Development and validation of Ni–Ni electrolytic enrichment method for tritium determination in samples of underground waters of Jeju Island

A method of tritium electrolytic enrichment was developed, optimized and validated. The enrichment parameters were compared with different current and total current charge variation and tritium separation factor was from 8 to 36 with a current density variation. The detection limit of tritium measurement is about 0.5 TU using 1,000 mL sample and 600 min counting time. Several samples of groundwaters were processed in our and another laboratory with good agreement of results within 15% deviation. Developed and validated method of tritium determination was applied groundwaters in Jeju Island with a liquid scintillation counter (LSC) and electrolytic enrichment method using Ni–Ni electrodes. The tritium concentrations in fifty eight groundwaters in Jeju Island were ranged <0.5 TU-3.9 TU and averaged value was 2.12 TU.     

Determination of tritium in natural waters

A study of the tritium content of precipitation and of river water samples, collected during a seasonal maximum of tritium concentration in 1976 is given. The measurements were made for precipitation in Belgrade from April to December 1976, and for river water from the Sava (in Belgrade), the Tisa at 137 km, and the Danube at 1425 km, 1174 km, 861 km from the confluence. The maximum monthly value of the tritium content of precipitation is 135 TU, and the Danube at 1425 km has a maximum of 196 TU (627 pCi/l). In general, there is no correlation between the amount of precipitation and river water with tritium content.     

Tritium activity levels in drinking water of Adana,Turkey

Tritium activity in potable drinking water samples from Adana city were measured using liquid scintillation counting after distillation procedure. The results exposed that the activity concentrations of the tritium measured in one-third of these samples were lower than minimum detectable activity which has a value of 2 Bq/L for counting time of 1,500 min. However, the maximum and mean value of the tritium activity was found to be 9.1 Bq/L (77.3 TU) and 7.0 Bq/l (59.4 TU), respectively. These values were substantially below the 100 Bq/L which is normative limit in Turkey for waters intended for human consumption. The highest values of annual effective dose received by infants, children and adults due to measured tritium activity were estimated as 0.041, 0.057 and 0.120 μSv/y, respectively.     

Tritium activity concentration along the Western shore of the Black Sea

The Black Sea tritium level was investigated in 33 places southward the Danube Delta covering about 360 km of the Black Sea Western Shore. Both surface (10 cm depth) and bottom (up to 20 m depth) water samples were collected. In the close vicinity of Danube Delta, the tritium activity concentration in the surface water was around 28 TU, which is almost the same as that of the Danube River waters, but it decreased to about 5 TU in the bottom water. This discrepancy slowly diminished wherein at about 120 km southward, the tritium content in both surface and bottom water reached almost the same constant value of 6.5 ± 2.3 TU. This value, about two and a half times smaller than that reported 17 years ago, remained almost unchanged for the last 240 km of shore up to the Turkish border.     

Determination of Hg isotopic compositions in certified reference material NIES No. 13 Human Hair by cold vapor generation multi-collector inductively coupled plasma mass spectrometry

Hg isotopic ratios of NIES CRM No. 13 Human Hair were analyzed using cold vapor generation coupled to multi-collector inductively coupled plasma mass spectrometer to meet the growing demand for better understanding of Hg exposure routes by using Hg isotopic compositions in human hair samples. To validate and assure the accuracy of our analytical method, (1) the reproducibility of the Hg isotopic measurement was monitored and (2) the Hg isotopic compositions of four secondary reference materials—IAEA-085, IAEA-086, and CRPG-RL24H—were measured. Our results for NIES CRM No. 13 show the mass-dependent fractionation values of δ ¹⁹⁹Hg = (2.13 ± 0.07) ‰, δ ²⁰⁰Hg = (0.98 ± 0.08) ‰, δ ²⁰¹Hg = (2.77 ± 0.10) ‰, δ ²⁰²Hg = (1.89 ± 0.10) ‰, and δ ²⁰⁴Hg = (2.76 ± 0.16) ‰ (2SD, n = 11) and the mass-independent fractionation values of Δ ¹⁹⁹Hg = (1.65 ± 0.06) ‰, Δ ²⁰⁰Hg = (0.04 ± 0.04) ‰, Δ ²⁰¹Hg = (1.36 ± 0.07) ‰, and Δ ²⁰⁴Hg = (?0.04 ± 0.11) ‰ (2SD, n = 11). Interlaboratory comparison of the CRM performed at the University of Pau showed good agreement with the values obtained at NIES.     

Corrosion inhibition and adsorption behavior of imidazoline salt on N80 carbon steel in CO2-saturated solutions and its synergism with thiourea

The inhibition and adsorption behavior of 2-undecyl-1-sodium ethanoate-imidazoline salt (2M2) and thiourea (TU) on N80 mild steel in CO₂-saturated 3 wt.% NaCl solutions was studied at 25?°C, pH 4, and 1 bar CO₂ partial pressure using electrochemical methods. It was found that inhibition efficiency (η%) increased with increase in 2M2 concentration but decreased with increase in TU concentration with optimum η% value at 20 mg l^?1 TU. The data suggest that the compounds functioned via a mixed-inhibitor mechanism. The inhibition process is attributed to the formation of an adsorbed film of 2M2 and TU via the inhibitors polycentric adsorption sites on the metal surface which protects the metal against corrosion. A synergistic effect was observed between TU and 2M2. Potential of unpolarizability, E _u, was observed in the presence of 100 mg l^?1 TU which was shifted positively in the presence of 2M2–100 mg l^–1 TU blends, which suggests that the presence of 2M2 stabilized the adsorption of TU molecules on the surface of the metal. The adsorption characteristics of 2M2 were approximated by Langmuir adsorption isotherm.     

Changes in 13C/12C of oil palm leaves to understand carbon use during their passage from heterotrophy to autotrophy

The carbon isotope composition of leaf bulk organic matter was determined on the tropical tree Elaeis guineensis Jacq. (oil palm) in North Sumatra (Indonesia) to get a better understanding of the changes in carbon metabolism during the passage from heterotrophy to autotrophy of the leaves. Leaf soluble sugar (sucrose, glucose and fructose) contents, stomatal conductance and dark respiration, as well as leaf chlorophyll and nitrogen contents, were also investigated. Different growing stages were sampled from leaf rank ?6 to rank 57. The mean values for the δ¹³C of bulk organic matter were ?29.01 ± 0.9‰ for the leaflets during the autotrophic stage, ?27.87 ± 1.08‰ for the petioles and ?28.17 ± 1.09‰ for the rachises, which are in the range of expected values for a C₃ plant. The differences in δ¹³C among leaf ranks clearly revealed the changes in the origin of the carbon source used for leaf growth. Leaves were ¹³C‐enriched at ranks below zero (around ?27‰). During this period, the ‘spear’ leaves were completely heterotrophic and reserves from storage organs were mobilised for the growth of these young emerging leaves. ¹³C‐depletion was then observed when the leaf was expanding at rank 1, and there was a continuous decrease during the progressive passage from heterotrophy until reaching full autotrophy. Thereafter, the δ¹³C remained more or less constant at around ?29.5‰. Changes in sugar content and in δ¹³C related to leaf ranks showed an interesting similarity of the passage from heterotrophy to autotrophy of oil palm leaves to the budburst of some temperate trees or seed germination reported in the literature. Copyright © 2009 John Wiley & Sons, Ltd.     

An online method combining a Gasbench II with continuous flow isotope ratio mass spectrometry to determine the content and isotopic compositions of minor amounts of carbonate in silicate rocks

An online method using continuous flow isotope ratio mass spectrometry (CF‐IRMS) interfaced with a Gasbench II device was established to analyze carbon and oxygen isotopic compositions and to estimate the content of minor amounts of carbonate in silicate rocks. The mixtures of standard materials and high‐purity quartz are firstly used to calibrate different quantities of carbonate in silicates. The results suggest that the accuracy and precision of the online analysis are both better than those obtained using an offline method. There is a positive correlation between the carbonate weight and the Mass44 ion beam intensity (or peak area). When the weight of carbonate in the mixtures is greater than 70 µg (equal to ～1800 mV Mass44 ion beam intensity), the δ¹³C and δ¹⁸O values of samples usually have accuracy and precision of ±0.1‰ and ±0.2‰ (1σ), respectively. If the weight is less than 70 µg, some limitations (e.g., not perfectly linear) are encountered that significantly reduce the accuracy and precision. The measured δ¹⁸O values are systematically lower than the true values by ?0.3 to ?0.7‰; the lower the carbonate content, the lower the measured δ¹⁸O value. For samples with lower carbonate content, the required phosphoric acid doses are higher and more oxygen isotope exchanges with the water in the phosphoric acid. To guarantee accurate results with high precision, multiple analyses of in‐house standards and an artificial MERCK sample with δ¹³C values from ?35.58 to 1.61‰ and δ¹⁸O from 6.04 to 18.96‰ were analyzed simultaneously with the unknown sample. This enables correction of the measured raw data for the natural sample based on multiple‐point normalization. The results indicate that the method can be successfully applied to a range of natural rocks. Copyright © 2010 John Wiley & Sons, Ltd.     

Measurements of nitrogen isotope composition of plants and surface soils along the altitudinal transect of the eastern slope of Mount Gongga in southwest China

The natural abundances of stable nitrogen isotopes in plants and soils have been viewed as recorders that can be used to reconstruct paleoclimate and ecological processes or to indicate the biogeochemical cycle of nitrogen in nature. This study systematically measured the nitrogen isotope composition (δ¹⁵N) in plants and surface soils along an altitudinal transect of elevation range of 1200 to 4500 m on the eastern slope of Mount Gongga in southwest China. The influences of photosynthetic pathways on plant δ¹⁵N as well as the effects of temperature and precipitation on δ¹⁵N altitudinal trends in plants and surface soils are discussed. Across this altitude transect, the δ¹⁵N values of C₃ and C₄ plants on Mount Gongga range between ?9.87‰ and 7.58‰ with a mean value of ?1.33‰, and between ?3.98‰ and 4.38‰ with a mean value of ?0.25‰, respectively. There is an evident δ¹⁵N difference between C₃ plants and C₄ plants. If, however, you only compare C₄ plants with those C₃ plants growing at the same altitudinal range, no significant difference in δ¹⁵N exists between them, suggesting that photosynthetic pathway does not have an influence on the plant δ¹⁵N values. In addition, we found that C₃, C₄ plants and surface soil (0–5 cm depth) all trend significantly towards more negative δ¹⁵N with increasing elevation. Furthermore, this study shows that the mean annual temperature and the mean annual precipitation positively and negatively correlate with δ¹⁵N in C₃ and C₄ plants, respectively. This indicates that precipitation and temperature are the main controlling factors of the δ¹⁵N variation in plants with altitude. We propose that lower δ¹⁵N values of plants and soils at higher altitude should be attributed to lower mineralization and lower net nitrification rates induced by low temperature and abundant rainfall. Copyright © 2010 John Wiley & Sons, Ltd.     

Evaluation of measurement uncertainty in EA–IRMS: for determination of δ 13C value and C-4 plant sugar content in adulterated honey

In this study, the method for determining the stable carbon isotope ratio value was validated. Measurement uncertainty of stable carbon isotope ratio value of whole honey and its extracted protein derived from repeatability, reference gas, reference standards and calibration curve was calculated by applying the “bottom-up” approach according to Eurachem/CITAC guide. The expanded uncertainties for all results ranged from 0.14 to 0.19 ‰, with most of them between 0.15 and 0.16 ‰ (the coverage factor k = 2, the level of confidence p is approximately 95 %). The percentage contribution of each source to the relative combined uncertainty was calculated. The data indicated that calibration curves have more contribution to the relative combined uncertainty than repeatability and reference standards. On the other hand, the measurement uncertainty of C-4 sugar content in honey was estimated. Based on these results, 58 honey samples, such as acacia, chaste, Northeast China black bee, flowers and jujube honey, have been gathered to determine the C-4 plant sugar content adulteration in honey by elemental analyzer with an isotope ratio mass spectrometer. It can be found that all honey samples were not adulterated by C-4 plant sugar.     

Evaluation of groundwater tritium content and mixing behavior of Tatapani geothermal systems,Chhattisgarh, India

Isotopic investigations were carried out on hot springs, groundwater and surface water to evaluate the mixing processes within the geothermal system. Physico-chemical parameter (EC, pH, Temp.) and tritium content of groundwater, hot springs and surface water were measured. The temperature of the hot springs were varied from 60 to 98.8 °C and EC from 674 to 728 μS/cm. The tritium content of groundwater varies from 1.5 to 5 TU whereas, geothermal water have slightly less tritium and their values ranges from 1.4 to 4.4 TU. Low tritium, higher EC and high temperature of a few hot springs indicate insignificant mixing whereas high tritium, lower EC and low temperature indicates significant mixing of thermal and non-thermal water. The degree of mixing for geothermal springs is estimated. It is found that the groundwater components present in the diluted thermal waters are about 25–80%. It is also observed that mixing process is prominent along the fault and in the area where groundwater exploitation is more. Extensive pumping of groundwater causes an increase in the rate of mixing of thermal and non-thermal water. The tritium content of groundwater, surface water and hot springs are indicating, it is of modern recharge.     

Reconstructing bulk isotope ratios from compound‐specific isotope ratios

Carbon isotope analysis by bulk elemental analysis coupled with isotope ratio mass spectrometry has been the mainstay of δ¹³C analyses both at natural abundance and in tracer studies. More recently, compound‐specific isotope analysis (CSIA) has become established, whereby organic constituents are separated online by gas or liquid chromatography before oxidation and analysis of CO₂ for constituent δ¹³C. Theoretically, there should be concordance between bulk δ¹³C measurements and carbon‐weighted δ¹³C measurements of carbon‐containing constituents. To test the concordance between the bulk and CSIA, fish oil was chosen because the majority of carbon in fish oil is in the triacylglycerol form and ～95% of this carbon is amenable to CSIA in the form of fatty acids. Bulk isotope analysis was carried out on aliquots of oil extracted from 55 fish samples and δ¹³C values were obtained. Free fatty acids (FFAs) were produced from the oil samples by saponification and derivatised to fatty acid methyl esters (FAMEs) for CSIA by gas chromatography/combustion/isotope ratio mass spectrometry. A known amount of an internal standard (C15:0 FAME) was added to allow analyte quantitation. This internal standard was also isotopically calibrated in both its FFA (δ¹³C = ?34.30‰) and FAME (δ¹³C = ?34.94‰) form. This allowed reporting of FFA δ¹³C from measured FAME δ¹³C values. The bulk δ¹³C was reconstructed from CSIA data based on each FFA δ¹³C and the relative amount of CO₂ produced by each analyte. The measured bulk mean δ¹³C (SD) was ?23.75‰ (1.57‰) compared with the reconstructed bulk mean δ¹³C of ?23.76 (1.44‰) from CSIA and was not significantly different. Further analysis of the data by the Bland‐Altman method did not show particular bias in the data relative to the magnitude of the measurement. Good agreement between the methods was observed with the mean difference between methods (range) of 0.01‰ (?1.50 to 1.30). Copyright © 2010 John Wiley & Sons, Ltd.     

Stable carbon isotopes as an indicator for soil degradation in an alpine environment (Urseren Valley,Switzerland)

Analyses of soil organic carbon (SOC) content and stable carbon isotope signatures (δ¹³C) of soils were assessed for their suitability to detect early stage soil erosion. We investigated the soils in the alpine Urseren Valley (southern central Switzerland) which are highly impacted by soil erosion. Hill slope transects from uplands (cambisols) to adjacent wetlands (histosols and histic to mollic gleysols) differing in their intensity of visible soil erosion, and reference wetlands without erosion influence were sampled. Carbon isotopic signature and SOC content of soil depth profiles were determined. A close correlation of δ¹³C and carbon content (r > 0.80) is found for upland soils not affected by soil erosion, indicating that depth profiles of δ¹³C of these upland soils mainly reflect decomposition of SOC. Long‐term disturbance of an upland soil is indicated by decreasing correlation of δ¹³C and SOC (r ≤ 0.80) which goes in parallel with increasing (visible) damage at the site. Early stage soil erosion in hill slope transects from uplands to adjacent wetlands is documented as an intermediate δ¹³C value (?27.5‰) for affected wetland soil horizons (0–12 cm) between upland (aerobic metabolism, relatively heavier δ¹³C of ?26.6‰) and wetland isotopic signatures (anaerobic metabolism, relatively lighter δ¹³C of ?28.6‰). Carbon isotopic signature and SOC content are found to be sensitive indicators of short‐ and long‐term soil erosion processes. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of Vegetables by Stable Isotopic and Elemental Signatures

ABSTRACT

109 Romanian parsley, celery and parsnip root, cucumber, vegetable marrow, onion, and pepper samples were characterized by their stable isotope ratios and elemental concentrations in comparison to imported varieties. Organic and conventional agriculture practices were also compared as well as a differentiation between eggplant and peppers grown in greenhouses and those in the field. δ²H values were between ?70.8 and 5.6‰, while the δ¹⁸O values were between ?9.0 and 4.1‰. The δ¹⁵N values for white onions were from 2.8 to 11.1‰. For Romanian organic onions, the carbon isotopic values were lower (?29.2 to ?28.2‰) compared to conventional onions from other countries (?27.8‰ to ?23.8%). Linear discriminant analysis was used to characterize agricultural practices and the geographic origin of the vegetables.     

Natural tritium determination in groundwater on Mt. Etna (Sicily, Italy)

Tritium is a naturally occurring radionuclide, due to interactions of cosmic-rays with the upper layers of the atmosphere; but its presence in the environment is mainly due to residual fallout from nuclear weapons atmosphere tests, carried out from 1952 till 1980. Tritium reaches the Earth’s surface mainly in the form of precipitation, becoming part of the hydrological cycle, then the interest of tritium content analysis in drinking water is both for dosimetry and health-risk and for using tritium as a natural tracer in the groundwater circulation system. This paper presents results from a survey carried out in the Mt. Etna area (east and west flanks) and in the southern side of Nebrodi in Sicily (Italy), in order to determine tritium activity concentrations in water samples by using liquid scintillation counter. The investigated areas show quite low tritium concentrations, much below the Italian limit of 100 Bq L^?1 for drinking water and even comparable with the minimum detectable activity value. The effective dose due to tritium for public drinking water consumption was also evaluated.     

Stable Isotope Fingerprinting for Pharmaceutical Authentication

ABSTRACT

The ¹³C stable isotopic composition of 38 pharmaceutical products was investigated for six medicine analgesics classes ibuprofen, diclofenac, paracetamol, metamizole, ketoprofene, and combinations containing paracetamol to evaluate differences between manufacturers and production batches. Complementary measurements were performed by inductively coupled plasma-mass spectrometry. Linear discriminant analysis was applied on experimental obtained data set for differentiation of three investigated drug types. The carbon isotopic compositions were between ?32.9 and ?22.6‰. The lowest values of ¹³C (mean of ?31.3‰) were obtained for metamizole from all six categories of investigated analgesics. The highest δ¹³C values were obtained for diclofenac (mean of ?25.9‰). The most accurate elemental predictors were V, Al, Sb, As, Pb, and Mn.     

Measurement of 137Cs in the soil in Korea by low-level background gamma-ray spectrometer

¹³⁷Cs was measured in soil samples collected in Korea from 2006 to 2008 using a low-level background gamma-ray spectrometer that was designed and developed by KRISS (Korea Research Institute of Standards and Science). The objectives of this study are to evaluate the newly developed low-level background gamma-ray spectrometer and, consequently, to provide information on the horizontal and vertical distribution of ¹³⁷Cs in Korean soil. ¹³⁷Cs concentrations in surface soil varied from 12.8 ± 0.9 to 108 ± 4 Bq kg^?1, and the vertical profiles of ¹³⁷Cs from the Nari basin in Ulleung Island in the East Sea/Sea of Japan and Seongsan Ilchulbong Peak, Jeju Island, showed a higher concentration in the surface layer that gradually decreased with depth. On the other hand, the ¹³⁷Cs concentration in soil samples collected from Bukhan Mountain National Park in Seoul showed a subsurface maximum and decreased with depth. The ¹³⁷Cs inventories in the soil column were calculated to be 1,830–4,360 Bq m^?2 with a mean of 2,770 Bq m^?2, which was the same order of magnitude as the global fallout inventories in the mid-latitude region of the Northern Hemisphere.     

Determination of the stable carbon isotopic compositions of 2‐methyltetrols in ambient aerosols from the Changbai Mountains

Isoprene is one of the most important non‐methane hydrocarbons (NMHCs) in the troposphere: it is a significant precursor of O₃ and it affects the oxidative state of the atmosphere. The diastereoisomeric 2‐methyltetrols, 2‐methylthreitol and 2‐methylerythritol, are marker compounds of the photooxidation products of atmospheric isoprene. In order to obtain valuable information on the δ¹³C value of isoprene in the atmosphere, the stable carbon isotopic compositions of the 2‐methyltetrols in ambient aerosols were investigated. The 2‐methyltetrols were extracted from filter samples and derivatized with methylboronic acid, and the δ¹³C values of the methylboronate derivatives were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The δ¹³C values of the 2‐methyltetrols were then calculated through a simple mass balance equation between the 2‐methyltetrols, methylboronic acid and the methylboronates. The δ¹³C values of the 2‐methyltetrols in aerosol samples collected at the Changbai Mountain Nature Reserves in eastern China were found to be ?24.66 ± 0.90‰ and ?24.53 ± 1.08‰ for 2‐methylerythritol and 2‐methylthreitol, respectively. Based on the measured isotopic composition of the 2‐methyltetrols, the average δ¹³C value of atmospheric isoprene is inferred to be close to or slightly heavier than ?24.66‰ at the collection site during the sampling period. Copyright © 2010 John Wiley & Sons, Ltd.     

Tritium along the banks of the Danube and the Black Sea shore of Romania

Journal of Radioanalytical and Nuclear Chemistry - Determination of tritium along Danube River Banks, in shallow waters, from Bazia? to Sulina, led to an average value of 29 TU and to a slight...     

J-dependence of the isotope shift in Gd I 4f 7 5d 2 6s(a 11 F)

TheJ-dependence of the isotope shift in the terma ¹¹ F of 4f ⁷ 5d ² 6s between six stable Gd isotopes was found to be represented by these parameter values (in MHz):z _5d (160?158)=19.4(1.8),z _5d (160?157)=37.2(1.0),z _5d (160?156)=42.4(1.7),z _5d (160?155)=49.1(2.0),z _5d (160?154)=59.0(2.0). The normalization with the corresponding changes in the mean-square nuclear charge-radiiδ〈r ²〉 yields values which are almost constant, mean value:z _5d /δ〈r ²〉=134(14) MHZ/fm². This indicates a second order IS interaction of the magnetic and the field shift operator.