Application of Experimental Design to the Optimization of a Wet Acid Digestion Procedure for Cd Determination in Plastic Materials by Atomic Absorption Spectrometry

ABSTRACT

A simple and reliable method for Cd determination in plastic materials using optimized wet acid digestion procedure and atomic absorption spectroscopy was developed. In order to obtain the best experimental conditions for plastic digestion, a 2^7–4 Plackett-Burman design for screening the significant factors and a 2^4–1 central composite design to optimize the significant experimental variables were carried out. The polyethylene European Reference Material ERM-EC680 with certified Cd content was used in both the screening and the optimization steps. The optimized experimental conditions 0.200 g of plastic material digested with 2 mL nitric acid (30 min, 130°C) followed by 1 mL sulfuric acid (30 min, 140°C). The accuracy and precision was checked using ERM-EC680. The Cd recovery was 101.3% and the relative standard deviation was 5.6%. The limit of detection obtained was 0.23 mg kg^?1. The method was applied in the analysis of one PVC plastic material, several commercial packaging materials, and plastic toys.     

The determination of concentrations of radioisotopes in some granite samples in Turkey and their radiation hazards

The primordial radionuclides activity concentrations (²²⁶Ra, ⁴⁰K and ²³²Th) are measured in some granite samples in this study. The collected granite materials are analyzed with NaI(Tl) gamma-ray spectrometry. The specific activity of ²²⁶Ra, ²³²Th and ⁴⁰K values are in range 2.60?±?0.10 to 178.9?±?0.6?Bq?kg^?1, 1.46?±?0.10 to 162.50?±?0.75?Bq?kg^?1 and 19.8?±?0.3 to 579.7?±?2.8?Bq?kg^?1 respectively. The radium’s equivalent activity, annual effective dose, absorbed dose rate, hazard index, radioactivity level index, activity utilization’s index and exposure rate are calculated for determination of radiological risk. The concentration of ²²⁶Ra (in the 71.4% of samples), ²³²Th (in the 71.4% of samples) and ⁴⁰K (in the 14.3% of samples) in the granite samples are higher than average radioactivity concentrations of this radio-isotopes defined by ICRP (35.0, 30.0 and 400.0?Bq?kg^?1, respectively).     

Development of a portable analyzer using solid-phase microextraction coupled with thermal desorption digitally-controlled plasma optical emission spectrometry for the determination of mercury volatile compounds released from sediments

Novel multi-species analyzer based on thermal desorption and digitally-controlled plasma optical emission spectrometry followed by solid-phase microextraction has been developed for determining various organometallics in sediment samples. A helium plasma source operating at 10?kHz and an integrated small-sized spectrometer with a charge-coupled device detector is installed for cost-effective atomic emission measurement and signal acquisition. Moreover, the analyzer size of a portable device is achieved, while the system is capable of absorbing large amounts of measurement data. Specifically, the analyzer has been applied for the speciation of mercury species in sediments. Method detection limits for MeHg and Hg²⁺ are 35.4 and 9.6?ng L^?1. Thus, sediments containing above 0.2 µg kg^?1 of mercury can be analyzed with precision 1–3.5% of RSD. The developed methods are validated by the analysis of estuarine sediment certified reference material ERM CC580, GBW 07405 Chinese soil. [AQ1]     

Preparation of cadmium‐containing brown rice grains as calibration standards for X‐ray fluorescence analysis of cadmium in rice grains

A preparation method for Cd‐containing brown rice grains as calibration standards was developed for X‐ray fluorescence (XRF) analysis of Cd in rice grains. Calibration standards were prepared by adding 10 g of base rice grains (from Japan) to 100 ml of methanol containing 5?100 µg of Cd. The mixture was heated, cooled, and stored in a silica gel desiccator. Seven grams of each calibration standard was packed into a polyethylene cup (32‐mm internal diameter and 23‐mm height) covered with a 6‐µm‐thick polypropylene film and then subjected to XRF analysis. The calibration curves of Cd in brown and white rice grains showed good linearity in 0.50?10 mg kg^?1. The detection limits of Cd in brown and white rice grains were 0.14 and 0.12 mg kg^?1, respectively. The slopes of the calibration curves for Cd in brown and white rice grains were slightly different owing to absorption effects. The absorption effects were corrected using the ratio of the intensity of Cd Kα to that of Rh Kα‐Compton scattering. After correction, the calibration curves of Cd in brown and white rice grains showed identical slopes. The spike test for 5 mg kg^?1 of Cd in white rice grains (from Thailand), using the corrected calibration curves, showed quantitative recoveries (92?97%). Copyright © 2013 John Wiley & Sons, Ltd.     

Natural radioactivity and radiation hazards assessment of soil samples from the area of Tuzla and Lukavac,Bosnia and Herzegovina

The results of activity concentration measurements of natural occurring radioactive nuclides ²³⁸U, ²³⁵U, ²³²Th, ²²⁶Ra, and ⁴⁰K in surface soil samples collected in the area of cities Tuzla and Lukavac, northeast region of Bosnia and Herzegovina were presented. Soil sampling was conducted at the localities that are situated in the vicinity of industrial zones of these cities. The measured activity was in the range from (8?±?4) to (95?±?28) Bq kg^–1 for ²³⁸U, from (0.41?±?0.06) to (4.6?±?0.7) Bq kg^–1 for ²³⁵U, from (7?±?1) to (66?±?7) Bq kg^–1 for ²³²Th, from (6?±?1) to (55?±?6) Bq kg^–1 for ²²⁶Ra, and from (83?±?12) to (546?±?55) Bq kg^–1 for ⁴⁰K. In order to evaluate the radiological hazard of the natural radioactivity for people living near industrial zones, the absorbed dose rate, the annual effective dose and the radium equivalent activity have been calculated and compared with the internationally approved values.     

Natural radioactivity measurements in Pahang State,Malaysia

This study was aimed at providing the baseline data of terrestrial gamma dose rates and natural radioactivity to assess the corresponding health risk in the ambient environment of the Pahang State. Terrestrial gamma radiation (TGR) from 640 locations was measured with the mean value found to be 176?±?5 nGy h^?1. Ninety-eight soil samples were analysed using a high-purity germanium detector (HPGe), and the mean concentrations of the radionuclides ²²⁶Ra, ²³²Th and ⁴⁰K are 110?±?3, 151?±?5 and 542?±?51 Bq kg^?1, respectively.²²⁶Ra and ²³²Th concentrations were found to be three times the world average, while that of ⁴⁰K is quite higher than the world average value. The acid-intrusive geological formation has the highest mean concentrations for ²²⁶Ra (215?±?6 Bq kg^?1), ²³²Th (384?±?12 Bq kg^?1) and ⁴⁰K (1564?±?153 Bq kg^?1). The radium equivalent activities (Req) and the external hazard index (Hex) for the various soil types were also calculated. Some of the soil types were found to have values exceeding the internationally recommended levels of 370 Bq kg^?1 and the unity value, respectively.     

Statistical relationship between activity concentrations of radionuclides 226Ra, 232Th, 40K,and 137Cs and geological formations in surface soil of Jordan

An extensive study was conducted to determine the activity concentrations of natural and artificial radionuclides ²²⁶Ra, ²³²Th, ⁴⁰K, and ¹³⁷Cs in soil samples of each governate of Jordan. A total of 370 samples have been measured using a high-purity germanium detector. The activity concentration for ²²⁶Ra, ²³²Th, ⁴⁰K, and ¹³⁷Cs has mean values of 42?±?3, 23?±?3, 309?±?21, and 3.7?±?0.9 Bq kg^–1, respectively. The highest mean activity concentration for ²²⁶Ra was found to be 138?±?4 Bq kg^–1 in the Alkarak governate. In the Ajloun and Jarash governates, the highest mean activity concentration was 35?±?3 Bq kg^–1 for ²³²Th, and 14.2?±?1.9 Bq kg^–1 for ¹³⁷Cs, respectively. Geological influence on the activity concentrations was investigated using the one-way analysis of variance (ANOVA) and independent samples. The ANOVA results indicate that there are strong significant differences between the activity concentrations of ²³²Th, ⁴⁰K, and ¹³⁷Cs based on geological formations the radionuclides occur. The main contribution to gamma dose rate was due to ²²⁶Ra activity concentration. Radium equivalent and external hazard index are associated with a mean value of 98 Bq kg^–1, and 0.266, respectively.     

Soil depth profile of 137Cs, 210Pb and 40K in Algeria

ABSTRACT

Three soil depth profiles of ²¹⁰Pb, ¹³⁷Cs and ⁴⁰K at different areas of Algeria were studied. The soil sampling areas are near the location where the French nuclear tests took place at 1960–1966. The two depth soil profiles were collected at Ghardaia region and the third one at Reggane region. The vertical distributions of radionuclides at the two soil depth profiles from Ghardaia region are different, probably due to the different soil composition. The soil depth profile from sandy soil show uniformity in the distribution of radionuclides without a clear maximum (peak). The soil depth profile that characterised by silty sand show a clear peak at 20–50?cm depth for all studied radioactive nuclides, while the observed activities are two times higher than the corresponding values in sandy soil samples. More specifically in Ghardaia region the ²¹⁰Pb, ¹³⁷Cs, ⁴⁰K activity concentrations ranged between 27 and 50?Bq?kg^?1, 0.2 and 3?Bq?kg^?1 and 75 and 90?Bq?kg^?1 respectively in sandy soil type and between 37 and 75?Bq?kg^?1, 4 and 6?Bq?kg^?1 and 140 and 180?Bq?kg^?1 respectively in silty sand soil type. Finally, the third depth soil profile collected from Reggane site presents a completely different distribution of the studied radionuclides. The activity concentrations of ²¹⁰Pb, ¹³⁷Cs, ⁴⁰K ranged between 37 and 51?Bq?kg^?1, 0.16 and 0.39?Bq?kg^?1 and 120 and 309?Bq?kg^?1 respectively. Three peaks in the ¹³⁷Cs distribution revealed, were most probably, Chernobyl related ¹³⁷Cs accounts for the surface peak, while the deeper peaks are connected to the weapons fallout.     

Radioactive caesium (134Cs and 137Cs) in mushrooms of the genus Boletus from the Reggio Emilia in Italy and Pomerania in Poland

Activity concentrations of ¹³⁴Cs and ¹³⁷Cs were determined in mushrooms of the Boletus species B. aereus, B. reticulatus, B. appendiculatus, B. calopus, B. edulis, B. erythropus, B. fechtneri, B. pinophilus, B. pseudoregius, B. rhodopurpureus, B. rhodoxanthus collected in the Reggio Emilia, Italy, in 1993 and 1994 and in B. edulis collected in Pomerania in northern Poland in the period from 1995–2015. Boletus edulis from the Reggio Emilia showed presence of ¹³⁷Cs at 330?±?220?Bq?kg^?1 dry biomass in 1993 and at 370?±?180?Bq?kg^?1 dry biomass in 1994. In B. edulis sampled in the Reggio Emilia in 1993 and 1994, the pre-Chernobyl ¹³⁷Cs from global fallout amounted to 39–46?% of the total activity concentrations of isotope ¹³⁷Cs. B. edulis from Pomerania contained ¹³⁷Cs in caps at 270?±?15?Bq?kg^?1 dry biomass in 1995, and in whole fruiting bodies it was found to be 470?±?9?Bq?kg^?1 dry biomass in 2015. The activity concentrations of ¹³⁷Cs determined in fruiting bodies of B. edulis from Pomerania fluctuated but persisted over the period from 1995 to 2015, while the maximum activity concentrations were well below the tolerance limit of 600?Bq?kg^?1 fresh product.     

Vertical-slate-like MoS2 nanostructures on 3D-Ni-foam for binder-free,low-cost,and scalable solid-state symmetric supercapacitors

Here, we report binder-free vertical-slate-like MoS₂ nanostructures on 3D-Ni-Foam (VSL-MoS₂@3D-Ni foam) for low-cost high-performance solid-state symmetric supercapacitors (SSCs). The cost-effective, ecofriendly and scalable solvothermal method and its direct incorporation of VSL-MoS₂@3D-Ni-foam yield SSCs with excellent electrochemical properties with a wide potential window of 1.0?V. Furthermore, high specific capacitance of 34.1?F?g^?1 at a current density of 1.3?A?g^?1, an energy density of 4.7?W?h?kg^?1 at a high-power density of 650?W?kg^?1, and excellent stability with ～82.5% capacitance retention after 10,000 cycles were demonstrated even for SSCs with a binder free MoS₂ electrodes on 3D-Ni-foam. These excellent features of the SSCs with VSL-MoS₂@3D-Ni-foam substantiate their potential opportunity for future energy applications.     

Loose‐powder technique for X‐ray fluorescence analysis of ancient pottery using a small (100 mg) powdered sample

A molded‐loose‐powder technique using a small powdered sample (100 mg) was developed for the X‐ray fluorescence analysis of 22 components (Na₂O, MgO, Al₂O₃, SiO₂, P₂O₅, K₂O, CaO, TiO₂, MnO, Fe₂O₃, V, Cr, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, and Pb) in ancient pottery. This loose powder specimen was prepared by pressing the small powdered sample into a sample holder, formed from a stainless steel disk (48‐mm diameter × 0.8‐mm height) with a hole (11‐mm diameter), by hand. Calibration standards were prepared by homogenizing chemical reagents containing these 22 analytes using the concentration ranges of 166 ancient potteries and three clay materials from Japan. The calibration curves of these benchmark mixtures exhibited a good linearity (correlation coefficient, r = 0.990–1.000), accuracy, and reproducibility compared with those of other synthesized specimens and three reference standards. The lower limits of detection were less than tens of mg kg^?1 (e.g., 94 mg kg^?1 for Na₂O, 11 mg kg^?1 for P₂O₅, 1.1 mg kg^?1 for Rb, and 0.9 mg kg^?1 for Y). Using the present method, we determined 22 components in two prehistoric potteries from Japan. The advantage of this method is that only a small amount of sample is required, which can be prepared easily and rapidly and reused for other analyses. Copyright © 2012 John Wiley & Sons, Ltd.     

Online Copper Removal for Selenium Determination by Hydride Generation–Inductively Coupled Plasma Optical Emission Spectrometry

Abstract

Selenium determination in samples with a high copper content by hydride generation–inductively coupled plasma optical emission spectrometry (HG‐ICP‐OES) after online copper removal and selenium (VI) reduction is described. An activated carbon minicolumn was used for the retention of copper and its subsequent separation of Se. Se(VI) was then online reduced by heating into a PTFE coiled reactor with 12 M HCl. The analyte was introduced into a water stream containing sodium tetrahydroborate (NaBH₄) in order to generate selenium hydride (H₂Se). The detection limit (DL) obtained was 0.8 µg L^?1, and the precision, expressed by the relative standard deviation (RSD), was 2.5% (n=10; 10 µg L^?1 selenium level). The current method was applied to the Se determination in two copper reference materials, MBH‐39DK 3601 (with a Se content of 90 mg kg^?1) and MBH‐39 DK 3604 (with a Se content of 15 mg kg^?1).     

Microwave-assisted digestion for trace elements analysis of tree nut oil: evaluation of residual carbon content

Abstract

An inductively coupled plasma mass spectrometer method for estimating trace elements in tree nut oils has been developed which employs microwave digestion equipped with high pressure subassembly. Residual carbon content and residual acidity were determined to evaluate the efficiency of digestion. The best digestion efficiency was obtained using Easyprep? system with 0.5?g of oil, 4?mL concentrated nitric acid, and 2?mL hydrogen peroxide, and a final temperature of 235?°C. Residual carbon content and residual acidity were estimated as 1.7% (corresponding to 852?mg L^?1 of carbon in sample solution) and 7.5%, respectively, and recovery values ranged from 90.7% to 107.7%. Whereas, only 0.2?g of oil could be digested through conventional microwave system with 5?mL concentrated nitric acid and 2?mL hydrogen peroxide at 205?°C (residual carbon content?=?3.2%). The developed method has been applied to determine nine trace elements (Cr, Mn, Fe, Ni, Cu, As, Zn, Cd, and Pb) in different categories of tree nut oils, and high content of Fe, Mn, and Zn were found in some of those oils. To the best of our knowledge, the present investigation is the first attempt to analyze trace elements in different categories of tree nut oils consumed in China.     

Radium equivalent and annual effective dose from geological samples from Pedra – Pernambuco – Brazil

The natural radioactivity of an uranium-anomalous area utilized for agricultural activities in Pedra, Brazil, was monitored. For this, samples from the granite and calcium-silicate amphibole rocks underlying this area and also from samples of the soil derived from these rocks were collected and analyzed by high-resolution gamma spectrometry. The equivalent radium (Ra_eq) was used as a reference for estimating the rate of the effective equivalent dose. The average, minimum and maximum values for the samples were of 319.2 Bq kg^?1 (91.1–758.5 Bq kg^?1) for soil; 327.5 Bq kg^?1 (36.3–1624.0 Bq kg^?1) for granitic rocks and 70,124.5 Bq kg^?1 (16,979.6–147,159.0 Bq kg^?1) for the calcium-silicate amphibole rocks. An estimation of the external exposition was carried out based on the calculation of the parameters obtained.     

Polyaniline-coated cerium oxide nanoparticles as an efficient adsorbent for preconcentration of ultra-trace levels of cadmium (ІІ) followed by electrothermal atomic absorption spectrometry

For the first time, polyaniline-coated cerium oxide nanoparticles were synthesized in alkaline media and applied for preconcentration of ultra-trace levels of cadmium (??) in different real samples followed by electrothermal atomic absorption spectrometry. Cerium oxide nanoparticles were synthesized by a microwave method and modified by polyaniline to produce polyaniline-coated cerium oxide nanoparticles. Fourier-transform infrared spectroscopy and scanning electron microscopy were used to characterize the synthesized adsorbent. To optimize the critical experimental conditions; surface response methodology—Box–Behnken experimental design was used. On the basis of the results, pH 8.4, 10?mg of polyaniline-coated cerium oxide nanoparticles, 14.4?min extraction time, and 4.3?min desorption time were selected as the optimum conditions. Under the optimum conditions the calibration curve of cadmium (??) was linear in the range of 0.02–0.4?ng?mL^?1 with a correlation coefficient of 0.9976. The relative standard deviation based on seven replicate analysis of 0.1?ng?mL^?1 cadmium (??) was 4.2% and limit of detection was 0.005?ng?mL^?1 cadmium (??). The analysis of certified reference material shows very good agreement with the certified value. Finally, the proposed method was applied for the determination of ultra-trace levels of cadmium (??) in different water, rice, and tea samples.     

Validation of an extraction chromatographic method with SrResin® for determination of 210Pb in various matrices

A radiochemical method for the determination of ²¹⁰Pb in various types of samples was validated. An extraction chromatographic material Eichrom SrResin® was used for Pb separation. From the resin, Pb was eluted with 6 M HCl. The method was tested for water, inorganic and organic matrices. As a main result of the study, activity concentrations of ²¹⁰Pb in 19 food samples of the main Czech food-basket items were determined. Results ranged from 0.03±0.01 Bq kg^?1 to 1.54±0.40 Bq kg^?1, fresh mass.     

Amorphous Cobalt Coordination Nanolayers Incorporated with Silver Nanowires: A New Electrode Material for Supercapacitors

The 2D amorphous cobalt coordination framework/silver nanowires nanocomposites (A‐CoL/Ag NC) are successfully synthesized by one‐step solution agitation at room temperature. The experimental data reveal that the hybrid provides sufficient contact between active materials and electrolyte, and facilitates the transfer of ions/electrons, resulting in high specific capacitance, high output potential, great rate capacity at high current density, and good cycle stability. As supercapacitor electrode materials, the as‐prepared A‐CoL/Ag NC electrode exhibits a great specific capacitance which can reach up to 1467 mF cm^?2 at 1.0 mA cm^?2, and 1060 mF cm^?2 even at 10.0 mA cm^?2. The A‐CoL/Ag NC// activated carbon asymmetric supercapacitor (AC ASC) displays a maximum energy density (110 W h kg^?1 at 760 W kg^?1) and maximum power density (6410 W kg^?1 at 63 W h kg^?1) in 3.0 m KOH. Moreover, the developed solid‐state A‐CoL/Ag NC//AC ASC has a broad operated potential window within 0–1.6 V, long cycle life (95.2% after cycling 7000 cycles), delivering an energy density of 151 W h kg^?1 (at 790 W kg^?1), and a power density of 7972 W kg^?1 (at 70 W h kg^?1). The well‐synthesized nanocomposite provides a novel way to synthesize prominent electrode materials for supercapacitors.     

Sulfur speciation in two typical soil samples using X-ray absorption near-edge structure spectroscopy and chemical fractionation

Sulfur K-edge X-ray absorption near-edge structure spectroscopy and chemical sequential extraction was respectively used to study the speciation of sulfur in two sulfur-rich soils samples. Sulfur K-edge X-ray absorption near-edge structure spectroscopy analysis obtained a variety of spectra. Spectral fitting of the X-ray absorption near-edge structure spectra utilizing a large set of model compounds showed great differences between these two sulfur-rich soil samples. It was found that both of the soil samples had high sulfur content (8.40 and 11.57?g?kg^?1, respectively). Chemical extraction results suggested that sulfur mainly existed as organic in the ancient paddy soil (7.37?g?kg^?1) and more reduced sulfur was identified in it. X-ray absorption near-edge structure spectroscopy also got similar results. These organic forms of sulfur existed in organic matter across a range of oxidation states. There was high proportion of oxidized sulfur in the sulfuric acid plant that mainly existed as sulfate.     

Radiocaesium pollution of fly agaric Amanita muscaria in fruiting bodies decreases with developmental stage

Amanita muscaria collected from a forested area in northern Poland in 2015 were analysed for activity concentrations of ¹³⁷Cs and ⁴⁰K. Total K concentration values were calculated from ⁴⁰K data. Mushrooms were grouped in six fruiting bodies size classes regarding to their developmental stage. The ¹³⁷Cs activity concentrations declined in A. muscaria as the fruiting bodies maturated. The contents of ⁴⁰K/K activity remained constant in caps at different developmental stage, while for stipes an increase was around twofold (⁴⁰K from 925?±?55 Bq kg^?1 dry biomass in the baby individuals and 1600?±?63–1700?±?53 Bq kg^?1 dry biomass in two oldest classes). A. muscaria is a weak accumulator of ¹³⁷Cs, while a steep drop in activity concentrations of this nuclide in the fruiting bodies as they maturate has not been reported earlier for mushrooms. Clearly, a fate of ¹³⁷Cs in A. muscaria is highly different from that of ⁴⁰K/K that is an essential element to fungi. In parallel, an observed increase in the content of ⁴⁰K/K in stipes of fruiting bodies with developmental state can be related to its ‘hardening’ and more fibrous nature with age and basic function to support the cap, but this has not been studied.