New lead (II) selective membrane potentiometric sensors based on chiral 2,6-bis-pyridinecarboximide derivatives

New membrane sensors with cylindrical configuration for lead (II) ions are described based on the use of three newly synthesized pyridine carboximide derivatives as neutral ionophores in plasticized PVC membranes. The sensors exhibit significantly enhanced response towards lead (II) ions over the concentration range 4×10⁻⁶-1×10⁻² mol l⁻¹ at pH 4.5-7 with a lower detection limit of 0.4-3.7 μg ml⁻¹. The sensors display near-Nernstian slope of 26.0-33.1 mV per decade for Pb(II) ions. Effects of plasticizers, lipophilic salts and various foreign common ions are tested. The sensors show long life span, good selectivity for Pb(II) over a wide variety of other metal ions, long term stability, high reproducibility, and fast response. Validation of the method by measuring the lower detection limit, range, accuracy, precision, repeatability and between-day-variability reveals good performance characteristics of the proposed sensors. The sensors are used for direct determination of lead in stack emissions of lead smelters, assay of lead in rocks and monitoring of potentiometric titration of Pb(II) with EDTA. The results obtained agree fairly well with data obtained by atomic absorption spectrometry.     

The determination of hydrogen chloride in ambient air with diffusion/denuder tubes

A manual method for the determination of hydrogen chloride in air, based on diffusion/denuder tube separation from particulate chloride aerosol is described. When air is drawn through a tube coated with a selective absorbent (sodium fluoride), separation is achieved because gaseous hydrogen chloride diffuses much more rapidly to the tube walls than particulate chloride aerosol, which passes through virtually unabsorbed. After the sampling period (the length of which depends on the concentration of gaseous hydrogen chloride expected), the sorbed hydrogen chloride is washed from the tube and measured with a highly sensitive chloride ion-selective electrode with a mercury (I) chloride membrane. The method is examined theoretically and experimentally. The experimentally derived absorption efficiencies of the diffusion/denuder tubes were > 90% and the standard deviation of the method was 0.023 μg m^?3 for hydrogen chloride concentrations of 0.16–0.55 μg m^?3. Interference from particulate chloride salts was negligible; this was confirmed by tests with artificially generated aerosol particles from an aerosol generator. The diffusion/denuder tubes have high capacity; level as high as 330 μg m^?3 hydrogen chloride can be sampled for 60 min without affecting performance. A detection limit of (50/t) μg m^?3 can be achieved, where t is the sampling rime (min); e.g., 1μg m^?3 hydrogen chloride can be detected with a sampling period of 50 min.     

Evaluation of pulsed radiofrequency glow discharge time-of-flight mass spectrometry for precious metal determination in lead fire assay buttons

In this paper, an exploration of the capabilities and limitations of pulsed radiofrequency glow discharge time-of-flight mass spectrometry (GD-TOFMS) for the determination of the precious metals Ag, Au, Pd, Pt and Rh in lead buttons obtained by Pb fire assay is reported on. Since the matrix consists almost entirely of lead (>99%), the occurrence of doubly charged Pb (Pb²⁺) ions can hinder accurate determination of Rh. This problem was counteracted by relying on the time-resolved formation of different ion types over the pulse period of the glow discharge, which allows discrimination against the Pb²⁺ ions. The formation of ArCu⁺ ions as a result of the use of a copper anode was assessed to pose no threat to the accuracy of the results obtained for the set of samples analyzed as its contribution to the total signal at m/z = 103 could be adequately corrected for. The method developed was evaluated in terms of accuracy and precision using a set of Pb button standards with analyte concentrations between 5 and 100 μg g⁻¹. For the purpose of validation, a 10 μg g⁻¹ standard was considered as a sample. Overall, an acceptable accuracy was obtained with a bias of <5% between the experimental results and the corresponding reference values, except for Au, for which a larger deviation occurred. Precision values (repeatability) of typically <5% relative standard deviation (RSD) (for N = 3) were obtained and the limits of detection (LODs) vary from ∼0.020 μg g⁻¹ for Ag to ∼0.080 μg g⁻¹ for Pt.     

Activated carbon as adsorbent for alkyllead in air

A method is described for the determination of alkyllead in air with activated carbon as adsorbent. The main factor affecting the adsorption capacity of the activated carbon for alkyllead was the concentration of hydrocarbons in the sampled air, as these were also adsorbed. Particulate inorganic lead was collected on a membrane filter in front of the adsorbent. The alkyllead was extracted from the adsorbent into hot nitric acid, and the concentration determined by electrothermal atomic absorption spectrometry. The detection limit was 0.002 μg Pb m^?3 (sample volume 1 m³), and precision was 9.5% r.s.d. at 2.1 μg Pb m^?3 alkyllead. The method was used to monitor exposure of gasoline tank truck drivers to alkyllead. During the filling of tank trucks with leaded gasoline, alkyllead concentrations from 1 to 750 μg Pb m^?3 were found in the drivers' breathing zone, but most were well below the Norwegian TLV of 75 μg Pb m^?3.     

Iodine speciation in size fractionated atmospheric particles by isotope dilution mass spectrometry

An isotope dilution mass spectrometric method has been developed for the accurate and sensitive determination of iodide and iodate in aerosol particles of the atmosphere. The direct iodine speciation has been possible by the use of species specifically ¹²⁹I enriched spike solutions and separation of the isotope diluted species by anion exchange chromatography after water extraction of the filters. Size fractionated collection of aerosol particles by a six stage impactor system shows different distributions of iodide and iodate for particles of different size with specific patterns for anthropogenically influenced continental and unpolluted marine aerosols, respectively. The detection limit for particulate iodide and iodate has been (3–5) pg/m³ for sampling volumes of 3000 m³. Oil, used for heating plants, could be identified as one but not the only anthropogenic iodine source.Dedicated to Professor Dr. D. Klockow on the occasion of his 60th birthday     

Inductively coupled plasma optical emission spectrometric determination of trace element in PM10 airborne particulate matter collected in an industrial area of Argentina

Trace metals of relevance from the environmental and toxicological point of view were quantified in the city of Campana, Buenos Aires, Argentina. The collection of particulate matter was performed on ash-free fiber glass filters using high-volume samplers with a PM₁₀ sampling head, during a 3-month period in 2002. An acid leaching of elements deposited on the filters was adopted paying special attention to the recovery of volatile elements. Analysis was performed by inductively coupled plasma optical emission spectrometry (ICP OES) to ascertain the concentrations of 12 key elements, namely, Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn. The validation of the procedure was performed by the analysis of the standard reference material NIST 1648, urban particulate matter, and good agreement between concentrations found and the reported certified values was achieved. Blank filters were spiked with the analytes investigated and the recoveries varied between 83% and 92%. Metal concentrations spanned the range 0.03 ng m⁻³ (equivalent to 0.42 μg g⁻¹) for Cd to 1.9 μg m⁻³ (equivalent to 29.7 mg g⁻¹) for Fe. The results obtained show that the pollutants of special environmental and health concern are As and Pb. Mean As concentration was higher than the guideline value associated with an excess cancer risk of 1:10⁻⁶, reported by the World Health Organization (WHO). Lead is the only element that showed higher concentrations than those recently measured in the large and heavily trafficked metropolitan area of Buenos Aires. Cadmium>Pb>As>Zn>Cu are the elements more enriched in airborne PM₁₀.     

Rhodium as permanent modifier for atomization of lead from biological fluids using tungsten filament electrothermal atomic absorption spectrometry

Rhodium (Rh) was investigated as a permanent modifier for the atomization of Pb from biological fluids in W-filament atomic absorption spectrometry (AAS). Heating the W-filament with a Rh solution provided a protective coating for subsequent determinations of Pb in blood and urine matrices. The W-filament AAS instrumentation used was based on a prototype design that utilized self-reversal background correction scheme and peak area measurements. We found that Rh not only stabilized Pb during the pyrolysis step, but also facilitated the removal of carbonaceous residues during the cleaning step, requiring much less power than with phosphate modifier. Thus, the filament lifetime was greatly extended to over 300 firings. Periodic reconditioning with Rh was necessary every 30 firings or so. Conditioning the filament with Rh also permitted direct calibration using simple aqueous Pb standards. The method detection limit for blood Pb was approximately 1.5 μg dl⁻¹, similar to that reported previously. Potential interferences from concomitants such as Na, K, Ca and Mg were evaluated. Accuracy was verified using lead reference materials from the National Institute of Standards and Technology and the New York State Department of Health. Blood lead results below 40 μg dl⁻¹ were within ±1 μg dl⁻¹ of certified values, and within ±10% above 40 μg dl⁻¹; within-run precision was ±10% or better. Additional validation was reported using proficiency test materials and human blood specimens. All blood lead results were within the acceptable limits established by regulatory authorities in the US. When measuring Pb in urine, sensitivity was reduced and matrix-matched calibration became necessary. The method of detection limit was 27 μg l⁻¹ for urine Pb. Urine lead results were also validated using an acceptable range comparable to that established for blood lead by US regulatory agencies.     

Liquid chromatography with tandem mass spectrometry method for the determination of nicotine and minor tobacco alkaloids in electronic cigarette refill liquids and second‐hand generated aerosol

A liquid chromatography with tandem mass spectrometry method for the simultaneous quantification of nicotine and seven minor tobacco alkaloids in both refill liquids for electronic cigarettes and their generated aerosol was developed and validated. The limit of detection and limit of quantification values were 0.3–20.0 and 1.0–31.8 ng/mL, respectively. Within‐laboratory reproducibility was 8.2–14.2% at limit of quantification values and 4.8–12.7% at other concentration levels. Interday recovery was 75.8–116.4%. The method was applied to evaluate the compliance of commercial liquids (n = 95) with their labels and to assess levels of minor alkaloids. Levels of nicotine and its corresponding compounds were also evaluated in generated aerosol. About 47% of samples showed differences above ±10 % of the stated nicotine concentration. About 78% of the “zero nicotine” liquids showed traces in the range of 1.3 ± 0.1–254.0 ± 14.6 μg/mL. Nicotine‐N ′‐oxides, myosmine, and anatabine were the most common minor alkaloids in liquids containing nicotine. Nicotine and N ′‐oxides were detected in all air samples when aerosol was generated from liquids containing nicotine. Nicotine average emissions from electronic cigarette (2.7 ± 0.9 μg/m³) were significantly lower (p < 0.01, t‐test) with respect to conventional cigarette (30.2 ± 1.5 μg/m³).     

Characterization of lead and lead leaching properties of lead glazed ceramics from the Solis Valley, Mexico, using inductively coupled plasma-mass spectrometry (ICP-MS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFT)

Ingestion of relatively small amounts of lead is now recognized to cause significant neurological and cognitive effects in humans. Large quantities may be fatal, yet lead poisoning, especially of children, is still a major public health concern in many parts of the world. In rural Mexican communities lead oxide (PbO) is added to ceramic glaze as a fluxing agent, lowering starting firing temperatures to 500 °C. The purpose of this study is to characterize the lead chemical forms in ceramic glazes from the Solis Valley, Mexico, to investigate lead leaching properties of these ceramics, and to demonstrate the applicability of lead isotope signatures as a means of tracing lead source origins. Ceramics were collected from the rural village of Santa Maria de Canchesda, State of Mexico, Mexico. Dried liquid glazes, post-fired glaze material, and pure PbO were analyzed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). Results from DRIFT analysis indicate that PbO (1429 cm⁻¹ band) is the active form of lead found in liquid glazes and ceramics. Some shifting of 1429 cm⁻¹ PbO peak to lower wavenumbers occurs in post-fired ceramics, and this may be due to the formation of lead bisilicate during firing. Ceramics samples were leached in 0.02 M citric acid solution for 1 min, and leached lead concentrations were measured using inductively coupled plasma-mass spectrometry (ICP-MS). Lead concentrations in these leachates varied from 0.4-80.4 μg ml⁻¹, while the control pottery from the US leached only 0.1 μg ml⁻¹ lead. Elemental distributions on glaze surfaces were identified by laser ablation (LA)-ICP-MS. Nitric acid extracts of soils, teeth, and ceramic glazes were analyzed for lead isotope ratios (²⁰⁷Pb/²⁰⁶Pb vs. ²⁰⁸Pb/²⁰⁶Pb) using ICP-MS. Similarities of tooth and ceramic lead isotope ratios indicate that ceramics may be a substantial source of body lead burden in the Solis Valley. This study demonstrates the applicability of lead isotope ratios for lead source identification, and it identifies potential health risks from ceramic use induced lead toxicity within the Solis Valley.     

Determination of water-soluble and insoluble compounds in size classified airborne particulate matter

The elemental composition of water soluble and acid soluble size-fractionated airborne particulate matter (APM) was investigated. PM2.5 and PM2.5-10 samples were collected every three days from October 2006 to October 2007 in Buenos Aires, Argentina. The collection was performed on Nucleopore® filters using a GENT sampler. Samples containing fine and coarse particles were subjected to an aqueous leaching to obtain information on the dissolution behaviors of ions, metal and metalloids. Key elements namely, Al, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Se, Ti and Zn were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). In the aqueous fractions, Cl⁻, SO₄²⁻, Na⁺ and NH₄⁺ were determined by high performance liquid chromatography (HPLC). A (6:2:5) mixture of nitric, hydrochloric and perchloric acids was used for leaching metals from the residual filters. For validation of the extraction procedure, the ICP OES measurements the Standard Reference Material NIST 1648 (Urban particulate matter) was subjected to the same analytical procedure that the samples loaded with APM. Total analyte concentration varied from 333.2 μg g^− 1 (equivalent to 3.7 ng m^− 3) for Ti to 692 mg g^− 1 (equivalent to 2.47 μg m^− 3) for Ca.     

Atmospheric Hydrocarbon Concentrations in the Baltic Sea Area

Abstract

During a marine research expedition in 1983 in the Baltic Sea area air samples were collected for the analysis of several organic and inorganic pollutants. The aim of the expedition was to obtain information on the airborne load in the sea as well as to measure the concentrations of the pollutants far away from source areas. In this paper the background concentrations of the primarily traffic originated aromatic hydrocarbons benzene, toluene and xylenes will be presented.

The concentrations of benzene were from 0.2 to 2μg/m³, of toluene between 0.4–3μg/m³, of m-xylene 0.02–0.60μg/m³ while the concentrations of o-xylene were 0.01–0.1 μg/m³. The concentrations did not depend too much on the origin (continental/sea type) of the air masses. A weak minimum in the concentrations of the measured hydrocarbons was noticed in the central Baltic Sea area. When comparing lead concentrations in fine particles (< 2.5 μm) with those of benzene, toluene and m-xylene some coincidence between them could be observed.     

Determination of water-soluble and insoluble (dilute-HCl-extractable) fractions of Cd,Pb and Cu in Antarctic aerosol by square wave anodic stripping voltammetry: distribution and summer seasonal evolution at Terra Nova Bay (Victoria Land)

Eight PM10 aerosol samples were collected in the vicinity of the “Mario Zucchelli” Italian Antarctic Station (formerly Terra Nova Bay Station) during the 2000–2001 austral summer using a high-volume sampler and precleaned cellulose filters. The aerosol mass was determined by differential weighing of filters carried out in a clean chemistry laboratory under controlled temperature and humidity. A two-step sequential extraction procedure was used to separate the water-soluble and the insoluble (dilute-HCl-extractable) fractions. Cd, Pb and Cu were determined in the two fractions using an ultrasensitive square wave anodic stripping voltammetric (SWASV) procedure set up for and applied to aerosol samples for the first time. Total extractable metals showed maxima at midsummer for Cd and Pb and a less clear trend for Cu. In particular, particulate metal concentrations ranged as follows: Cd 0.84–9.2 μg g⁻¹ (average 4.7 μg g⁻¹), Pb 13.2–81 μg g⁻¹ (average 33 μg g⁻¹), Cu 126–628 μg g⁻¹ (average 378 μg g⁻¹). In terms of atmospheric concentration, the values were: Cd 0.55–6.3 pg m⁻³ (average 3.4 pg m⁻³), Pb 8.7–48 pg m⁻³ (average 24 pg m⁻³), Cu 75–365 pg m⁻³ (average 266 pg m⁻³). At the beginning of the season the three metals appear widely distributed in the insoluble (HCl-extractable) fraction (higher proportions for Cd and Pb, 90–100%, and lower for Cu, 70–90%) with maxima in the second half of December. The soluble fraction then increases, and at the end of the season Cd and Pb are approximately equidistributed between the two fractions, while for Cu the soluble fraction reaches its maximum level of 36%. Practically negligible contributions are estimated for crustal and sea-spray sources. Low but significant volcanic contributions are estimated for Cd and Pb (∼10% and ∼5%, respectively), while there is an evident although not quantified marine biogenic source, at least for Cd. The estimated natural contributions (possibly including the marine biogenic source) cannot account for the high fractions of the metal contents, particularly for Pb and Cu, and this suggests that pollution from long-range transport is the dominant source. Figure Aerosol sampling in Antarctica     

Hydride generation atomic absorption spectrometry with different flow systems and in-atomizer trapping for determination of cadmium in water and urine-overview of existing data on cadmium vapour generation and evaluation of critical parameters

An overview of literature data on vapour generation techniques for cadmium and comparison with own experiments by means of several different types of hydride generation-electrothermal atomic absorption spectrometric systems (HG-ETAAS) (batch, semi-batch (SB), continuous-flow (CF) and flow-injection (FI) as well as different gas-liquid separators (GLS) exhibits apparent variations and inconsistency. However, if data for optimal chemical conditions are re-plotted in another coordinates: C_HCl (mol l⁻¹) vs. the ratio of reductant-to-acid molar input rates (i.e. millimoles per minute), [BH₄⁻]:[H⁺], much better consistency of data is revealed: more than half of data are clustered around 0.2-0.3 mol l⁻¹ HCl which appears an optimal acidity at moderate BH₄⁻ concentrations; the tetrahydroborate molar input rates should always be in excess versus the H⁺ molar input rates (1.1 to tenfold); relatively high flow rates of argon purge gas are required (≥120 ml min⁻¹); special attention to the blank control at ng l⁻¹ levels as well as to the construction of gas-liquid separator and vapour transfer lines should be paid. ‘Milder’ conditions for HG could be provided with some of the examined systems and GLSs, thus minimizing reagent consumption, blanks, vigorous reactions, foaming, aerosol production and drift in measurements: e.g. 0.4 mol l⁻¹ HCl—3% m/v NaBH₄ with the semi-batch system and 0.25 mol l⁻¹ HCl—2% m/v NaBH₄ in continuous flow mode. Experimental system is based on the Transversely Heated Graphite Atomizer coupled with flow injection system FIAS 400. Integrated platforms are treated for permanent modification with Zr (110 μg) or W (240 μg) and then with Ir (8 μg). Temperatures of trapping, pyrolysis and atomization are 350, 500 and 1300 °C, respectively. The best overall efficiency of HG, transportation and trapping is 41%. The characteristic mass for peak area measurements is m_o=2.8 pg and the limit of detection is 0.002 μg l⁻¹. The long-term stability of characteristic mass (within-day, 8 h) is m_o=2.8±0.1 pg (R.S.D. 4.0%, n=8), whereas the corresponding between-day figures (1 mo) are m_o=2.8±0.2 pg (R.S.D. 6.6%, n=6). The linear range is 0.002-0.12 μg l⁻¹ with a sample loop of 1.8 ml, being strongly impaired with smaller sample volumes in FI mode. The sample throughput rate is 10 h⁻¹ with the semi-batch system. Applications to real human and bovine urine samples and CRMs of sea water (CASS-3), river water (SLRS-1 and SLRS-3) and urine (SRM 2670) are presented.     

Semi-online preconcentration of Cd, Mn and Pb on activated carbon for GFASS

This paper presents a method whereby trace elements in NH₄Cl-NH₃ medium are adsorbed on activated carbon in a micro-flow-injection (FI) semi-online sorbent extraction preconcentration system and then determined by graphite furnace atomic absorption spectrometry (GFAAS). The analytical performance of the proposed method for determining Cd, Mn and Pb was studied. A microcolumn packed with activated carbon was used as a preconcentration column (PCC). The metals to be determined were preconcentrated onto the column for 60 s and then rinsed with 0.02% (v/v) HNO₃ and eluted with 30 μl of 2 mol l⁻¹ HNO₃. Compared with the direct injection of 30 μl of aqueous sample solution, enrichment factor of 32, 26, and 21 and detection limits (3σ) of 0.4, 4.7, and 7.5 ng l⁻¹ for Cd, Mn and Pb, respectively, were obtained with 60 s sample loading at 3.0 ml min⁻¹ for sorbent extraction, 30 μl of eluate injection, and peak area measurement. The precisions (RSD, n=6) were 2.8% at the 0.05 μg l⁻¹ level for Cd, 3.0% at the 0.3 μg l⁻¹ level for Mn, and 3.1% at the 0.5 μg l⁻¹ level for Pb. The experimental results indicate that the procedure can eliminate the fundamental interferences caused by alkali and alkaline earth metals and the application of it to the determination of Cd, Mn and Pb in some water samples is successful.     

A study of bismuth-film electrodes for the detection of trace metals by anodic stripping voltammetry and their application to the determination of Pb and Zn in tapwater and human hair

This work reports the simultaneous determination of Cd(II), Pb(II) and Zn(II) at the low μg l⁻¹ concentration levels by square wave anodic stripping voltammetry (SWASV) on a bismuth-film electrode (BFE) plated in situ. The metal ions and bismuth were simultaneously deposited by reduction at −1.4 V on a rotating glassy carbon disk electrode. Then, the preconcentrated metals were oxidised by scanning the potential of the electrode from −1.4 to 0 V using a square-wave waveform. The stripping current arising from the oxidation of each metal was related to the concentration of each metal in the sample. The parameters for the simultaneous determination of the three metals were investigated with the view to apply this type of voltammetric sensor to real samples containing low concentrations of metals. Using the selected conditions, the limits of detection were 0.2 μg l⁻¹ for Cd and for Pb and 0.7 μg l⁻¹ for Zn at a preconcentration time of 10 min. Finally, BFE's were successfully applied to the determination of Pb and Zn in tapwater and human hair and the results were in satisfactory statistical agreement with atomic absorption spectroscopy (AAS).     

Spectrophotometric determination of trace lead in water after preconcentration using mercaptosephadex

A highly sensitive and selective spectrophotometric method for determination of trace lead in water after pre-concentration using mercaptosephadex (MS-50) has been developed, the method based on the color reaction of lead(II) with dibromohydroxylphenylporphyrin. Under optimal condition, lead(II) reacts with the reagent to form a 1:2 yellow complex in presence of TritonX-100, which has a maximum absorption peak at 479 nm. The color reaction can complete rapidly and remain stable for 24 h in room temperature. The molar absorption coefficient of the lead complex, the limit of quantification, the limit of detection and relative standard deviations were found to be 2.35×10⁵ l mol⁻¹ cm⁻¹, 4.3, 1.4 ng ml⁻¹ and 1.0%, respectively. The absorbance of the lead complex at 479 nm is linear up to 0.48 μg ml⁻¹ of lead(II). The effect of various co-existing ions in water were examined seriously. No interference was observed. Moreover, a simple pre-concentration method for trace lead in water was also studied using MS-50. It was found that trace lead in water can be adsorbed in 1.0 mol l⁻¹ HCl and dissociated from MS-50 with 4.0 mol l⁻¹ HCl quantitatively, that improves the selectivity and the sensitivity of method (its detection limit (3 s) changed into 0.2 ng ml⁻¹ of lead) obviously. The proposed method has been applied to determine trace lead in water samples with satisfactory results.     

210Pb and 210Po radionuclides in the urban air of Lodz, Poland

The concentration of two important radionuclides: ²¹⁰Pb and its decay product ²¹⁰Po in the urban air in the center of the Polish city of Lodz were measured during the winter and spring seasons of 2008–2009. Urban airborne particulate matter was collected using two methods: an Anderson 9-stage impactor, and a high-volume aerosol sampler type ASS500 working in the frames of the aerosol sampling network in Poland, established for radionuclide monitoring. Average concentrations for 10 months sampling period for ²¹⁰Pb and ²¹⁰Po were 0.556 and 0.067 mBq/m³, respectively. However remarkable fluctuations due to meteorological condition were observed: from 0.010 to 0.431 mBq/m³ for ²¹⁰Po and from 0.167 to 1.847 mBq/m³ for ²¹⁰Pb. The highest concentrations, almost 60% of the total activities, of both radionuclides were found in the first two fine aerosol fractions with particle diameters below 0.36 μm. The aerosol residence times calculated from the ²¹⁰Po/²¹⁰Pb ratio ranged from 7 to 120 days.     

Development of a headspace-gas chromatography (HS-GC-PID-FID) method for the determination of VOCs in environmental aqueous matrices: Optimization, verification and elimination of matrix effect and VOC distribution on the Fortaleza Coast, Brazil

An analytical protocol combining a headspace technique with gas chromatography and detection by photoionization detector and flame ionization detector (HS-GC-PID-FID) was developed. This procedure was used to measure volatile organic compounds (VOCs) in environmental aqueous matrices and was applied in determination of VOCs on the coast of Fortaleza, Brazil. At optimum operating conditions, analytical figures of merit such as linearity (R ranged from 0.9983 to 0.9993), repeatability (5.62 to 9.63% and 0.02 to 0.19% for the quantitative and qualitative analyses, respectively), detection limits (0.22 to 7.48 μg L⁻¹) and sensibility were estimated. This protocol favors a fast sampling/sample preparation (in situ), minimizes the use of laboratory material, eliminates the matrix effect from environmental samples, and can be applied to river, estuarine and oceanic waters. The advantage of detectors in series is that a low sensitivity in detection in one is compensated by the other. Toluene was the most abundant VOC in the studied area, with an average concentration of 1.63 μg L⁻¹. It was followed by o-xylene (1.15 μg L⁻¹), trichloroethene (1.08 μg L⁻¹), benzene (0.86 μg L⁻¹), ethylbenzene (0.74 μg L⁻¹), carbon tetrachloride (0.55 μg L⁻¹), m/p-xylene (0.48 μg L⁻¹) and tetrachloroethene (0.46 μg L⁻¹), compounds which are very commonly detected in urban runoff from most cities. The results of the VOC distribution showed that port activity was not the main source of VOCs along the Fortaleza Coast, but that the contribution from urban runoff seemed more significant.     

Stepwise injection photometric determination of nickel in air aerosols

A procedure is developed for the automated determination of nickel in air aerosols; it involves the adhesive separation of aerosols on a fiberglass column in the on-site mode followed by the photometric determination of analytes with dimethyl glyoxime under the conditions of stepwise injection analysis of aerosol concentrates. The analytical range for nickel is 1.5–38 μg/m³; the detection limit of the method is 0.5 μg/m³ at an air sample volume of 30 L. The duration of sampling to an adhesive column and concentrate analysis were 15 and 10 min, respectively.     

Comparison of sample preparation methods for the ICP-AES determination of minor and major elements in clarified apple juices

Inductively coupled plasma atomic emission spectrometry (ICP-AES) was used for the determination of minor and major elements present in apple juices. Prior to ICP-AES measurement, samples were diluted with nitric acid or digested in a microwave assisted digestion system. The differences in the measured element concentrations after application of different types of sample preparation procedures are discussed. The direct measurement compared to closed microwave dissolution was found to be the best sample preparation procedure. Prior to the measurements the ICP-AES method was validated and optimized for the determination of elements in apple juices. For diluted apple juice samples the lowest limits of detection (LOD) were obtained for Ba and Cd (< 20 μg L^{− 1}), moderate ones for Cu, Mn, Ni, Fe, Ag, Ca, Cr, Zn, Mg, and Sr (20–100 μg L^{− 1}), and the highest LODs for K, Pb, Na, and Al (> 110 μg L^{− 1}). The results obtained for the repeatability (< 0.9%), the intermediate precision (< 4.5%), the day-to-day reproducibility (< 5.2%), and the overall uncertainty of measurement (approx. 4–7%) for all elements analyzed demonstrated the good applicability of the proposed method. Differences in major element content in fresh and commercial apple juice are discussed.