László Rinyu

Performance test of a new graphite target production facility in ATOMKI

We present our new graphite target production system, developed in the Institute of Nuclear Research of the Hungarian Academy of Sciences (ATOMKI), for accelerator mass spectrometry (AMS) radiocarbon dating measurements. The system consists of a gas handling line and a graphite target production system. Results of AMS measurements, stable isotope mass spectrometry measurements, and gravimetric/pressure yield determinations have been used to find the proper conditions for the graphitization process. We have also investigated the C-14 contamination and the memory effect of the system during the graphitization processes. This paper covers the details of these experiments and a discussion of the results.

Dating of total soil organic matter used in kurgan studies

We investigated Csipo-halom, one of the kurgans that served as a burial place in the Hortobagy area of the Hungarian Great Plain. For pedological description and other studies of the protected mound and its surroundings, only a few monitoring drillings were permitted to get soil samples. On the basis of morphological and visual studies, the structure and layers of the mound were reconstructed. The Laboratory of Environmental Studies of the Institute of Nuclear Research at the Hungarian Academy of Sciences (INR/HAS) performed radiocarbon measurements of soil samples, applying a bulk combustion pretreatment method. The measured (super 14) C ages of soil samples from reference points, such as the top layer of the mound, the center of mound body, the base layer of the mound, the near surroundings, and the distant surroundings, are in good agreement with the preliminary archaeological concept for this field and give substantial information about the rate of soil generation processes in this area.

A mass spectrometric line for tritium analysis of water and noble gas measurements from different water amounts in the range of microlitres and millilitres

This paper describes the procedure followed for noble gas measurements for litres, millilitres and microlitres of water samples in our laboratory, including sample preparation, mass spectrometric measurement procedure, and the complete calibrations. The preparation line extracts dissolved gases from water samples of volumes of 0.2 μ l to 3 l and it separates them as noble and other chemically active gases. Our compact system handles the following measurements: (i) determination of tritium concentration of environmental water samples by the 3He ingrowth method; (ii) noble gas measurements from surface water and groundwater; and (iii) noble gas measurements from fluid inclusions of solid geological archives (e.g. speleothems). As a result, the tritium measurements have a detection limit of 0.012 TU, and the expectation value (between 1 and 20 TU) is within 0.2 % of the real concentrations with a standard deviation of 2.4 %. The reproducibility of noble gas measurements for water samples of 20–40 ml allows us to determine solubility temperatures by an uncertainty better than 0.5 °C. Moreover, noble gas measurements for tiny water amounts (in the microlitre range) show that the results of the performed calibration measurements for most noble gas isotopes occur with a deviation of less than 2 %. Theoretically, these precisions for noble gas concentrations obtained from measurements of waters samples of a few microlitres allow us to determine noble gas temperatures by an uncertainty of less than 1 °C. Here, we present the first noble gas measurements of tiny amounts of artificial water samples prepared under laboratory conditions.

Flame-Sealed Tube Graphitization Using Zinc as the Sole Reduction Agent: Precision Improvement of EnvironMICADAS 14 C Measurements on Graphite Targets

The flame-sealed tube zinc reduction graphitization method has been successfully adapted and optimized for radiocarbon measurements on EnvironMICADAS in the Institute for Nuclear Research of the Hungarian Academy of Sciences, Hertelendi Laboratory of Environmental Studies (ATOMKI HLES). To reduce the cost and treatment time of producing graphite targets from samples of about 1 mg carbon content, we have omitted the titanium hydride (TiH 2 ) reagent and used a decreased amount of zinc as the sole reductant in our new method. These changes have also helped to eliminate methane formation during the graphitization processes as well as to recover higher ion current at the same background level. These conditions have led to improved efficiency in the 14 C measurements; furthermore, the instrument background level remained sufficiently low (<49,000 yr BP). After determining the optimum parameters of the new Zn graphitization method (2.5 mg Fe powder, 15.0 mg Zn powder, 10 hr graphitization at 550°C in heating block, reaction cells with reagent pretreated at 300°C for 1 hr), verification of the accuracy was carried out by the preparation and measurement of IAEA standard samples (C2, C6, C7, C8) with known 14 C activity. The sensitivity of the method for gas contamination was tested and determined by comparing the results to measurements of reserved portions of previously processed real samples. DOI: 10.2458/azu_rc.57.18193

Combined techniques to date the first Turkish bridge over the Tisza river, Hungary

Given the fluctuating nature of the radiocarbon calibration curve, the precision of single 14C dates on the calendar timescale is limited. However, 14C dating combined with dendrochronology enabled us to date timbers found in the Tisza River, Hungary, during the dry period of summer 2003. Routine preparation of wood samples gave 14C results spread over 4 centuries. By extracting alpha-cellulose from the samples, 2 distinct and relatively narrow historical time periods were obtained: the first period (AD 15051595 and 16121673, respectively) coincided with the Turkish occupation period, while the second interval (17331813) obtained in the case of 2 samples did not exclude the existence of another bridge constructed later. The dendrochronological data confirmed that the bridge was constructed from oak timbers felled between 1558 and 1565. The 14C and dendrochronological dates correspond with the date of a letter written in 1562 by Antal Verancsics, Bishop of Eger, mentioning the construction of the first bridge. In conclusion, the archaeological excavation revealed proof of the first historically attested wooden bridge over the Tisza River.

Real-Time Sensing of Hydrogen Peroxide by ITO/MWCNT/Horseradish Peroxidase Enzyme Electrode

The accurate and sensitive determination of H2O2 is very important in many cases because it is a product of reactions catalysed by several oxidase enzymes in living cells and it is essential in environmental and pharmaceutical analyses. The fabrication of enzyme protein activity based biosensors is a very promising way for this purpose because the function of biological molecules is very specific, sensitive, and selective. Horseradish peroxidase HRP is the most commonly used enzyme for H2O2 detection because it can oxidize hydrogen atoms and, for example, xenobiotics in the presence of H2O2. In order to define the limit of detection LOD of H2O2 we made calibrations with guaiacol and amplex red AR, which are hydrogen donors of HRP. The accumulation of the reaction products, tetraguaiacol, and resorufin, respectively, then can be easily detected by absorption or emission fluorescence spectroscopy. In our experiments an enzyme electrode was fabricated from ITO indium tin oxide, functionalized multiwalled carbon nanotubes f-MWCNTs, and HRP. Although the enzyme activity was smaller by about two orders of magnitude when the enzyme was bound to the f-MWCNTs ca. 10−2 M H2O2/M HRP·sec compared to ca. 2 M H2O2/M HRP·sec and 5 M H2O2/M HRP·sec with AR and guaiacol in buffer solution, LOD of the H2O2 decomposition was about 6 pM H2O2/sec and 10 pM H2O2/sec in the case of AR and guaiacol, respectively.

Modulation of Cosmogenic Tritium in Meteoric Precipitation by the 11-year Cycle of Solar Magnetic Field Activity

The relationship between the atmospheric concentration of cosmogenic isotopes, the change of solar activity and hence secondary neutron flux has already been proven. The temporal atmospheric variation of the most studied cosmogenic isotopes shows a significant anti-correlation with solar cycles. However, since artificial tritium input to the atmosphere due to nuclear-weapon tests masked the expected variations of tritium production rate by three orders of magnitude, the natural variation of tritium in meteoric precipitation has not previously been detected. For the first time, we provide clear evidence of the positive correlation between the tritium concentration of meteoric precipitation and neutron flux modulated by solar magnetic activity. We found trends in tritium time series for numerous locations worldwide which are similar to the variation of secondary neutron flux and sun spot numbers. This variability appears to have similar periodicities to that of solar cycle. Frequency analysis, cross correlation analysis, continuous and cross wavelet analysis provide mathematical evidence that the correlation between solar cycle and meteoric tritium does exist. Our results demonstrate that the response of tritium variation in precipitation to the solar cycle can be used to help us understand its role in the water cycle.

Development of an Automatic Sampling Unit for Measuring Radiocarbon Content of Groundwater

An automatic water sampling unit was developed to monitor the radioactive emission (radiocarbon and other corrosion and fission products) from nuclear facilities into the groundwater. Automatic sampling is based on the principal of ion exchange using built-in resin columns in the submerging samplers. In this way, even the short-term emissions can be detected. According to our experiments, the 14C activity concentrations and the δ13C values of the samples made by the ion exchange method are systematically underestimated compared to the real values. The carbonate adsorption feature of the sampling unit was studied under laboratory and field conditions. For this purpose, a test method was developed. The observed sampling efficiencies and additionally some carbon contamination for the sampling method itself have to be taken into consideration when we estimate the amount of 14C contamination introduced into the groundwater from a nuclear facility. Therefore, a correction factor should be made for the 14C anion exchange sampling. With the help of this correction, the results converge to the expected value.

A hydrochemical and isotopic case study around a near surface radioactive waste disposal

As part of the site characterisation program for the near surface radioactive waste treatment and disposal facility (RWTDF) at Püspökszilágy, Hungary, water quality and environmental isotope investigations have been carried out. Water samples for major ion chemistry, tritium, 14C and stable isotope ratio measurements (δ18O, δD, δ34S, δ13C) were taken quarterly from the observation wells, the streams and the precipitation during the period 1999–2001. The chemical composition of groundwaters presented a continuous transition from waters situated on one side to waters on the top and on the other slope of the disposal suggesting the mixing of the three hydrochemical “endmembers”. Most of δD and δ 18O data were situated between GMWL and LMWL (δD = 7.2 × δ 18O − 1‰) with Oligocene aquifer presenting recharge of Pleistocene origin and water on the top and the gentle slope of the hill presenting recharge of Holocene origin. δ 34S values of dissolved sulphates varied in a wide range (-14.2‰ to + 5.4‰). The tritium in precipitation varied between 4.4 and 18.1 TU with an annual weighted average of 10 ± 0.3 TU. The streams showed larger fluctuations than the wells, but the changes of δ 18O, δD and T were small compared to those in precipitation (showing seasonal variation). Stable isotope, tritium and radiocarbon data proved that the replenishment of groundwater is slow on the steeper side and the direction of water movement is toward the gentle slope of the hill. It was judged that this path is the one that is most likely to give rise to high doses and, therefore, was used in the hydrological modelling of the safety assessment that followed the present work. The possibility that there may also be transport through the unsaturated zone and systems of perched water tables in layers 1 and 2 to both the Szilágyi and Némedi streams cannot be excluded; the transport along these pathways is likely to be intermittent.