Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Validation of atmospheric aerosols parallel sampling in a multifold device

In this work, particulate matter was collected using an active sampling system consisting of a PM₁₀ (<10 μm) inlet coupled to a multifold device containing six channels, connected to a vacuum pump. Each channel was equipped with a filter holder fitted with adequately chosen filters. The system was fixed on a metallic structure, which was placed on the roof of the laboratory building, at the Faculty of Sciences, in Lisbon. Sampling took place under flow-controlled conditions. Aerosols were extracted from the filters with water, in defined conditions, and the water-soluble fraction was quantified by ion chromatography (IC) for the determination of inorganic anions (Cl^?, NO₃ ^? and SO₄ ^2?). Equivalent sampling through the various channels was validated. Validation was based on the metrological compatibility of the content results for the various filters. Ion masses are metrologically equivalent when their absolute difference is smaller than the respective expanded uncertainty. When this condition is verified, the studied multifold device produces equivalent samples.     

Inorganic nitrogen transformations in the treatment of landfill leachate with a high ammonium load: A case study

The inorganic nitrogen transformations occurring at a municipal waste leachate treatment facility were investigated. The treatment facility consisted of a collection well and an artificial wetland between two aeration ponds. The first aeration pond showed a decrease in ammonium (from 3480 (± 120) to 630(± 90) mg ⋅ L⁻¹), a reduction in inorganic nitrogen load (3480 to 1680 mg N ⋅ L⁻¹), and an accumulation of nitrite (< 1.3 mg-N ⋅ L⁻¹ in the collection well, to 1030 mg-N ⋅ L⁻¹). Incomplete ammonium oxidation was presumably the result of the low concentration of carbonate alkalinity (∼2 mg ⋅ L⁻¹), which may cause a limitation in the ammonium oxidation rate of nitrifiers. Low carbonate alkalinity levels may have been the result of stripping of CO₂ from the first aeration pond at the high aeration rates and low pH. Various chemodenitrification mechanisms are discussed as the reason for the reduction in the inorganic nitrogen load, including; the reduction of nitrite by iron (II) (producing various forms of gaseous nitrogen); and reactions involving nitrous acid. It is suggested that the accumulation of nitrite may be the result of inhibition of nitrite oxidizers by nitrous acid and low temperatures. Relative to the first aeration pond, the speciation and concentration of inorganic nitrogen was stable in the wetlands and 2nd aeration pond. The limited denitrification in the wetlands most probably occurred due to low concentrations of organic carbon, and short retention times.     

Fast simultaneous determination of traces of Cu(II) and Co(II) in soils and sediments with the luminol/perborate chemiluminescent system

A flow injection analysis method based on ion chromatography and luminol chemiluminescence detection was used for the simultaneous determination of copper (II) and cobalt (II) trace levels in soils and sediments following microwave-assisted acid digestion. Detection was based on chemiluminescence (CL) of the luminol–perborate system in an alkaline medium, which is catalyzed by both transition metals. The concentration and pH of the eluent (oxalic acid) was found to affect CL intensities and retention times, both of which were inversely proportional to the oxalic acid concentration. The calibration curves for both metal ions were linear and allowed a limit of detection of 0.003 μg l^?1 for cobalt (II) and 0.014 μg l^?1 for cooper (II) to be calculated. The proposed method was successfully used to determine both metal ions in certified reference materials of stream and river sediments and soil samples. Based on the results, the determination is free of interferences from the usual concomitant ions.     

Extraction of DNA from amniotic fluid cells for the early prenatal diagnosis of genetic disease

Ten-ml samples of amniotic fluid were taken from pregnancies being terminated at 8–14 weeks' gestation. DNA was extracted from the amniotic cells by sequential centrifugation and analysed using the polymerase chain reaction (PCR). Fifteen samples were analysed for evidence of maternal contamination using Mfd5 oligo-nucleotide primers for repeat polymorphisms. Ten amniotic fluid samples were tested for the Delta-F₅₀₈ deletion characteristic of cystic fibrosis to demonstrate a diagnostic application for the technique. In each case, DNA extracted from fetal tissue from the same pregnancy was included in the controls. In 14 of the 15 cases tested with the Mfd5 primers, both the amniotic fluid DNA and the fetal DNA showed no evidence of contaminating DNA. In one case, neither the amniotic fluid cells nor the fetal cells yielded results. In nine of the ten cases tested with the Delta-F₅₀₈ primers, the amniotic fluid cell DNA provided accurate information about the genetic status of the fetus; in the tenth, the fetal DNA failed to amplify. The results indicate that adequate DNA can be extracted from amniotic fluid from 8 weeks' gestation onward and these samples are suitable for prenatal diagnosis using PCR.     

Leaching behaviour of Cd, Cu, Pb and Zn in surface soils derived from dredged sediments

Leaching of heavy metals from land-disposed dredged sediment spoils is a potential environmental hazard. The leaching behavior of Cd, Cu, Pb and Zn in surface soils sampled from abandoned dredged sediment disposal sites was assessed. Using simple mass-balance calculations, the significance of the leaching test results with respect to metal migration into underlying clean soil was appraised. The potential leachability, defined as the amounts released at constant pH 4, decreased in the order (% of total contents): Zn (58%) approximately equal to Cd (49%)>Cu (5%) approximately equal to Pb (2%). The kinetics of metal release were determined in a cascade shaking test using de-mineralized water acidified to pH 4 (HNO(3)). Metal concentrations in the leachates were low and metal migration was, assuming uniform convective flow, predicted to be of no environmental concern. It is emphasized that any long-term prediction of metal migration is uncertain.