Phantom studies of Cd, Hg and Cl by prompt gamma neutron activation analysis using a Pu-Be neutron source

Prompt gamma neutron activation analysis is a means of non-invasive monitoring for occupational exposure to toxic heavy metals such as Cd and Hg. Preliminary kidney detection limits from previous phantom studies at McMaster were 13.6 ± 0.2 ppm for Cd (125 mL phantom) and 315 ± 24 ppm for Hg (125 mL phantom) using the ²³⁸Pu-Be neutron source and 0.88 ± 0.01 ppm for Cd (125 mL phantom) and 16.91 ± 0.05 ppm for Hg (30 mL phantom) using the thermal neutron beam port at the McMaster Nuclear Reactor. The detection limits vary greatly between the two methods due to differences in experimental set-up, neutron energy spectra and a difference in dose by more than a factor of 100. The Hg detection limit from preliminary data is much higher than expected for both neutron source types. In order to explain the apparent detection limit discrepancy, measurements of Hg and Cd phantoms were performed using the ²³⁸Pu-Be neutron source. The results were compared to phantom measurements of Cl, a well-known neutron activation element.     

Ionic liquids as passive monitors of an atmosphere rich in mercury

An ionic liquid (IL) is a compound at dynamical equilibrium in which at any time more than 99.99% of it is shifted toward the ionic rather than the molecular species. ILs have raised considerable attention during the past few years due to their extremely low vapor pressure, good electrolytic properties and wide electrochemical window. Also, they remain liquid at a wide range of temperature. ILs are able to dissolve some non polar chemical species as well as some very polar ones. Their main applications have been so far in environmental chemistry and can be considered as environmental friendly solvents. Mercury is a naturally occurring element that is found in the atmosphere, generally present in three forms: elemental (Hg⁰), oxidized, and particulate-bounded. It is a very toxic element and its assessment in the environment is highly desired, however due to its volatility is an element difficult to detect by conventional sampling methods. This paper presents the results of a research on mercury binding using ILs. The following ILs were tested: 1-butyl-3-methyl-imidazolium-hexafluorophosphate [BMIM][PF₆] and 1-butyl-3-methyl-imidazolium thiocyanate [BMIM] [SCN]. Known amounts of ILs were introduced, in the form of bulk or thin coating layer, to a 70 mL glass tube with a known amount of metallic Hg and sealed with a PTFE® cap. The concentration of Hg in the IL was measured after 12 weeks of exposure. Total Hg determination was performed by particle X-ray emission (PIXE). Changes in the spectroscopic properties due to the Hg binding were followed by Raman and infrared (IR) spectroscopy. The sorption efficiency for the ILs under different experimental conditions is discussed.     

Optimization of contact conditions between iron base alloys and mercury at room temperature

The intimate contact or wetting of iron-base alloys by mercury is obtained at room temperature by varying the environmental conditions, quasi immediately for Armco iron and a high purity Fe-25Ni alloy, after ∼30 min of contact for the 316L/Hg couple, after one week of contact for the T91/Hg couple. Careful mechanical polishing allows for wetting the notches of CCT specimens made in T91 steel with Hg, whereas chemical etching in 4%HCl is required to wet 316L SS identical specimens. Using ICP-OES measurements, values of solubility limit are given for both Fe (45.5 ± 0.4 wt ppm) and Cr (0.56 ± 0.07 wt ppm) in mercury at room temperature, the one of nickel (2.6 ± 0.39 wt ppm) being in agreement with the literature data.     

Liquid metal embrittlement of an austenitic 316L type and a ferritic-martensitic T91 type steel by mercury

The susceptibility to liquid metal embrittlement (LME) of 316L and T91 steels by mercury has been studied at room temperature. A dedicated experimental device using center crack tension (CCT) specimens was built. We developed a specimen preparation procedure that must be rigorously applied in order to investigate the embrittling effect of Hg. The high strength ferritic-martensitic steel of type T91 is embrittled by Hg at room temperature over a large range of crosshead speeds, between 6.67 × 10⁻⁷ and 6.67 × 10⁻³ m s⁻¹. More surprisingly, the austenitic steel of type 316L is also embrittled by Hg between 1.67 × 10⁻⁸ and 2.5 × 10⁻⁴ m s⁻¹. The fracture of the T91 and 316L CCT specimens in contact with Hg occurs by shear band decohesion over the above-mentioned range of crosshead speeds.     

PIXE measurements of Renaissance silverpoint drawings at VERA

Silverpoint drawings from the Renaissance are among the most precious and rarest treasures of graphical art. Our research group is particularly interested in the analysis of silverpoint drawings by Albrecht Dürer (1471-1528). A very sensitive and non-destructive analytical method, either spatially resolved synchrotron-radiation induced X-ray fluorescence (SY-XRF) or proton-induced X-ray emission (PIXE), is needed to determine the chemical composition of the very faint silver marks on such drawings. Dürer drawings from the collection of the Albertina, Vienna, were analyzed to amend existing data on Dürer drawings. For this purpose an external-beam PIXE setup was installed at the Vienna Environmental Research Accelerator (VERA). It allows to analyze a spot of ∼0.15 mm on the object in air with 3 MeV protons, and to detect the emitted X-rays that are characteristic for the chemical composition with very good sensitivity and without harming the precious objects. After successful measurements on artificial test samples, four original silverpoint drawings were investigated: two portraits from Albrecht Dürer’s very early period (self-portrait and portrait of his father) and two drawings from Dürer’s sketch book of his travel to the Netherlands 1520/21.     

Fusion-Fission Transmutation Scheme—Efficient destruction of nuclear waste

A fusion-assisted transmutation system for the destruction of transuranic nuclear waste is developed by combining a subcritical fusion-fission hybrid assembly uniquely equipped to burn the worst thermal nonfissile transuranic isotopes with a new fuel cycle that uses cheaper light water reactors for most of the transmutation. The center piece of this fuel cycle, the high power density compact fusion neutron source (100 MW, outer radius <3 m), is made possible by a new divertor with a heat-handling capacity five times that of the standard alternative. The number of hybrids needed to destroy a given amount of waste is an order of magnitude below the corresponding number of critical fast-spectrum reactors (FRs) as the latter cannot fully exploit the new fuel cycle. Also, the time needed for 99% transuranic waste destruction reduces from centuries (with FR) to decades.     

同位素稀释质谱法在丙烯腈-丁二烯-苯乙烯聚合物标准物质汞定值中的应用

为应对欧盟的RoHS指令，中日韩三国建立了标准物质联合定值工作机制。文章系统介绍第一次联合定值合作中应用同位素稀释质谱法 （IDMS）为日本丙烯腈-丁二烯-苯乙烯聚合物（ABS）塑料标准物质中汞定值的方法。首先利用MC-ICP-MS准确测量了202Hg稀释剂、国家标准物质和ABS塑料中汞的全丰度，然后采用国家标准物质标定202Hg稀释剂的浓度，最后利用IDMS测定ABS塑料中汞的浓度。为消除汞的记忆效应，采用5μg/g的Au（2%硝酸溶液）清洗1min，而后用5μg/g的EDTA清洗2min的程序。实验结果验证了实验室的测量能力，首次联合定值为下阶段工作奠定了技术基础。     

Experimental study on mercury content in flue gas of coal-fired units based on laser-induced breakdown spectroscopy

Accurate measurement of trace heavy metal mercury(Hg) in flue gas of coal-fired units is great significance for ecological and environmental protection.Mixed gas was used to simulate the actual flue gas of a power plant in this study.A laser-induced breakdown spectroscopy(LIBS)system for Hg measurement in mixed gas was built to study the effect of mixed gas pressure,Hg concentration in mixed gas and delay time on Hg measurement.The experimental results show that the appropriate low mixed gas pressure can obtain high Hg signal intensity and signal to noise ratio.The Hg signal intensity and signal to noise ratio increased with the increase of Hg concentration in mixed gas.The Hg signal intensity and signal to noise ratio decreased with the increase in delay time.According to the above results,the optimized measurement conditions can be determined.Different Hg concentrations in mixed gas were quantitatively analyzed by the internal standard method and traditional calibration method respectively.The relative error of prediction of the test sample obtained by the internal standard method was within 11.11%.The relative error of prediction of the traditional calibration method was less than 14.54%.This proved that the internal standard method can improve the accuracy of quantitative analysis of Hg concentration in flue gas using LIBS.     

PIXE characterization of Lebanese excavated amphorae from Jiyeh archeological site

Archaeological excavations were undertaken in the Jiyeh archeological site which is located north of Sidon, identified as the Greco-Roman Porphyreon. The first investigations raised suggest a probable pottery production centre. About 40 sherds were analyzed by Proton Induce X-ray Emission technique PIXE in order to identify and characterize the elemental composition of four types of amphorae, using the 1.7 MV tandem accelerator in Beirut. The analysis protocol provided almost 24 elements in one spectrum, including majors, minors and traces. The elemental composition provided by PIXE and based on 12 most abundant elements, ranging from Mg to Zr, was used in a multivariate statistical program and consequently the studied objects were classify into well defined groups.     

Combining non-destructive nuclear techniques to study Roman leaded copper coins from Ilipa (II-I centuries B.C.)

A set of 32 bronze coins (II-I centuries B.C.) from the Roman city of Ilipa Magna (present-day Alcalá del Río, Seville) have been analyzed by means of non-destructive techniques. These coins are classified in different series according to their numismatic characteristics. They are very interesting from the archaeological point of view because a freshwater fish is depicted on the obverse (unusual in Mediterranean Cultures) and a spike on the reverse (also unusual but frequent in the South of the Iberian Peninsula). A comparative study has been made by PIXE (Proton Induced X-ray Emission) and XRF (X-ray Fluorescence) both corrected by GRT (Gamma Ray Transmission) in order to avoid the polishing of the coins. The results show that after the correction with GRT both independent methods give compatible concentrations for all of the coins that can be assumed as the actual bulk compositions [1]. The average concentrations of the different series have been calculated and they could help to classify the series of coins chronologically.     

Activation cross-sections of deuteron induced nuclear reactions on gold up to 40 MeV

Cross-sections of deuteron induced nuclear reactions on gold were measured up to 40 MeV by using the standard stacked foil irradiation technique and high resolution gamma-ray spectroscopy. Experimental cross-sections and derived integral yields are reported for the ¹⁹⁷Au(d,xn)^{197m,197g,195m,195g}Hg and ¹⁹⁷Au(d,x)^{198g,196m,196g,195,194}Au nuclear reactions. The experimental data are analyzed and compared to literature and predictions of the ALICE-IPPE, EMPIRE and TALYS theoretical model codes. The application of the new cross-sections for accelerator technology, medical radioisotope production, thin layer activation and dose calculation is discussed.     

Plating of archaeological metallic objects - studies by differential PIXE

The differential PIXE method using an external proton beam up to 3 MeV energy was applied to examine plated layers of tin, silver and gold on bronze, brass, iron and silver objects from Roman and Early Medieval period. The concentration profiles were deduced from the measurements by the method of virtual slicing the target into layers, and minimizing the differences between the measured and calculated X-ray yields. The tinned layers were usually thin (about 1 μm), but the thickness of silver and gold layers was in several cases thicker and exceeded the proton range. The plating techniques were identified as application of the molten metal for tinning, and as fire gilding for the gilded objects.     

Stability studies of Hg implanted YBa2Cu3O6+x

High quality YBa₂Cu₃O_6+x (YBCO) superconducting thin films were implanted with the radioactive ^197mHg (T_1/2=24 h) isotope to low fluences of 10¹³ atoms/cm² and 60 keV energy. The lattice location and stability of the implanted Hg were studied combining the Perturbed Angular Correlation (PAC) and Emission Channeling (EC) techniques. We show that Hg can be introduced into the YBCO lattice by ion implantation into a unique regular site. The EC data show that Hg is located on a highly symmetric site on the YBCO lattice, while the PAC data suggests that Hg occupies the Cu(1) site. Annealing studies were performed under vacuum and O₂ atmosphere and show that Hg starts to diffuse only above 653 K.     

X-ray microfluorescence analysis of pigments in decorative paintings from the sarcophagus cartonnage of an Egyptian mummy

This work characterized the elemental composition of the pigments used in decorative paintings from the sarcophagus cartonnage fragments of an Egyptian mummy, using μXRF with Synchrotron Radiation. This female mummy (n.158) is considered one of the most important pieces of the National Museum (Rio de Janeiro, Brazil) because of its unconventional embalming with legs and arms swathed separately. The measurements were performed at the XRF beamline D09B of the Brazilian Synchrotron Light Laboratory (LNLS), using white beam and a Si(Li) detector with resolution of 165 eV at 5.9 keV. The elements found in the samples were: Si, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Sr, Hg and Pb.     

Radiation damage annealing of Hg implanted InP

The formation of shallow p-type layers in InP has been previously achieved by Hg implantation. In this work, for the first time, microscopic information of the near surrounding of the Hg dopant and the recovery of the damaged layer is derived combining RBS and hyperfine interactions studies. It is shown that most of the radiation damage created by the implantation can be recovered with a two step furnace annealing at 400°C and 800°C using a proximity cap.     

缪子对小尺寸中低原子序数物质三维成像技术的模拟研究

缪子成像是一种利用天然本底辐射中极具穿透力的缪子射线通过散射或透射技术对高原子序数Z或隐藏物体进行无损成像的技术。当前的研究对象是大尺寸的高Z物质,而针对小尺寸的中低Z物质的成像技术在国内鲜见报道。本文提出了一种针对小尺寸中低Z物质的三维成像技术,利用Geant4软件模拟了缪致次级粒子的产生过程,模拟结果表明次级粒子主要为电子和γ光子,通过缪致次级粒子与入射缪子符合探测技术筛选入射缪子径迹,利用有限角度成像算法对待测物体进行了三维图像重建,结果表明,该技术适合于小尺寸的中低Z物质成像,尤其对小尺寸中Z物质的重建效果明显,重建图像可区分08 cm的凹槽。     

Measurement of focal spot size in a 5.5 MeV linac

High energy X-ray beams allow to perform analysis on different materials and objects of relevant interest that cannot be investigated with conventional X-ray sources. A 5.5 MeV endpoint energy bremsstrahlung source has been characterized by evaluating the size of X-ray emitting area. In order to perform a proper characterization, an ‘ad hoc’ slit-camera has been designed and a specific technique has been adopted. Due to the characteristics of the beam, a highly attenuating slit with variable aperture has been designed using Monte Carlo simulations of the X-ray beam and set up. Since the slit camera is far from the ideal model (negligible X-ray transmission and very thin aperture), a whole set of image profiles of the slit at different width sizes have been acquired and analyzed. Imaging correction procedures and data fitting lead to satisfactory experimental results according to the theoretical model.     

Cavitation-erosion resistance of 316LN stainless steel in mercury containing metallic solutes

Room temperature cavitation tests of vacuum annealed type 316LN stainless steel were performed in pure mercury and in mercury with various amounts of metallic solute to evaluate potential mitigation of erosion/wastage. Tests were performed using an ultrasonic vibratory horn with specimens attached at the tip. All of the solutes examined, which included 5 wt% In, 10 wt% In, 4.4 wt% Cd, 2 wt% Ga, and a mixture that included 1 wt% each of Pb, Sn, and Zn, were found to increase cavitation-erosion as measured by increased weight loss and/or surface profile development compared to exposures for the same conditions in pure mercury. Qualitatively, each solute appeared to increase the tenacity of the post-test wetting of the Hg solutions and render the Hg mixture susceptible to manipulation of droplet shape.     

PIXE-PIGE analysis of Carolingian period glass from Slovenia

Glass artifacts excavated from the Late Roman and Carolingian period site at Bašelj Slovenia were analyzed by the combined PIXE-PIGE method using a proton beam in air. The results show that the majority of objects and glass ingots were made of traditional Roman, natron-type glass. Increased titanium and other impurities were found indicating that the glass had been recycled several times. As the composition of the ingots was similar to the other objects, a possibility exists of a secondary glass workshop in the local vicinity. The typologically and stratigraphically dated objects confirm that the Roman glassmaking continued in the area of Eastern Alps well into the 9th century.     

Radiation cross-linking of small electrical wire insulator fabricated from NR/LDPE blends

A low voltage, radiation-crosslinked wire insulator has been fabricated from blends of natural rubber block (STR-5L) and LDPE with phthalic anhydride (PA) as a compatibilizer. Physical properties of the NR/LDPE blend ratios of 50/50 and 60/40 with 0.5, 1.0, and 1.5 wt% PA were evaluated. The gel content increased as the radiation dose increased. Tensile at break exhibited a maximum value of 12 MPa at 120 kGy for 1.0 and 1.5 wt% PA of both blend ratios. A higher PA content yielded a higher modulus for the same blend ratio. Blends of 60/40 ratio with 1.0 wt% PA and 0.8 wt% antimony oxide flame retardant gave the highest limiting oxygen index (LOI) of >30% at above 150 kGy. Other electrical properties of the wire insulator were investigated. It was found that an insulator fabricated from a PA content of 1.0 wt% in the NR/LDPE blend ratio of 50/50, after gamma ray cross-linked at a dose of 180 kGy in low vacuum (1 mm Hg), met the Thai Industrial Standard 11-2531 for low voltage wire below 1.0 kV. To comply with the standard for vertical flame test, a more suitable flame retardant was needed for the insulator.