to be 8.6x10(5) l mol(-1) cm(-1) and 0.0002 mug cm(-2), respectively. The method has been satisfactorily applied to the determination of isoproturon in environmental and biological samples.     

Flame atomic absorption spectrometric determination of trace amounts of Pb(II) and Cr(III) in biological, food and environmental samples after preconcentration by modified nano-alumina

A new solid-phase extraction sorbent was used for the preconcentration of Pb(II) and Cr(III) ions prior to their determination by flame atomic absorption spectrometry. It was prepared by immobilization of 2,4-dinitrophenylhydrazine on nano-alumina coated with sodium dodecyl sulfate. The sorbent was characterized by scanning electron microscopy, N₂ adsorption and Fourier transform infrared spectrometry, and used for preconcentration and separation of Pb(II) and Cr(III) from aqueous solutions. The ions on the sorbent were eluted with a mixture of nitric acid and methanol. The effects of sample pH, flow rates of samples and eluent, type of eluent, breakthrough volume and potentially interfering ions were studied. Linearity is maintained between 1.2 and 350???g?L^-1 of Pb(II), and between 2.4 and 520???g?L^-1 of Cr(III) for an 800-mL sample. The detection limit (3?s, N?=?10) for Pb(II) and Cr(III) ions is 0.43 and 0.55???g?L^-1, respectively, and the maximum preconcentration factor is 267. The method was successfully applied to the evaluation of these trace and toxic metals in various water, food, industrial effluent and urine samples.

Simultaneous determination of arsenic and antimony species in environmental samples using bis(trifluoroethyl)dithiocarbamate chelation and supercritical fluid chromatography.

Simultaneous separation and quantitation of arsenic(III) and antimony(III) can be achieved by extraction with lithium bis(trifluoroethyl)dithiocarbamate followed by supercritical fluid chromatographic (SFC) analysis. Arsenic(V) and antimony(V) are extracted after reduction with potassium iodide and sodium thiosulfate. Detection limits of 7 pg As and 11 pg Sb are achieved using this extraction method and SFC. Application to natural water and biological sample analysis is discussed.     

Rapid determination of antimony in biological and environmental samples using instrumental neutron activation analysis

A rapid non-destructive activation analysis method has been developed for the determination of antimony. A high resolution low energy Ge detector is used to measure the 61.6 keV γ-ray from^122mSb (T=4.2 min). Sensitivities and detection limits for biological and environmental samples activated with thermal and epithermal neutrons are listed. The time required for the anlaysis is about 12 min per sample using thermal activation and 22 minutes using epithermal activation analysis.     

Spectrophotometric determination of lead in industrial, environmental, biological and soil samples using 2,5-dimercapto-1,3,4-thiadiazole

A very simple, ultra-sensitive and fairly selective non-extractive spectrophotometric method for the determination of trace amounts of lead with 2,5-dimercapto-1,3,4-thiadiazole (DMTD) has been developed. DMTD reacts in slightly acidic (0.0015-0.01 M HCl) aquatic media with lead(II) to give a greenish-yellow chelate, which has an absorption maximum at 375 nm. The reaction is instantaneous and absorbance remains stable for 24 h. The average molar absorption coefficient and Sandell's sensitivity were found to be 4.93x10(4) lmol(-1)cm(-1) and 15 ngcm(-2) of Pb, respectively. Linear calibration graphs were obtained for 0.1-40 mugml(-1) of Pb; the stoichiometric composition of the chelate is 1:2 (Pb-DMTD). The interference from over 50 cations, anions and complexing agents has been studied at 1 mugml(-1) of Pb. The method developed was used successfully in the determination of lead in several standard reference materials (alloys and steels), environmental waters (potable and polluted), biological samples (human blood and urine), soil samples, solutions containing both lead(II) and lead(IV) and complex synthetic mixtures. The method has high precision and accuracy (S=+/-0.01 for 0.5 mugml(-1)).     

Comparative studies of methylmercury determination in biological and environmental samples

Some parameters affecting the accuracy of various approaches to methylmercury (MeHg) determination in biological and environmental samples were studied. Different isolation techniques (ion-exchange, extraction, volatilization, distillation) and final measurement via cold vapour atomic absorption spectroscopy (CV AA) or gas chromatography (GC) were compared. Results obtained by the various isolation techniques are comparable for almost all biological and environmental samples, except for soils and some sediments, where disagreement between the results obtained by GC and CV AA was found. In order to resolve these problems, a new separation technique based on distillation of MeHg from the sample followed either by CV AA or GC was developed. The new method results in very good recovery and reproducibility (95 ± 2%) for all samples examined (fish, mussel, shrimp, blood, hair, algae, sediment, etc.), is specific for MeHg and provides for its differentiation from other species by an indirect CV AA determination. Gas-chromatographic measurement of the isolated MeHg using different packings and conditioning of the columns is also discussed. The distillation method with GC detection is advantageous in producing cleaner chromatograms and in prolonging the life-time of the packing and the intervals between reconditioning.     

HPLC-MS/MS multiclass determination of steroid hormones in environmental waters after preconcentration on the carbonaceous sorbent HA-C@silica

In this study, a sensitive and multiclass method has been developed for analysis of three families of steroid hormones, i.e. progestins, oestrogens, androgens, by SPE-HPLC-ESI-MS/MS. The extraction efficiency of thermally condensed humic acids onto silica sorbent (HA-C@silica), here for the first time studied for multiclass enrichment of these sex hormones, was tested in different environmental waters (tap and river water, urban wastewater treatment plant effluent) spiked at the nanograms per litre levels (5–1000 ng L⁻¹). Quantitative adsorption was achieved using 200 mg sorbent for preconcentration of 250–1000 mL sample, at the native pH (pH = 6.5–7.7). Elution was performed by two sequential fractions (methanol followed by acetonitrile), obtaining in all the matrices investigated satisfactory recoveries (71% to 124% for river waters and 71–113% for urban wastewater treatment plant effluent) and RSDs below 15% (n = 3). The high enrichment factors (up to 4000) coupled with high-performance liquid chromatography tandem mass spectrometry quantification (MRM mode) provided low limits of detection and quantification (a few ng L⁻¹), that are suitable for environmental monitoring. Most of the analytes were detected in river water and in wastewater effluent samples (in the ng L⁻¹ concentration range), attesting their environmental diffusion. The proposed method was extended to a fourth class, Glucocorticoids, achieving good results in river samples, by the same SPE cartridge and chromatographic run.     

Determination of trace amounts of cadmium,copper and nickel in environmental water and food samples using GO/MgO nanocomposite as a new sorbent

A solid phase extraction method based on graphene oxide (GO) modified with magnesium oxide (MgO) nanoparticles was developed for the preconcentration and determination of trace amounts of cadmium, copper and nickel ions. The adsorbed analytes were eluted by 4.0 mL of 0.1 M (EDTA) and injected to flame atomic absorption spectrometer. The factors influencing the complex formation and extraction of these heavy metals were optimized. Studies on potential interference by various anions and cations showed the method to be highly selective. The preconcentration factor was about 11 with relative standard deviation of <4.0 for 8 replication determination. The detection limits for the Cd, Cu, Ni were found to be 0.5, 3.4 and 25 µg L^?1, respectively. The method was successfully applied for the determination of cadmium, copper and nickel in tap water, well water, sea water, rice and macaroni samples with spike recoveries ranging 93–105 %.     

A new functionalized resin and its application in preconcentration system with multivariate optimization for nickel determination in food samples

In this work, Amberlite XAD-2 resin functionalized with 4,5-dihydroxy-1,3-benzenedisulfonic acid was synthesized, characterized and applied as a new packing material for an on-line system to nickel preconcentration. The method is based on the sorption of Ni(II) ions in a minicolumn containing the synthesized resin, posterior desorption using an acid solution and measurement of the nickel by spectrophotometry (PAR method). The optimization of the system was performed using factorial design and Doehlert matrix considering five variables: eluent concentration, PAR solution pH, sample flow rate, PAR solution concentration and sample pH. Signals were measured as peak height by using an instrument software. Using the experimental conditions defined in the optimization, the method allowed nickel determination with achieved sampling rate of 25 samples per hour, detection limit (3 s) of 2 μg l⁻¹ and precision (assessed as the relative standard deviation) of 8.2-2.6%, for nickel solutions of 10.0-200.0 μg l⁻¹ concentration, respectively. The experimental enrichment factor of the proposed system was 46, for 120 s preconcentration time. The proposed procedure was applied for nickel determination in food samples. Recoveries of spike additions (5 or 10 μg g⁻¹) to food samples were quantitative (94-110%).