Next-generation germanium spectrometer background reduction techniques at 2 Me

Summary The Majorana project, a next-generation ⁷⁶Ge neutrinoless double-beta decay experiment being undertaken by a large international collaboration, has the goal of measuring the neutrinoless double-beta decay rate by observing monochromatic events at 2039 keV in 500 kg of isotopically enriched ⁷⁶Ge gamma-ray spectrometers. In order to achieve the desired sensitivity limit, the background in the 2037-2041 keV region must be reduced to <1 event per year in the entire germanium array. The effects of various background reduction techniques, and the combination thereof, to produce a huge ⁷⁶Ge spectrometer array with virtually zero background are discussed.     

A new signal processing method to observe weak P and O NMR peaks

In NMR spectroscopy, situations may arise where sample concentrations are below the threshold for FT NMR detection, or sample lability constrains allowable acquisition times. In ³¹P NMR, for example, observation of ¹³C satellites may not be practical under given conditions. For ¹⁷O NMR, which is useful to characterize ¹⁷O-labeled phosphate derivatives, similar considerations may apply, and added factors are the cost of isotopically enriched samples and the requirement to obtain spectra at relatively high temperatures if narrow spectral peak line widths are desired. We report here application of a new signal processing method [S.D. Kunikeev, H.S. Taylor, J. Phys. Chem. A 108, 2004 743] to observation of weak ³¹P and ¹⁷O NMR peaks.     

Differentiation and characterization of isotopically modified silver nanoparticles in aqueous media using asymmetric-flow field flow fractionation coupled to optical detection and mass spectrometry

The principal objective of this work was to develop and demonstrate a new methodology for silver nanoparticle (AgNP) detection and characterization based on asymmetric-flow field flow fractionation (A4F) coupled on-line to multiple detectors and using stable isotopes of Ag. This analytical approach opens the door to address many relevant scientific challenges concerning the transport and fate of nanomaterials in natural systems. We show that A4F must be optimized in order to effectively fractionate AgNPs and larger colloidal Ag particles. With the optimized method one can accurately determine the size, stability and optical properties of AgNPs and their agglomerates under variable conditions. In this investigation, we couple A4F to optical absorbance (UV–vis spectrometer) and scattering detectors (static and dynamic) and to an inductively coupled plasma mass spectrometer. With this combination of detection modes it is possible to determine the mass isotopic signature of AgNPs as a function of their size and optical properties, providing specificity necessary for tracing and differentiating labeled AgNPs from their naturally occurring or anthropogenic analogs. The methodology was then applied to standard estuarine sediment by doping the suspension with a known quantity of isotopically enriched ¹⁰⁹AgNPs stabilized by natural organic matter (standard humic and fulvic acids). The mass signature of the isotopically enriched AgNPs was recorded as a function of the measured particle size. We observed that AgNPs interact with different particulate components of the sediment, and also self-associate to form agglomerates in this model estuarine system. This work should have substantial ramifications for research concerning the environmental and biological fate of AgNPs.     

Synthesis and characterization of isotopically enriched methylmercury (CH3201Hg+)

A simple procedure for the synthesis of an important standard, isotopically enriched methylmercury, which is not commercially available, has been established successfully. The isotopically enriched standard synthesized is utilized in conventional isotope dilution mass spectrometry (IDMS), as well as in speciated IDMS (SIDMS), for determination of the true concentration of methylmercury in environmental samples. The CH₃²⁰¹Hg⁺ standard has been synthesized from commercially available ²⁰¹HgO and tetramethyltin. The synthesis time required is 1 h at 60°C. The product is highly pure, yielding more than 90% as ²⁰¹Hg in CH₃²⁰¹Hg⁺. Hazardous dimethylmercury does not occur during this synthesis procedure. The product synthesized was analyzed using high‐performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (ICP‐MS) and ICP‐MS alone in order to determine its concentration, isotopic composition and purity. The stability of the product was also evaluated for over 6 months and found to be stable at 4°C in the dark. The isotopically enriched methylmercury synthesized can be used in SIDMS and IDMS analyses as a standard. Copyright © 2003 John Wiley & Sons, Ltd.     

Use of electrodeposition for sample preparation and rejection rate prediction for assay of electroformed ultra high purity copper for 232Th and 238U prior to inductively coupled plasma mass spectrometry (ICP/MS)

The search for neutrinoless double beta decay in ⁷⁶Ge has driven the need for ultra-low background Ge detectors shielded by electroformed copper of ultra-high radiopurity (<0.1 μBq/kg). Although electrodeposition processes are almost sophisticated enough to produce copper of this purity, to date there are no methods sensitive enough to assay it. Inductively coupled plasma mass spectrometry (ICP/MS) can detect thorium and uranium at femtogram levels, however, this assay is hindered by high copper concentrations in the sample. Electrodeposition of copper samples removes copper from the solution while selectively concentrating thorium and uranium contaminants to be assayed by ICP/MS. Spiking ²³²Th and ²³⁸U into the plating bath simulates low purity copper and allows for the calculation of the electrochemical rejection rate of thorium and uranium in the electroplating system. This rejection value will help to model plating bath chemistry.     

Positional Enrichment by Proton Analysis (PEPA): A One‐Dimensional 1H‐NMR Approach for 13C Stable Isotope Tracer Studies in Metabolomics

A novel metabolomics approach for NMR‐based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of ¹³C‐satellite peaks using 1D‐¹H‐NMR spectra. In comparison with ¹³C‐NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of ¹³C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high‐throughput of ¹H‐NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D‐NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts.     

Determination of counting losses and pile-up rejection in ionizing radiation spectrometry

The spectrometric system for ionizing radiation measurement with pile-up rejection and counting losses correction has been described. The results for HpGe, Ge(Li), Si(Li) and surface barrier detectors have been presented. The total count rate ranged from 500 to 10⁵ cps and different radioisotopes have been used. The counting losses correction accuracy has been within ±1% with tenfold reduction of background from pile-up pulses. The possibility of the system application for radiation intensity measurement of the mixture of short- and longlived radioisotopes has been discussed.     

Instrumental activation analysis for determining the composition of micro-ingots of multi-constituent alloys

A procedure for the instrumental neutron activation analysis of micro-ingots of alloys containing In, Sb, Au, Ga, Ni, Sn and Bi is proposed. The non-destructive analysis of the irradiated samples is performed by γ-spectrometry techniques including one-crystal scintillation detectors, dual-crystal sum-coincidence scintillation detectors and Ge(Li) semiconductor detectors. As a result, the cumbersome operations of radiochemical separation can be eliminated. The sensitivity of quantitative determinations using scintillation detectors in alloys of the above composition is 10⁻¹⁰ g for indium, gold, antimony and gallium and 10⁻⁶ g for nickel and tin. The use of semiconductor detectors yields sensitivities of 10⁻¹⁰ g for indium and gold and 10⁻⁹ g for gallium and antimony.     

Cyclotron isotopes and radiopharmaceuticals XXVI. A carrier-free separation of77Br from se

A silver chloride co-precipitation and ion exchange separation method is described for the carrier-free isolation of⁷⁷Br bromide from isotopically enriched⁷⁷Se targets following dissolution of the irradiated⁷⁷Se in nitric acid. A cation exchange procedure has been devised to remove the silver and yield a dilute hydrochloric acid solution containing ≈90% of the precipitated⁷⁷Br as bromide. The radiochemical and chemical composition of several preparations have been analyzed. A method for the quantitative recovery of the isotopically enriched selenium is described. Research carried out under contract with the U.S. Department of Energy and supported by its Division of Basic Energy Sciences. Supported in part by the Massachusetts Heart Association and by NIH Grant No. HL 18487-01. All inquiries should be directed to R. M. Lambrecht. For earlier papers in this series see Ref.¹²     

High yield synthesis and characterization of isotopically enriched monoethylmercury chloride (C2H5201HgCl)

An important but commercially unavailable compound isotopically enriched monoethylmercury chloride (C₂H₅²⁰¹HgCl), has been synthesized from commercially available ²⁰¹HgO (98.11% enriched isotopic purity) and tetraethyltin. The required synthesis time is 1 h at 90 °C, and the product is the single product of monoethylmercury chloride, yielding more than 95% as ²⁰¹Hg in C₂H₅²⁰¹Hg⁺ (98.19 ± 0.22% enriched isotopic purity). The synthesized product was analyzed with high‐performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC‐ICP‐MS) to determine its concentration, isotopic composition and purity. The synthetic isotopically enriched monoethylmercury synthesized can be used in speciated isotope dilution mass spectrometry (SIDMS) and isotope dilution mass spectrometry (IDMS) analyses as a standard. Copyright © 2005 John Wiley & Sons, Ltd.     

A dual purpose Compton suppression spectrometer

A gamma-ray spectrometer with a passive and an active shield is described. It consists of a HPGe coaxial detector of 42% efficiency and 4 NaI(Tl) detectors. The energy output pulses of the Ge detector are delivered into the 3 spectrometry chains giving the normal, anti- and coincidence spectra. From the spectra of a number of ¹³⁷Cs and ⁶⁰Co sources a Compton suppression factor, SF and a Compton reduction factor, RF, as the parameters characterizing the system performance, were calculated as a function of energy and source activity and compared with those given in literature. The natural background is reduced about 8 times in the anticoincidence mode of operation, compared to the normal spectrum which results in decreasing the detection limits for non-coincident gamma-rays up to a factor of 3. In the presence of other gamma-ray activities, in the range from 5 to 11 kBq, non- and coincident, the detection limits can be decreased for some nuclides by a factor of 3 to 5.7.     

Working methods paper: Micro‐scale preparation and characterization of isotopically enriched monomethylmercury

A synthesis method for the micro‐scale laboratory preparation of isotopically enriched monomethylmercury (MMHg) has been successfully established. This compound is an important standard for species‐specific isotope dilution analysis. The isotopically enriched MMHg has been synthesized from commercially available mercury oxide (²⁰¹HgO) using methylcobalamin co‐enzyme as methylating agent. The time required is less than 2 h and the final yield is about 90%. The proposed method is faster than those previously reported in the literature. It allows work on a micro scale to control the use of expensive enriched isotope standard. It also allows control of unintentional formation of dimethylmercury. The enriched mercury‐containing reaction products were analyzed by capillary gas chromatography coupled to an inductively coupled plasma mass spectrometer after derivatization with sodium tetraethylborate. The isotopic composition, concentration, purity and stability of the synthesized, enriched MMHg have been investigated in order to establish standard protocols for MMHg isotope dilution analysis or isotope labeling incubation experiments. Copyright © 2002 John Wiley & Sons, Ltd.     

A comparative study of some nuclear methods for235U/238U isotopic ratios determination

In the present work, a comparative study is made among nuclear methods for²³⁵U/²³⁸U ratios determination: activation analysis followed by high-resolution gamma-ray spectrometry, delayed neutron counting, passive gamma-ray and alpha spectrometry. Activation analysis followed by high-resolution gamma-ray spectrometry yielded a relative standard deviation down to 0.1% and a relative error of about 1% for standards of uranium enriched to 14%. Passive gamma-ray spectrometry using Ge(Li) detectors yielded a relative error down to 0.1% for enriched uranium and values even lower for the standard deviation. Passive gamma-ray spectrometry using Low Energy Photon Detector (LEPD) yielded a precision of 0.2% and a still better accuracy for enriched standards. In the case of alpha spectrometry, a relative error down to 0.5% and a precision of about 1% were obtained, also for enriched uranium standards. Delayed neutron counting allowed a relative standard deviation of about 7% and a relative error of about 2%, for standards of depleted uranium.     

Sub-microgram per gram concentrations of mercury in orchard leaves determined by isotope dilution and spark-source mass spectrometry

A stable isotope dilution procedure in conjunction with the spark source mass spectrograph was developed for determining sub-μg g^-1 concentrations of mercury in orchard leaves. A 5-g sample was spiked with a solution of mercury, isotopically enriched in ²⁰¹Hg and ¹⁹⁸Hg. The ¹⁹⁸Hg served as a carrier. After wet-ashing the sample with nitric and perchloric acids under reflux and distilling most of the acid, the isotopically equilibrated mercury was electrodeposited onto high-purity gold wires for sparking in the mass spectrograph. The concentration was calculated from the altered isotope ratio, ²⁰¹Hg/²⁰²Hg, and other data. The results were compared with those obtained by atomic absorption spectrometry and neutron activation, leading to a certified value of 0.155 ± 0.015 μg g^-1 for the mercury content of Orchard Leaves, SRM 1571 of the National Bureau of Standards.     

Production of18F with an18O enriched water target

A target system for the production of nucleophilic 110-min¹⁸F from isotopically enriched /¹⁸O/H₂O is described. The process occurs via the nuclear reaction¹⁸O/p,n/¹⁸F, the available proton beam of 72 MeV must be degraded to the entrance energy of 15 MeV. This process is in regular use for the batch production of 0.8–1 Ci¹⁸F.     

Monte Carlo simulation of background characteristics of low-level gamma-spectrometers

Large volume Ge detectors require efficient methods of background reduction if radionuclide analyses at very low-levels are planned. It is advisable therefore to carry out simulations of background characteristics of Ge detectors in advance of installations of low-level Ge-spectrometers either in surface or underground laboratories. We present results of Monte Carlo simulations of background characteristics of Ge detectors in surface laboratories with various lead shielding without and with anticosmic shielding, as well as in underground laboratories operating at different depths.     

Gas-Chromatographic Determination of C<Subscript>1</Subscript>-C<Subscript>4</Subscript> Hydrocarbon Trace Impurities in Silicon Tetrafluoride

A procedure was developed for the gas-chromatographic determination of hydrocarbons in silicon tetrafluoride of natural and isotopically enriched compositions. For improving the efficiency of the chromatographic determination of impurities, it was proposed that the major compound be removed from the test sample with the subsequent cryofocusing of impurity hydrocarbons. The detection limits of C₁-C₄ hydrocarbons were 2 × 10^?6?6 × 10^?6 vol %.     

Practical considerations regarding high resolution gamma-spectrometry measurements of naturally occurring radioactive samples

High-resolution gamma-spectrometry provides fast, accurate, non-destructive isotopic analysis of natural radionuclides in environmental samples. Low energy HPGe detectors (30%) with resolution less than 2.0 keV at 1332 keV of ⁶⁰Co and with linked analytical software, provide good peakto-background performance and accurate unfolding of multiplet regions. A procedure regarding high-resolution gamma-spectrometry measurements of naturally occurring radioactive samples is presented here including calibration, background interference, self-absorption, practical considerations and validation with respect to IAEA reference materials. Recommended peaks for quantitative measurements, deriving from the analysis of observed spectral interferences as well as from radioactive equilibrium considerations, are reported.     

Autoionisation resonances in the photoabsorption spectra of Ge I and Sn I

We report new measurements in the photoabsorption spectra of Ge I and Sn I in the vacuum ultraviolet region. The spectra were recorded in the first order of a 1-metre vacuum spectrograph using synchrotron radiation as the background source of continuum. Autoionisation resonances above the first ionisation were observed which are identified as the 4s 4p ^{3 1} P ₁ and 5s5p ^{3 1} P ₁ levels in Ge I and Sn I respectively. Resonances due to excitation to these levels from thermally populatedms ² mp ^{2 3} P _{0, 1, 2} levels in the ground states have also been observed. Single configuration Hartree-Fock calculations are reported for the 4s4p ³ and 5s5p ³ configurations for Ge I and Sn I. Fano parameterisation was used to determine the Resonance wavelengths, the line widths and the asymmetry or line shape parameters.     

Zintl Clusters as Wet‐Chemical Precursors for Germanium Nanomorphologies with Tunable Composition

[Ge₉]^4? Zintl clusters are used as soluble germanium source for a bottom–up fabrication of Ge nanomorphologies such as inverse opal structures with tunable composition. The method is based on the assembly and oxidation of [Ge₉]^4? clusters in a template mold using SiCl₄, GeCl₄, and PCl₃ leading to Si and P‐containing Ge phases as shown by X‐ray diffraction, Raman spectroscopy, and energy‐dispersive X‐ray analysis. [Ge₉]^4? clusters are retained using ethylenediamine (en) as a transfer medium to a mold after removal of the solvent if water is thoroughly excluded, but are oxidized to amorphous Ge in presence of water traces. ¹H NMR spectroscopy reveals the oxidative deprotonation of en by [Ge₉]^4?. Subsequent annealing leads to crystalline Ge. As an example for wet‐chemical synthesis of complex Ge nanomorphologies, we describe the fabrication of undoped and P‐doped inverse opal‐structured Ge films with a rather low oxygen contents. The morphology of the films with regular volume porosity is characterized by SEM, TEM, and grazing incidence small‐angle X‐ray scattering.