Simultaneous determination of five common additives in insulating mineral oils by high-performance liquid chromatography with ultraviolet and coulometric detection.

Dielectric mineral oils are used to impregnate power transformers and large electrical apparatus, acting as both liquid insulation and heat dissipation media. Antioxidants and passivators are frequently added to mineral oils to enhance oxidation stability and reduce the electrostatic charging tendency, respectively. Since existing standard test methods only allow analysis of individual additives, new approaches are needed for the detection of mixtures. For the first time we investigate and discuss the performance of analytical methods, which require or do not require extraction as sample pretreatment, for the simultaneous reversed-phase high-performance liquid chromatography determination of passivators (benzotriazole, Irgamet(®) 39) and antioxidants (N-phenyl-1-naphtylamine, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol), chosen for their presence in marketed oils. Quick easy, cheap, effective, rugged and safe and solid phase extractions were evaluated as sample pretreatments. Direct sample-injection was also studied. Ultraviolet spectrophotometry and direct-current coulometry detection were explored. As less prone to additive concentrations variability, the direct-injection high-performance liquid chromatography with ultraviolet and coulometric detection method was validated through comparison with Standard Method IEC 60666 and through an ASTM interlaboratory proficiency test. Obtained detection limits are (mg kg(-1) ): benzotriazole (2.8), Irgamet(®) 39 (13.8), N-phenyl-1-naphtylamine (11.9), 2,6-di-tert-butylphenol (13.1), 2,6-di-tert-butyl-p-cresol (10.2). Simultaneous determination of selected additives was possible both in unused and used oils, with good precision and accuracy.

Determination of copper in liquid and solid insulation for large electrical equipment by ICP-OES. Application to copper contamination assessment in power transformers.

Copper is one of the main constituents of the components in power transformers and its presence both in liquid (mineral oil) and in solid (Kraft paper) insulators can lead to enhanced dielectric losses and to the subsequent deterioration of their insulating properties. Recently the latter have been correlated to plant failures which in turn may have severe impact on the environment. This paper describes the direct analysis of copper in insulating mineral oil by ICP-OES and how it was first optimized compared to the official American Society for Testing and Materials (ASTM) D7151 method. Detection and quantification limits of 8.8 µg kg(-1) and 29.3 µg kg(-1) were obtained. Secondly, copper determination was improved by coupling a microwave assisted dissolution procedure of the mineral oil which avoided the problems, in the real samples, due to the presence of solid species of copper which cannot be nebulized following traditional methods described in literature. Sixteen mineral insulating oils sampled from transformers in service were analyzed before and after dissolution. In order to evaluate copper speciation, size fractionation was performed by filtration on PTFE filters (0.45, 1 and 5 µm). This test was performed on all the oil samples. Finally, because of the key role of the solid insulator in failed transformers, the Authors applied the developed method to study the copper deposition tendency onto the insulating Kraft paper tapes exerted by two unused oils (a corrosive and a non-corrosive one) under defined ageing conditions.

Novel insights in Al-MCM-41 precursor as adsorbent for regulated haloacetic acids and nitrate from water.

High concentration of NO (3) (-) in groundwater has raised concern over possible contamination of drinking water supplies. In addition, the formation of haloacetic acids (HAAs) as by-products during disinfection with chlorine-based agents is still a relevant issue, since HAAs pose serious health hazard. In this work, we investigated the affinity of a precursor of Al-MCM-41 (a mesostructured hexagonal aluminosilicate containing the template surfactant) towards nitrate and HAAs, for its possible application in the removal of these pollutants from natural and drinking waters. Additionally, adsorption kinetics and isotherms were studied. The adsorbent was synthesized using cetyltrimethylammonium bromide as surfactant and characterized by physico-chemical techniques. Simulated drinking water was spiked with the EPA-regulated HAAs (monochloroacetic (MCAA), monobromoacetic (MBAA), dichloroacetic (DCAA), dibromoacetic (DBAA), and trichloroacetic (TCAA) acids) and placed in contact with the adsorbent. The effect of matrix composition was studied. Adsorption kinetic studies were performed testing three kinetics models. For the adsorption studies, three adsorption isotherm approaches have been tested to experimental data. The pollutant recoveries were evaluated by suppressed ion chromatography. The affinity of the adsorbent was TCAA = DBAA = DCAA > MBAA > MCAA with DCAA, DBAA, and TCAA completely removed. A removal as high as 77 % was achieved for 13 mg/L nitrate. The adsorption isotherms of NO (3) (-) and monochloroacetic acid can be modeled by the Freundlich equation, while their adsorption kinetics follow a pseudo-second-order rate mechanism. The adsorbent exhibited high affinity towards HAAs in simulated drinking water even at relevant matrix concentrations, suggesting its potential application for water remediation technologies.

Flow injection method for the determination of silver concentration in drinking water for spacecrafts.

A flow injection method has been developed for determination of silver. The method is based on a reduction reaction with sodium borohydride which leads to the formation of a colloidal species which is monitored at a wavelength of 390 nm. The reaction variables flow rate, sodium borohydride concentration and pH, which affect sensitivity, were investigated and their effects were established using a two-levels, three-factor experimental design. Further optimization of manifold variables (reaction coil and injection volume) allowed us to determine silver in the range 0.050-5.0 mg L(-1) with a minimum detectable concentration of 0.050 mg L(-1). Silver is added, as biocide, to drinking water for spacecrafts. The chemical species of silver, present in this kind of sample, were characterized by a procedure based on the selective retention of Ag(+) onto a 2.2.2. cryptand based substrate followed by determination of the non-bound and bound (after elution) Ag(+) by the FIA method. The method optimized was applied to a drinking water sample provided for the launch with the Automated Transfer Vehicle (ATV) module Jule Verne to the International Space Station (March 9, 2008).

Functionalized SBA-15 mesoporous silica in ion chromatography of alkali, alkaline earths, ammonium and transition metal ions.

The retention properties of a SBA-15 mesoporous silica functionalized with -(CH(2))(3)COOH groups, synthesized by a co-condensation route, were investigated for the ion chromatography of different cationic species. A systematic study on the effect of different eluent compositions containing non-complexing (methanesulfonic acid) or complexing (oxalic or pyridine-2,6-dicarboxylic acids) eluents, in the presence of organic modifiers (CH(3)CN, CH(3)OH, CH(3)NH(2)) on the retention of cations (Li(+), Na(+), K(+), Ca(2+), Mg(2+), Sr(2+), Ba(2+), NH(4)(+), Cu(2+), Ni(2+), Zn(2+), Cd(2+), Co(2+), Pb(2+), Fe(3+)) chosen as model analytes and for their environmental importance, allowed us to elucidate the mechanisms (cation-exchange or complexation) involved in the retention on the SBA-15 phase. For the first time separations of cations on SBA-15 based stationary phases are investigated, providing the basis for further development of mesoporous silica chemistry for in-flow ion-exchange applications.

Determination of sulfonic acids and alkylsulfates by ion chromatography in water.

A fast ion chromatographic method with suppressed conductivity detection has been developed for the simultaneous determination of methane-, ethane-, 1-propane-, 1-butane-, 1-pentane-, 1-hexane-, 1-heptane-, 1-octane-, 1-nonane-, 1-decane-, 1-dodecane-, dodecylbenzene-, p-toluene-, benzenesulfonic acids, octylsulfate and dodecylsulfate in water samples. Due to the high number of analytes and their heterogeneity, the effect of the mobile phase parameters (NaOH, CH(3)OH and CH(3)CN concentration) on the retention factors has been studied in detail, so achieving, for the first time, the separation among 15 of these analytes by a gradient elution. Detection limits included within 0.06-0.16 microM have been obtained. Interferences from Cl(-), NO(3)(-) and SO(4)(2-), possible anions present in water samples, have been considered and a SPE procedure has been developed for analytes enrichment and matrix removal in a seawater sample. This is the first application of an ion-exchange chromatographic method to a seawater sample for this kind of analytes.

High performance ion chromatography of haloacetic acids on macrocyclic cryptand anion exchanger.

A new high performance ion chromatographic method has been developed for the separation of the nine chlorinated-brominated haloacetic acids (HAAs) that are the disinfection by-products of chlorination of drinking water, using a macrocycle-based adjustable-capacity anion-exchange separator column (IonPac Cryptand A1). A gradient method based on theoretical and experimental considerations has been optimized in which 10 mM NaOH-LiOH step gradient was performed at the third minute of the analysis. The optimized method allowed us to separate the nine HAAs and seven possibly interfering inorganic anions in less than 25 min with acceptable resolution. The minimum concentrations detectable for HAAs were between 8.0 (MBA) and 210 (TBA) microg L(-1), with linearity included between 0.9947 (TBA) and 0.9998 (MBA). To increase sensitivity, a 25-fold preconcentration step on a reversed phase substrate (LiChrolut EN) has been coupled. Application of this method to the analysis of haloacetic acids in real tap water samples is illustrated.

Retention of heavy metal ions on SBA-15 mesoporous silica functionalised with carboxylic groups.

Three samples of SBA-15 functionalised with -(CH(2))(3)COOH groups have been prepared by co-condensation, starting from solutions of TEOS and 4-(triethoxysilyl)butyronitrile, acting as -(CH(2))(3)COOH precursor, of different molar compositions. Materials were characterised by X-ray diffraction, nitrogen adsorption, and FT-IR spectroscopy. The pK(a) and the acidic capacity were measured for all samples by potentiometric titration. The acidic capacity increases with increasing amount of -COOH precursor in the synthesis mixture only up to 10% molar of total alkoxysilane. The value for the pK(a)(4.75) is independent of the acidic capacity of the material. The sample prepared starting from an amount of -COOH precursor equal to 10% molar of total alkoxysilane was chosen to test selective interactions with heavy metals of environmental importance (Ag(+), Cd(2+), Fe(3+), Cu(2+), Zn(2+)) at different pH values and ionic strengths. The significant and selective adsorption exhibited by the material has been exploited in a preliminary cation-exchange chromatographic application showing the possibility of eluting the metal ions at different retention times.

Determination of epichlorohydrin by sulfite derivatization and ion chromatography: characterization of the sulfite derivatives by ion chromatography-mass spectrometry.

This work is an upgrade of a previously developed method (J. Chromatogr. A 884 (2000) 251] for epichlorohydrin determination by ion chromatography (IC) and conductivity detection. Here, an ion chromatography-mass spectrometry (IC-MS) coupling has been employed for the separation and the identification of products of epichlorohydrin when reacted with the nucleophilic agent SO3(2-). The high capacity column (IonPac AS11-HC) used for separation provided good resolution. This allowed evaluation of the IC behavior and mass spectrometric identification of epichlorohydrin sulfite derivatives. By using atmospheric pressure interfaces (ESI and APCI) the following species were tentatively identified: 2,3-dihydroxy-1-propanesulfonic, 2,3-epoxy-1-propanesulfonic,1,3-dihydroxy-2-propanesulfonic and 3-oxetanesulfonic acids and 2-hydroxy-1,3-propanedisulfonic acid (or its isomer 3-hydroxy-1,2-propanedisulfonic acid). The study showed that chlorine atoms are displaced from epichlorohydrin during the reaction, while mass spectrometry confirmed that none of the products formed contains chlorine atoms.

The use of mosses as environmental metal pollution indicators.

The possibility of using mosses as environmental indicators of metal pollution has been investigated. Mosses of the species Bryum argenteum were collected from different parts of Piedmont (Italy), ranging from highly polluted areas to nearly uncontaminated mountain areas. Periodical samplings were planned in every site on a monthly base, in order to check variations of metal uptake throughout one year; correlations with pluviometric and thermal patterns were investigated for all sampling stations. On every moss sample 20 elements, ranging from major (K, P, Al, Ca, Fe and Mg) to minor (Mn, Na, Ti and Zn) and trace (As, Ba, Cd, Co, Cr, Cu, Li, Ni, Pb and Sr), were quantitatively determined by inductively coupled plasma-atomic emission spectrometry or graphite furnace-atomic absorption spectrometry, depending on the needed sensitivity. Statistical analyses, carried out with principal component analysis and cluster analysis methods, revealed that a good correlation exists between metal content in mosses and pollution degree in the areas sampled.

Distribution and mobility of metals in contaminated sites. chemometric investigation of pollutant profiles.

The distribution and mobility of heavy metals in the soils of two contaminated sites in Piedmont (Italy) was investigated, evaluating the horizontal and vertical profiles of 15 metals, namely Al, Cd, Cu, Cr, Fe. La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr. The concentrations in the most polluted areas of the sites were higher than the acceptable limits reported in Italian and Dutch legislations for soil reclamation. Chemometric elaboration of the results by pattern recognition techniques allowed us to identify groups of samples with similar characteristics and to find correlations among the variables. The pollutant mobility was studied by extraction with water, dilute acetic acid and EDTA and by applying Tessier's procedure. The fraction of mobile species, which potentially is the most harmful for the environment, was found to be higher than the one normally present in unpolluted soils, where heavy metals are, to a higher extent, strongly bound to the matrix.

Recent developments in ion chromatography.

This paper summarizes how ion chromatography is now a multimode technique suitable for solving analytical problems in all areas of interest. Current and more recent applications will be overviewed within the new trends.

Determination of metals in wine with atomic spectroscopy (flame-AAS, GF-AAS and ICP-AES); a review.

Metals in wine occur at the mg l(-1) level or less and, though not directly related to the taste of the final product, their content should be determined because excess is undesirable, and in some cases prohibited, due to potential toxicity. Lead content in wine, for example, is restricted in several states by legislation to guarantee consumer health protection. Of several methods for metal determination, techniques of atomic spectroscopy are the most sensitive and rapid. Most of the elements present in wine can be determined with these techniques, at concentrations ranging from the mg l(-1) to the microg l(-1) level. Here, inductively coupled plasma-atomic emission spectrometry (ICP-AES), flame atomic absorption spectrometry (flame-AAS) and graphite furnace-atomic absorption spectrometry (GF-AAS) are compared for their characteristics as employed in metal determination in wine.