Determination of chlorpyrifos and acephate in tropical soils and application in dissipation studies

A rapid and accurate method for the extraction and determination of the two organophosphorus insecticides, chlorpyrifos and acephate in top- and subsoil materials of three tropical clayey soils from Sarawak has been developed. Soil samples were extracted with ethyl acetate and the pesticides were determined by GC-FPD. High recoveries of 76–102% and 76–100% were obtained for acephate and chlorpyrifos respectively, at fortification levels of 0.01, 0.1 and 1 mg kg^?1 with standard deviations below 9.0%. The addition of water prior to the extraction was important for obtaining high and reproducible recoveries. The method did not require clean-up of the extracts prior to GC analysis and could be detected down to 0.01 mg kg^?1. A field study was conducted using the modified method to measure the degradation kinetics and migration of acephate and chlorpyrifos in one of the soils over a period of 84 days. The degradation of acephate and chlorpyrifos were rapid with half-lives of 3.3 and 8.7 days, respectively. Both pesticides were detected in subsoils 2 h after application at the deepest (50 cm) soil layers examined and at concentrations up to 5.42 mg kg^?1. Subsoil concentrations of acephate were higher than for chlorpyrifos, and subsoil concentrations of acephate peaked after it had started to degrade in the top soil. The subsoil concentrations of the pesticides were attributed to transport with soil particles (chlorpyrifos) and via solution (acephate) through pores and cracks present in the soil profiles. The study demonstrates the high mobility of even strongly retained and fast degrading pesticides under tropical humid conditions.     

Evidence for the production of NO and N2O in two contrasting subsoils following the addition of synthetic cattle urine

Nitrogenous materials can be transferred out of the topsoil, either vertically to a greater depth, or in lateral pathways to surface waters, and they may also become transformed, with the potential of generating environmentally active agents. We measured the production of NO and N₂O in two contrasting subsoils (70 to 90 cm): one poorly drained and the other freely drained and compared this with the topsoil (0 to 20 cm) of the corresponding soils. The soils were incubated aerobically in jars with subtreatments of either synthetic cattle urine or deionised water and sampled at intervals up to 34 days. ¹⁵N‐NO was used to determine the processes responsible for NO and N₂O production. The headspace was analysed for the concentrations of N₂O, NO and CO₂ and ¹⁵N enrichment of N₂O. The soil samples were extracted and analysed for NO, NO and NH, and the ¹⁵N enrichment of the extracts was measured after conversion into N₂O and N₂. The study demonstrated the potential for NO, N₂O and NO to be generated from subsoils in laboratory incubations. Differences in these N dynamics occurred due to subsoil drainage class. In the freely drained subsoil the rates of NO and NO production were higher than those observed for the corresponding topsoil, with mean maximum production rates of 3.5 µg NO‐N g⁻¹ dry soil on day 16 and 0.12 µg NO‐N g⁻¹ dry soil on day 31. The calculated total losses of N₂O‐N as percentages of the applied synthetic urine N were 0.37% (freely drained subsoil), 0.24% (poorly drained subsoil), 0.43% (freely drained topsoil) and 2.09% (poorly drained topsoil). The calculated total losses of NO‐N as percentages of the applied synthetic urine N were 1.53% (freely drained subsoil), 0.02% (poorly drained subsoil), 0.25% (freely drained topsoil) and 0.08% (poorly drained topsoil). Copyright © 2010 John Wiley & Sons, Ltd.     

An adsorption study of Sr2+ from saline sources by coconut shell charcoal

The adsorption potential of charcoal for the removal of heavy metal ions is well documented in the literature. However, its exploration for uptake of technologically valuable metal ions such as Sr²⁺ is poorly known. In this work, the batch adsorption study of Sr²⁺ ion from aqueous solution as well as from saline matrix (>3% of NaCl) onto charcoal has been carried out. The experiments were conducted with two charcoals, i.e., our prepared charcoal (coconut shell charcoal) and commercial charcoal. Strontium adsorption has been investigated as a function of its initial concentration, contact time, and varied mass of adsorbent. Equilibrium adsorption data were evaluated for Langmuir and Freundlich isotherm models. The adsorption capacities (mg/g) of Sr²⁺ present in the salt matrix onto coconut shell charcoal and commercial charcoal was found to be 18.4 and 22.2, respectively. Uptake of Sr²⁺ from subsoil brine onto coconut shell charcoal has been successfully demonstrated in this work.     

Use of radiometric emanation method in the characterization of anthropogenic glass analogue for vitrification of nuclear waste

Anthropogenic analogues can be used as one of the sources of information about long-term behaviour of engineered barriers, used for geological disposal of radioactive waste. The radiometric emanation method, based on the measurement of radon release from the solid samples, was used in the study of the alteration of anthropogenic glass analogues for radioactive vitrified waste. The samples were labeled at their surface by a solution containing ²²⁸Th and ²²⁴Ra,serving as source of ²²⁰Rn nuclides. The radon ²²⁰Rn nuclides were introduced in the uranium glass samples due to the recoil energy of the α-decay of ²²⁸Th and ²²⁴Ra nuclides. The man-made uranium glass samples from a locality in the Czech Republic were used. The measurement, based on the release of radon atoms from the samples, was applied to characterize the radon diffusion permeability and microstructure changes of weathered and non-weathered uranium glass samples during heat treatments. The radon diffusion characteristics and microstructure stability of the uranium glass analogue samples were evaluated by using a mathematical model.     

Artificial radioactive contamination of sediments along the Romanian sector of the Danube river and the Black Sea coast

The concentrations of⁹⁰Sr,²³⁸Pu,^239,240Pu and²⁴¹Am were determined in 12 sediment samples, collected from the bed of the Romanian sector of the Danube river and the Black Sea coast during 1996–1997. The samples were dissolved using a microwave digestion technique which left the refractory part of the samples undissolved. Part of the samples were also dissolved totally by alkaline fusion. The results obtained after radiochemical separations and measurement of the radionuclides by the two dissolution methods were compared recommending the optimum method. The radioactive contamination of the investigated sector in 1996–1997 is compared with the results obtained for the same locations in 1994–1995 reported in previous papers.     

Influence of the mineral matter content on the rate of heat release from Turkish lignites

In this study, combustion curves of twenty-five original and demineralized Turkish lignite samples were obtained through use of a differential thermal analyser. The lignite samples were demineralized by treatment with hydrochloric and hydrofluoric acids. Samples of 20 mg were heated up to 1074 K at a constant rate of 10 K min^–1 in a 40 cm³ min^–1 flow of dry air. The rates of heat release from the original and demineralized samples were compared and are discussed.     

Radioactive impact of a bauxite beneficiation plant in the Itea Gulf (Gulf of Corinth, Greece)

Activity concentration measurements of natural radionuclides performed by γ-ray spectrometry and ICP-MS in sediment samples from the Gulf of Itea and in surface soil samples collected from the surrounding area of a bauxite beneficiation plant, showed that (1) the breaker zone of the Itea Gulf, in the vicinity of the bauxite beneficiation plant, is contaminated with ²³⁸U, ²³²Th and ²²⁶Ra, (2) the activities in sediment samples from the rest of the Gulf were at the background level, and (3) enhanced activities of the ²³⁸U, ²³²Th and ²²⁶Ra were found in a number of soil samples due to bauxite dust deposition from the nearby beneficiation plant. The application of the optimized BCR sequential extraction procedure on the surface sediment samples showed that the U and Th were strongly bound to the sediments.     

The determination of traces of iridium in rhodium by neutron activation analysis

Iridium traces were determined in rhodium by thermal neutron activation for 2 days at a flux of 4.10¹¹ n·cm^-2·sec^-1. After cooling for at least 1 week, the samples were analysed by γ-spectrometry. No radiochemical separations were required. Special attention was paid to self-absorption phenomena in the rhodium samples.     

Thermo-XRD analysis of the adsorption of Congo-red by montmorillonite saturated with different cations

The adsorption of the organic anionic dye Congo red (CR) by montmorillonite saturated with Na⁺, Cs⁺, Mg²⁺, Cu²⁺, Al³⁺ and Fe³⁺ was investigated by XRD of unwashed and washed samples after equilibration at 40% humidity and after heating at 360 and at 420°C. The clay was treated with different amounts of CR, most of which was adsorbed. Clay samples, untreated with CR, after heating showed collapsed interlayer space. Unwashed and washed samples, which contained CR, before heating were characterized by three peaks or shoulders, labeled A (at 0.96-0.99 nm, collapsed interlayers), B (at 1.24-1.36 nm) and C (at 2.10-2.50 nm). Peak B represents adsorbed monolayers of water and dye anions inside the interlayer spaces. Peak C represents interlayer spaces with different orientations of the adsorbed water and organic matter. Diffractograms of samples with small amounts of dye were similar to those without dye showing peak B whereas diffractograms of most samples with high amounts of dye showed an additional peak C. Heated unwashed and washed samples were also characterized by three peaks or shoulders, labeled A' (at 0.96 nm), B' (at 1.10-1.33 nm) and C' (at 1.61-2.10 nm), representing collapsed interlayers, and interlayers with charcoal composed of monolayers or multilayers of carbon. When the samples were heated from 360 to 420°C some of the charcoal monolayers underwent rearrangement to multilayers. In the case of Cu the charcoal decomposed and oxidized. The present results show that most of the adsorbed dye was located inside the interlayer space.This revised version was published online in November 2005 with corrections to the Cover Date.     

Role of mineralogical structure of sediments in accumulation of radionuclides and trace elements

Similar distributions for ²³⁸U, ²³²Th, ²²⁶Ra, ²¹⁰Po, ^238,239,240Pu, ¹³⁷Cs and trace elements were obtained in sediment samples collected along the Romanian sector of the Danube River and the Black Sea coast during 1994. The radionuclide and trace element accumulation in the investigated samples is discussed with respect to their geochemical behavior and the mineralogical structure of the samples. The latter, investigated by X-ray diffraction and cation exchange capacity of the same samples, proves to be an important factor in the selection of sampling sites for monitoring the pollution of river basins and the sea.     

Formability and properties of self-standing clay film by montmorillonite with different interlayer cations

Influences of exchangeable interlayer cations were investigated on self-standing film formability, film morphology, and properties of the clay films such as flexibility and gas barrier property. Ion-exchanged montmorillonite samples were prepared by a cation exchange from naturally bearing cation, mostly Na⁺, to Li⁺, Mg²⁺, Ca²⁺, Al³⁺, and Fe^{2+, 3+}. Self-standing films were prepared from aqueous colloidal dispersions of these montmorillonite samples with no additives. The montmorillonite samples with monovalent or divalent cation formed flat self-standing films while the Al-montmorillonite sample produced a distorted film. The Fe-montmorillonite sample formed many separated reddish-brown rod-shaped pieces. Clay film microstructures were different with interlayer cations. The films with monovalent interlayer cations were constructed by the stacking of units with delicately waved thin clay sheets in the whole film, but other films show different morphologies between the upper side and lower side; the upper side is laminated with thin sheets; the lower side is laminated with large thick sheets.The self-standing films’ flexibility and gas barrier property differed according to the interlayer cations. These properties were good in cases of samples with monovalent cations. The innumerable short wave and sheet thinness are considered to foster good flexibility and gas barrier properties. The differences in film formability and properties of the films are attributable to different swellability among samples with different interlayer cations. The montmorillonite samples with monovalent cations swell sufficiently by water, but those with polyvalent cations swell poorly. In the latter case, clay crystals aggregate in water, then the aggregate grows into large particles, creating a film with large particles.     

Neutron activation analysis and radioactivity measurements of Australian coals and fly ashes

Forty elements were determined by instrumental neutron activation analysis in a wide range of Australian coals and fly ash to update and extend earlier measurements. The natural radioactivity content of selected samples were analysed by high resolution gamma-ray spectrometry and low level radiochemistry. The results indicated a marked disequilibrium of the²³²Th decay series in some samples while a general enrichment of²¹⁰Pb in most fly ash samples disrupted the²³⁸U equilibrium.     

Kinetics of adsorption of zinc-ions by doped manganese dioxides

Using⁶⁵Zn-labelled solutions, the kinetics of the specific adsorption of Zn²⁺-ions by doped manganese dioxides was studied, at pH values corresponding to their isoelectric points (IEP's), by γ-ray scintillation counting. The rate of the fast adsorption of Zn²⁺-ions by doped dioxides increased in the series: Li⁺-doped<undoped<Mo(VI)-≈V(V)-doped samples. The uptake of Zn²⁺-ions in about 10 minutes exhibited a similar increase. Compared to the undoped sample, the extent and the rate of adsorption were lower for the samples doped with an ion of valence<4 but were higher for samples doped with ions of valence>4.     

Calibration and optimization of alpha-beta separation procedures for determination of radium/radon in single- and two-phase liquid scintillation systems

Liquid scintillation alpha beta discrimination technique based on pulse shape analysis (PSA) was evaluated for determination of ²²⁶Ra and ²²²Rn in water samples. In view of the significance of calibration, for the reliable and precise determination of ²²⁶Ra and ²²²Rn concentrations in water samples, calibration procedures were standardized for single and two phase systems using Quantulus 1220 liquid scintillation counter. PSA optimization and efficiency calibrations were performed using ²²⁶Ra standard rather than conventionally used pure alpha and beta standards and substantiated by measuring the activity concentrations of ²²⁶Ra and ²²²Rn in the spiked water samples.     

Artificial radioactive contamination of sediment samples along the Romanian sector of the Danube river and the Black Sea coast

The concentrations of¹³⁷Cs were determined by in 11 sediment samples, collected along the Romanian sector of the Danube river and the Black Sea coast during 1994 γ-ray spectrometry. The concentrations of⁹⁰Sr in the same sediment samples were determined by β-counting of the⁹⁰Y oxalate, precipitated after strontium separation using a strontium extraction chromatography column. The concentration distributions of¹³⁷Cs and⁹⁰Sr are compared with the²³⁸Pu and^239,240Pu concentration distributions in the same samples, reported in a previous paper. The accumulation potential of¹³⁷Cs,⁹⁰Sr and plutonium isotopes in the river and sea sediments analysed is discussed.     

Determination of Bitterness of Extra Virgin Olive Oils by Amperometric Detection

A flow injection system with amperometric detection at potentials poised at +0.4 and +0.9 V was used to evaluate intensity of the bitter taste in monovarietal Extra Virgin Olive Oils (EVOO). Results from the proposed method were based on the extraction of the bitter constituents of the virgin olive oil samples in methanol‐water, followed by the direct amperometric measurement. These potentials were selected according to the hydrodynamic voltammogram of oleuropein, one of the most prominent and bitter phenolic compound found in EVOO. The amperometric detection was applied on 32 monovariatal EVOO samples. Results were correlated with the phenolic profile measured by high performance liquid chromatography (HPLC). The amperometric signal at +0.9 V mainly correlated with the total phenols of the samples (R²=0.81), whereas the signal at +0.4 V mainly correlated with oleuropein aglycone (3,4 DHPEA‐EDA, R²=0.79). Bitterness intensity of the samples was evaluated by a trained sensory panel of experts and the results compared to those obtained by the amperometric flow system. The best correlation with the bitter taste was achieved by the sensor at +0.4 V (R²=0.72). A calibration model based on partial least squares was built with three variables, namely the sensors set at +0.4 and +0.9 V and the total phenol content of the EVOO extracts. The model showed a moderate capacity to predict the bitterness of the EVOO samples using leave one out method, (R²=0.75) and in prediction of a test set of samples (R²=0.7). Such approach is very promising for future studies.     

Direct synthesis of Nd3+ doped mesoporous TiO2 and investigation of its photocatalytic performance

Nd³⁺ doped mesoporous TiO₂ samples with different molar ratio of Nd/Ti were synthesized by a sol?Cgel method. The textural and optical properties of the samples were systematical characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption?Cdesorption isotherms, Fourier transform infrared spectroscopy and UV?CVisible absorbance spectroscopy. It was revealed that Nd³⁺ doping inhibited the phase transformation from anatase to rutile after calcination, and the mesoporous structure of doped samples was still retained with the increase of Nd/Ti molar ratio. The surface area of the samples varied from 137 to 210 m²g^?1 and the average pore size of them ranged between 5.7 and 8.2?nm. The photocatalytic activities of all the samples were evaluated by degradation methyl orange (MO) in aqueous solution as a model reaction under UV light irradiation. The results showed that the doped samples demonstrated a higher photocatalytic activity than the mesoporous TiO₂, and the 3?mol% Nd³⁺ doped mesoporous TiO₂ exhibited the best photocatalytic performance. Meanwhile, a promotion effect of the H₂O₂ added was verified in the degradation of MO.     

Survey of concentration of polycyclic aromatic hydrocarbons in lake balaton by HPLC with fluorescence detection

Summary Concentrations of polycyclic aromatic hydrocarbons (PAHs) were determined in water and sediment samples at 15 sites in Lake Balaton during three sampling campaigns in 1996. PAHs were concentrated from water samples by solid phase extraction. Sediment samples were extracted with acetone in an ultrasonic bath then cleaned by solid phase extraction. The total concentration of PAHs ranged from 30–360 ng g⁻¹ and from 170–720 ng L⁻¹ in sediment and water samples, respectively. Spatial and temporal variations of the concentration of PAHs were also investigated. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.     

Determination of total mercury and methylmercury in hair samples from residents of Kuala Lumpur, Malaysia by neutron activation analysis

to estimate the level of total mercury and methylmercury in Kuala Lumpur residents, 400 hair samples were analysed by neutron activation analysis. Separation of methylmercury from hair samples were carried out prior to neutron activation. The average level of total mercury and methylmercury in hair samples were 3.38 mg^.kg^-1 (in range of 0.59-18.73 mg^.kg^-1) and 1.13 mg^.kg^-1 (in range of 0-4.65 mg^.kg^-1), respectively. The average percentage ratio of methylmercury to total mercury was 31.15% (in range of 0 to 75.81%). This revised version was published online in August 2006 with corrections to the Cover Date.     

Structural and magnetic impact of Cr+-implantation into GaN thin film

Thin films of GaN with thickness of 2 μm were synthesized on sapphire. Cr⁺ ions were implanted into GaN with150 keV energy at a fluence of 3 × 10¹⁵ cm⁻². The annealing of the samples was carried out for a short time using rapid thermal annealing (RTA). Structural properties of the implanted samples were undertaken by XRD and Rutherford backscattering. The annealed samples demonstrated lattice recovery and damages caused by implantation. The structural properties were also studied by High-resolution X-ray Diffraction (HRXRD). Magnetic measurements of the samples were performed by Alternating Gradient Magnetometer (AGM) at room temperature and by SQUID in the range of 5–380 K. The SQUID results showed ferromagnetic behavior at T = 5 K and above 380 K for Cr⁺-implanted GaN.