A novel procedure for phase separation in dispersive liquid-liquid microextraction based on solidification of the aqueous phase.

In this paper, an alternative for handling the organic phase after a dispersive liquid-liquid microextraction using organic solvents lighter than water is presented. It is based on solidification (at -18°C) of the aqueous phase obtained after centrifugation, and the decantation, collection and analysis of the liquid organic layer. The extraction of nicotine in toluene, and its determination in eggplant samples was conducted as a proof of concept. The study has been carried out using standards prepared in water and the formation of the dispersion was assisted by sonication. The organic extract was analysed using gas chromatography coupled to mass spectrometry. Satisfactory analytical figures of merit as: limit of detection (0.4µgL(-1), 2ngg(-1) wet sample), limit of quantification (1.2µgL(-1), 6.5ngg(-1) wet sample), within-day precision (RSD=7%), and linearity interval (up to 384µgL(-1) nicotine) were achieved. It constituted a contribution to the handling of organic extracts after microextraction processes.

Distribution of trace metals in marine sediments of the Bay of Palma de Mallorca (Mallorca Island, Spain).

Metals were determined in surface bottom marine sediments of the Bay of Palma de Mallorca (Spain) by microwave-assisted acid-oxidant digestion and inductively coupled plasma-optical emission spectrometry in order to assess the level and distribution of potentially metallic pollutants. Average concentrations found were 1.2 ± 0.3 Al and 1.9 ± 0.9 Fe (in milligrams per gram), and 8 ± 2 Cr, 2 ± 1 Cu, 60 ± 10 Mn, 4 ± 1 Ni, 6 ± 4 Pb, 50 ± 7 Sn and 10 ± 3 Zn (in micrograms per gram). Enrichment factors using normalized values to Al were also calculated which indicated that sediments were Sn and Pb enriched. Sediments were fractionated by grain size: <63, 63-250, 250-500 and >500 (in micrometres), and the metals' affinity towards the different fractions was studied. The metals' affinity to the finer fraction was evidenced, excluding Sn and Mn that showed practically no affinity for fine grains. Latent variables were extracted from the data using principal components analysis. It allowed samples to be grouped in two clusters, and most of the metals (Al, Cr, Cu, Fe, Ni, Pb and Zn) showed a similar distribution pattern. Sn and Mn showed a distinct pattern.

Application of in-vial membrane assisted solvent extraction to the determination of polycyclic aromatic hydrocarbons in seawater by gas chromatography-mass spectrometry.

A device for membrane assisted solvent extraction from an aqueous sample to an organic solvent within a micro-vial compatible with a chromatography auto-sampler was used to extract trace amounts of seven polycyclic aromatic hydrocarbons from seawater. The device consisted in an assembly of a volumetric flask containing the sample and a micro-vial containing the organic solvent by means of a screw stopper in which the septum was replaced by a sized piece of a membrane. Extraction conditions (nature of the organic solvent, extraction time, presence of ethanol in the donor phase, ionic content of the donor phase, characteristics of the membrane and volumes of donor and acceptor phases) were studied in order to find the conditions for maximum extraction. Analytical performance characteristics have also been established. The extraction efficiency was between 12.5 and 23%, which implies an enrichment factor value above 40. The repeatability and reproducibility were in the range of 8.6-10.0% and 13-19%, respectively. Detection limits were in the range of 24-39 ng L(-1). Nine seawater samples have been studied. Most of the concentrations were under the limits of detection. Naphthalene and phenanthrene contents have been determined in a sample using the method of standard additions, and concentrations 100 and 91 ng L(-1), respectively.

A simple novel configuration for in-vial microporous membrane liquid-liquid extraction.

A novel arrangement for microporous membrane liquid-liquid extraction from the aqueous donor phase to the organic acceptor phase within a micro-vial, which is compatible with the chromatograph autosampler is presented. The device consisted of a stoppered glass micro-vial containing the organic solvent where the septum of the screw stopper was replaced by a sized piece of membrane which is hermetically assembled to the volumetric flask containing the aqueous donor solution. The placement of the membrane in alternative contact with the solutions was achieved by orbital agitation. As a preliminary study, 2-ethylhexyl 4-(dimethylamino)benzoate has been determined (limit of quantification 0.11 microg L(-1), precision 7.4%). The small quantity of organic solvent used, the achieved sample cleanup, and the minimal handling and risk of cross-contamination are significant operational advantages.

Determination of 2-ethylhexyl 4-(dimethylamino) benzoate using membrane-assisted liquid-liquid extraction and gas chromatography-mass spectrometric detection.

A flow-cell for micro-porous membrane liquid-liquid extraction with a sheet membrane was used to extract 2-ethylhexyl 4-(dimethylamino) benzoate (EDB) from urine of solar-cream users and spiked wine samples. The cell enabled the target analyte to be extracted from 7.9 mL of donor solution into 200 microL of acceptor solution (decane). After extraction, the acceptor solution was transferred to a micro-vial for GC-MS analysis without derivation. In this work, variables affecting the enrichment factor were also studied, such as organic solvent, extraction time, recirculation flow of the donor solution through the donor chamber, presence of potassium chloride and ethanol in the donor solution and pH. The method has been evaluated in terms of linearity, sensitivity, precision, limits of detection and quantification and extraction efficiency. Limits of quantification were 1 and 3 microg L(-1) EDB for urine and wine, respectively. Quantitative analysis has been carried out by applying the method of standard additions. Within- and between-day relative standard deviations were lower than 12% and 20%, respectively. EDB was found in the urine of users of cream containing EDB in the concentration interval 1.2-7.2 microg L(-1). Therefore, this provides evidence of EDB dermal absorption and subsequent excretion through the urinary tract. EDB was not found in the analysed wine samples.

An environmental friendly method for the automatic determination of hypochlorite in commercial products using multisyringe flow injection analysis.

A multisyringe flow injection analysis system was used for the determination of hypochlorite in cleaning agents, by measurement of the native absorbance of hypochlorite at 292 nm. The methodology was based on the selective decomposition of hypochlorite by a cobalt oxide catalyst giving chloride and oxygen. The difference of the absorbance of the sample before and after its pass through a cobalt oxide column was selected as analytical signal. As no further reagent was required this work can be considered as a contribution to environmental friendly analytical chemistry. The entire analytical procedure, including in-line sample dilution in three steps was automated by first, dilution in a stirred miniature vessel, second by dispersion and third by in-line addition of water using multisyringe flow injection technique. The dynamic concentration range was 0.04-0.78 gL(-1) (relative standard deviation lower than 3%), where the extension of the hypochlorite decomposition was of 90+/-4%. The proposed method was successfully applied to the analysis of commercial cleaning products. The accuracy of the method was established by iodometric titration.

Breakpoint chlorination curves of greywater.

A study on chlorination of raw greywater with hypochlorite is reported in this paper. Samples were chlorinated in a variety of conditions, and residual chlorine (Cl2) was measured spectrophotometrically. For each sample, the chlorination curve (chlorine residuals versus chlorine dose) was obtained. Curves showed the typical hump-and-dip profile attributable to the formation and destruction of chloramines. It was observed that, after reactions with strong reductants and chloramines-forming compounds, the remaining organic matter exerted a certain demand of chlorine. The evolution of chlorination curves with addition of ammonia and dodecylbencene sulfonate sodium salt and with dilution of the greywater sample were studied. In addition, chlorination curves at several contact times have been obtained, resulting in slower chlorine decay in the hump zone than in the dip zone. In addition, the decay of coliforms in chlorinated samples was also investigated. It was found that, for a chlorination dosage corresponding to the maximum of the hump zone (average 8.9 mg Cl2/ L), samples were negative in coliforms after 10 to 30 minutes of contact time. After-growth was not observed within 3 days after chlorination. Implications in chlorination treatments of raw greywater can be derived from these results.

A green method for the determination of hypochlorite in bleaching products based on its native absorbance.

A new, green method for the determination of hypochloride in bleaching products is here presented. The method, based on a flow injection system and measurement of the native absorbance of hypochlorite at 292nm, allows the determination of hypochlorite in the range 0.07-0.42gCl(2)l(-1). In order to achieve high selectivity a mini-column containing cobalt oxide, which effectively catalyses hypochlorite decomposition to chloride and oxygen, was inserted in the flow system. The difference in absorbance of samples no circulated and circulated through the mini-column was selected as analytical signal; thus, the method only requires 20mg of solid, reusable catalyst, and a NaOH solution of pH 10.4; providing a sample throughput of 12 samplesh(-1) in triplicate injection. Its usefulness for analysis of bleaching products is demonstrated.

Learning from samples of one or fewer. 1991.

Organizations learn from experience. Sometimes, however, history is not generous with experience. We explore how organizations convert infrequent events into interpretations of history, and how they balance the need to achieve agreement on interpretations with the need to interpret history correctly. We ask what methods are used, what problems are involved, and what improvements might be made. Although the methods we observe are not guaranteed to lead to consistent agreement on interpretations, valid knowledge, improved organizational performance, or organizational survival, they provide possible insights into the possibilities for and problems of learning from fragments of history.

Determination of residual chlorine in greywater using o-tolidine.

The determination of chlorine with o-tolidine in greywater has been studied, and a batch method and a sequential injection method have been proposed. It was found that the reaction of o-tolidine with chlorine was slower in a greywater matrix. Grey water samples must be filtered before analysis, or alternatively, a blank of sample must be measured. The samples are very unstable, and after 2 h of storage in dark conditions at 4 degrees C the chlorine concentration can diminish. The standard addition method, in some samples gave unsatisfactory results as a consequence of matrix effects. It was concluded that samples with a total organic carbon (TOC) higher than 60 mgCl(-1) can not be accurately analysed using these methods. However, samples with a TOC lower than 60 mgCl(-1) gave 100+/-3% recoveries. The linear range of the methods was 0-3.0 and 0-5.0 mgCl(2)l(-1), and the limit of quantification 0.2 and 0.5 mgCl(2)l(-1), for the batch method and the sequential injection method, respectively. This is the first paper devoted to grey water from the analytical chemistry point of view.

Determination of pyrophosphate in renal calculi and urine by means of an enzymatic method.

An enzymatic method for the determination of pyrophosphate which has been applied to renal calculi is described. The method involves the preconcentration of pyrophosphate using anionic exchange resin and development of the enzymatic reactions with the pyrophosphate retained on the resin. The study of calculi treatment according to calculi composition is also reported. The pyrophosphate content was dependent on the calculi composition. The highest amount of pyrophosphate was found in hydroxyapatite calculi (of the order of 10 microg/g), struvite and oxalate calculi showed a lower amount (the order was 2.5 and 4.5 microg/g, respectively) and was not detected in uric acid and cystine stones. The method was also successfully applied to the determination of pyrophosphate in human urine. For urinary pyrophosphate determination, a modification based on a clean-up of urine using activated carbon has been proposed. Pyrophosphate in human urine was of the order of 4 mg l(-1).

Absorption and excretion of orally administered inositol hexaphosphate (IP(6) or phytate) in humans.

A study of the pharmacokinetic profile (oral absorption and renal excretion) of inositol hexaphosphate or phytate (IP(6)) is presented. Seven healthy volunteers were following a IP(6) poor diet (IP(6)PD) in a first period, and on IP(6) normal diet (IP(6)ND) in a second one. When following the IP(6)PD they become deficient in IP(6), the basal levels found in plasma (0.07+/- 0.01 mg/L) being clearly lower than those found when IP(6)ND was consumed (0.26+/- 0.03 mg/L). During the restriction period the maximum concentration in plasma were obtained 4 h after the ingestion of a single dose of IP(6), observing almost the same renal excretion profiles for the three different commercial sources and doses. After the IP(6) restriction period, volunteers were on IP(6)ND, reaching normal plasma and urinary IP(6) values in 16 days. Thus, the normal plasma and urinary concentrations, can be obtained either by consumption of a IP(6)ND taking a long time or in a short period by IP(6) supplements.

Sequential injection spectrophotometric determination of oxybenzone in lipsticks.

A sequential injection (SI) procedure for the spectrophotometric determination of oxybenzone in lipsticks is reported. The colorimetric reaction between nickel and oxybenzone was used. SI parameters such as sample solution volume, reagent solution volume, propulsion flow rate and reaction coil length were studied. The limit of detection was 3 microg ml(-1). The sensitivity was 0.0108+/-0.0002 ml microg(-1). The relative standard deviations of the results were between 6 and 12%. The real concentrations of samples and the values obtained by HPLC were comparable. Microwave sample pre-treatment allowed the extraction of oxybenzone with ethanol, thus avoiding the use of toxic organic solvents. Ethanol was also used as carrier in the SI system. Seventy-two injections per hour can be performed, which means a sample frequency of 24 h(-1) if three replicates are measured for each sample.

Phytate levels in diverse rat tissues: influence of dietary phytate.

Phytate (inositol hexaphosphate; InsP6) was determined in rat tissues fed on diets with different phytate contents, using a GC-mass detection methodology that permitted the evaluation of the total amount of this substance present in such tissues. The highest InsP6 concentrations were found in brain 5.89 x 10(-2)(SE 5.7 x 10(-3)) mg/g DM), whereas the concentrations detected in kidneys, liver and bone were similar to each other 1.96 x 10(-3) (SE 0.20 x 10(-3), 3.11 x 10(-3) (SE 0.24 x 10(-3), 1.77 x 10(-3) (SE 0.17 x 10(-3)) mg/g DM respectively) and 10-fold less than those detected in brain. When rats were fed on a purified diet in which InsP6 was undetectable, the InsP6 levels of the organs mentioned earlier decreased dramatically (9.0 x 10(-4), 3.8 x 10(-5), 1.4 x 10(-5) mg/g DM in brain, kidneys and liver respectively) and in some cases became undetectable (bone). The addition of InsP6 to this purified diet led to the increase of InsP6 levels in these tissues. This clearly demonstrated that the majority of the InsP6 found in organs and tissues has a dietary origin and is not a consequence of endogenous synthesis. Consequently, considering that InsP6 could be involved in some important biological roles, the value of any diet on supplying this substance is noteworthy.

Determination of phytic acid by gas chromatography-mass spectroscopy: application to biological samples.

A GC-MS method is reported for the determination of phytic acid based on purification by anion-exchange chromatography, enzymatic hydrolysis of phytic acid to myo-inositol and derivation to trimethylsilyl derivative, with scyllo-inositol as an internal standard. Analytical features of the method are: limit of detection 9 microg l(-1) phytic acid, linear working range 18-500 microg l(-1) phytic acid, and coefficient of variation 1.9%. The method has been successfully applied to a variety of biological samples: various rat organs (kidney, liver, brain and bone), human plasma and urine and kidney stones. A comparative study of sample treatments, including deproteization, lipid extraction and the presence of a chelator, is also reported. Phytic acid amounts found in rat organs ranged from 1.07 g kg(-1) for bone to 32.0 g kg(-1) for brain. Phytic acid in human plasma was of the order of 0.14 mg l(-1). In kidney stones, phytic acid was found in calcium containing stones.

Efficient flow injection and sequential injection methods for spectrophotometric determination of oxybenzone in sunscreens based on reaction with Ni(II).

Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LOD are adequate to the analysis requirements. The sample frequency obtained by FI is three-fold higher than that of SI analysis. SI is less reagent-consuming than FI.

Determination of phosphate in urine by sequential injection analysis.

Two simple turbidimetric methods for the determination of phosphate in urine are presented and compared. One method is based on the calcium phosphate crystallisation, and the other one on the inhibitory action of phosphate on the calcium carbonate crystallisation. The analytical features of both methods were: linear range = 0.2-1.5 g L-1, LOD = 14 mg L-1 and RSD 1.1-2.0% for the calcium phosphate method, linear range = 0.1-1.8 mg L-1, LOD = 0.01 mg L-1 and RSD 0.97-1.90% for the inhibitory method. Urines with high calcium content (> or = 400 mg L-1) can interfere the method based on the crystallisation of calcium phosphate. This interference was solved using a cation exchange resin as a part of the manifold. Considering the low toxicity of used reagents, these methods can be considered as a contribution to Green Analytical Chemistry.

Variation of InsP(4),InsP(5) and InsP(6) levels in tissues and biological fluids depending on dietary phytate.

Due to the increasing interest of InsP(6) on human health, the aim of this paper is to compare the levels of highly phosphorilated inositols (InsP(4), InsP(5) and InsP(6)) in organs and biological fluids of rats and to study the influence of the presence and absence of InsP(6) in diets. Thus, for this purpose, the variation of InsP(4), InsP(5) and InsP(6) levels in organs and biological fluids of rats submitted to two different diets were studied. In the AIN-76A diet no InsP(6) was present, yet the other was a 1% InsP(6) modified diet (AIN-76A + 1% InsP(6)). The highest InsP(4), InsP(5) and InsP(6) levels were found to be 10-fold superior in the brain than those found in the kidney. When the InsP(6) was eliminated from the diet, the InsP(6) levels decreased dramatically (97.2% in kidney, 89.8% in brain, 100% in bone, 90.5% in plasma and 98.1% in urine), the InsP(5) levels showed an important decrease (61.2% in kidney, 45.5% in brain, 28.1% in bone, 30% in plasma and 88.6% in urine) and the InsP(4) levels in organs only changed slightly. From these results, it can be deduced that the majority of InsP(6) present in the organism is of dietary origin and its endogenous synthesis is not important. According to the results, it can be evidenced that the endogenous synthesis of InsP(5) can occur, besides InsP(6) can be transformed by enzymatic dephosphorilation in InsP(5).

Dietary phytate and mineral bioavailability.

The relation between the dietary phytate (InsP6), mineral status and InsP6 levels in the organism, using three controlled diets (AIN-76A, AIN-76A + 1% phytate, AIN-76A + 6% carob seed germ), are studied. AIN-76A is a purified diet in which InsP6 is practically absent. No important or significant differences in the mineral status (Zn, Cu, Fe) of blood, kidneys, liver, brain and bone, were observed, except iron in the brain. Thus, the amounts of iron found in the brain of rats fed AIN-76A + 1% InsP6 were significantly inferior to those found in rats fed AIN-76A diet. The amounts of InsP6 found in organs of rats fed AIN-76A diet became very low or even undetectable while the ones found in rats fed diets that contained 1% and 0.12% (AIN-76A + 6% carob seed germ) InsP6, were considerably higher and similar. Moreover the majority of rats fed AIN-76A diet exhibited calcifications at the corticomedullary junctions, whereas no calcifications were detected in rats fed the other two diets. From these results, it can be deduced that there was no important adverse effects on mineral status as a consequence of the presence of InsP6 in the studied diets. Besides, considering that a 0.12% InsP6 contained in the AIN-76A purified diet through the addition of a 6% of carob seed germ to this diet, produced the same beneficial effects as the direct addition of a 1% of InsP6 and no negative effects on mineral status was observed, it can be concluded that the value of the presence of InsP6 at adequate amounts in the diet is remarkable and must be favourably considered.

Urinary phytate in calcium oxalate stone formers and healthy people--dietary effects on phytate excretion.

The phytate urinary levels in a group of active calcium oxalate stone formers were studied and compared with those found in healthy people. Urinary phytate was significantly lower for stone formers. If deficit of the capacity to inhibit crystallization of calcium salts is considered an important factor related to calcium stone formation, the excretion of low phytate amounts could be an important risk factor in the development of this type of renal calculi. The influence of dietary phytate on urinary excretion was also studied. Clearly maintenance of a phytate-free diet significantly decreased the urinary excretion of phytate (about 50% after 36 h). This demonstrated the importance of dietary phytate in maintaining adequate urinary levels to permit effective crystallization inhibition of calcium salts and consequently preventing renal stone development.