Heliuim-3 mass spectrometry for low-level tritium analysis of environmental samples

Helium-3 (³He) mass spectrometry for the analysis of low-level tritium (³H) concentrations (0.5 to 5 Bq·l^–1) in environmental sample matrices was compared with conventional low-level -decay counting methods. The mass-spectrometry method compared favorably, equalling or surpassing conventional decay-counting methods with respect to most criteria. Additional research and method refinements may make³He mass spectrometry the method of choice for routine, low-level to very-low-level (L<0.5 Bq·l^–1)³H measurements in a wide variety of environmental samples in the future.     

Removal of the impurities from environmental water samples for tritium measurement by liquid scintillation counting

Liquid scintillation counting is the most popular method for tritium measurement, however, it takes much time and a lot of doing to distill off the impurities before mixing the sample water and liquid scintillation cocktail. We have investigated the possibility of an alternative method to the distillation. We have found out that the filtration can be an alternative to distillation for the environmental water samples before electrolytic enrichment.     

Levels of tritium concentration in the environmental samples around JAERI TOKAI

By the operation of research reactors, tritium-handling facilities, nuclear power plants, and a reprocessing facility around JAERI TOKAI, tritium is released into the environment in compliance with the regulatory standards.To investigate the levels of tritium concentration in environmental samples around JAERI, rain, air (vapor and hydrogen gas), and tissue-free water of pine needles were measured and analyzed from 1984 to 1993. Sampling locations were determined by taking into consideration wind direction, distance from nuclear facilities, and population distribution. The NAKA site (about 6 km west-northwest from the TOKAI site) was also selected as a reference point.Rain and tissue-free water of pine needles were sampled monthly. For air samples, sampling was carried out for two weeks by using the continuous tritium sampler. After the pretreatment of samples, tritium concentrations were measured by a low background liquid scintillation counter (detection limit is 0.8 Bq/l).Annual mean tritium concentrations in rain observed at six points for 10 years was 0.8 to 8.9 Bq/l, which decreased with distance from the nuclear facilities. Tritium concentrations in rain obtained at Chiba City were around 0.8 Bq/l (1987–1988) and those at the NAKA site were 0.8 to 3.8 Bq/l.Annual mean HTO concentrations in air at three points for 10 years were 9.2×10^–2 to 1.1 Bq/m³, although HT concentrations in air, ranging from 1.7×10^–2 to 5.8×10^–2 Bq/m³, were not influenced by the operation of the nuclear facilities.Annual mean tritium concentrations in tissue-free water of pine needles at four points for 10 years were 1.4 to 31 Bq/l. Those at the NAKA site ranging from 1.4 to 6.2 Bq/l were in good agreement with the reported value by Takashima of 0.78 to 3.0 Bq/l at twenty-one locations in Japan.Monthly mean HTO concentrations in air for 10 years showed a good correlation with absolute humidity, while other samples showed no seasonal variation.Higher level tritium concentrations in rain, in air (vapor), and in tissue-free water of pine needles at the TOKAI site were caused by the tritium released from the nuclear facilities.The committed effective dose equivalent to the member of general public, estimated using the maximum tritium concentration in air (1.1 Bq/m³), was 0.23 Sv, which was about 1/4000 of dose limit for general public.     

Determination of low-level99Tc in environmental samples by high resolution ICP-MS

An analytical method has been developed for the determination of low-level⁹⁹Tc in environmental samples by High Resolution ICP-MS. The method consists of leaching of⁹⁹Tc by HNO₃ and separation by three different solvent extractions with 30% TOA-xylene, MEK, and cyclohexanone. Finally, purification of⁹⁹Tc was made by using an anion exchange resin column to reduce dissolved solids content. The final solution was adjusted to 1M HNO₃ for introducing into the HR-ICP-MS. The accuracy and precision of the method was confirmed to be satisfactory by applying this technique to the determination of⁹⁹Tc in IAEA marine algae sample (AG-B-1). Measurements of⁹⁹Tc using 0.5–2.5 g of sediment samples from the Irish Sea, UK, were successfully performed by the present method.     

A method for the determination of tritium distribution in environmental and biological samples

A method for the determination of the tritium distribution in environmental and biological samples is described. Tritium as HTO is removed by freeze-drying and the residue is combusted to obtain organically bound tritium. Each tritium fraction is electrolytically enriched and determined by liquid scintillation spectrometry. Enrichment and large sample sizes are required due to the low environmental tritium levels. During the analyses of more than 600 samples over a two-year period all aspects of the method (freeze-drying, combustion, enrichment and counting) have provided reproducible and precise results.     

Application of a low-level anti-coincidence gamma-spectrometer for environmental radioactivity measurement

Sensitive environmental radioactivity measurement using direct γ-spectroscopy needs to be carried out under particular low-level conditions as the quantity to be determined generally is very close to the natural background. Passive shielding of the detectors in addition to electronic suppression of Compton background resulting from scattering of high energy γ-rays in the gemanium detector seems to be the most promising approach to obtain statistically well defined peaks within reasonable measurement time. Results obtained with a heavily shielded anti-coincidence spectrometer installed at the Research Center Jülich, ideally suited for the measurement of low-level environmental radioactivity in various materials are described.     

A comparison of three analytical techniques for the measurement of steroidal estrogens in environmental water samples

Research into the analysis and monitoring of steroidal estrogens has grown significantly over the last decade, resulting in the emergence of a range of applicable techniques. In this study, three popular techniques, gas chromatography-mass spectrometry (GC-MS), gas chromatography-tandem mass spectrometry (GC-MS-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS) for the analysis of three highly potent steroidal estrogens in the aquatic environment have been compared. It has been observed that overall, the three techniques appear comparable in generating similar estrogen concentrations for river and effluent samples. Of the three techniques, the GC-MS technique is the simplest to operate, but fails to detect the estrogens at the lower-end of environmentally relevant concentrations. The tandem MS techniques are more selective than MS, and therefore able to detect lower concentration levels of the three steroidal estrogens of interest. However, the LC-MS-MS technique is more susceptible to matrix interferences for the analysis of samples, resulting in a reduction of the signal-to-noise ratio and a subsequent reduction in reliability and stability compared to GC-MS-MS. With the GC-MS-MS technique offering increased selectivity, the lowest limits of detection, and no false positive identification, it is recommended to be the preferred analytical technique for routine analysis of estrogens in environmental water samples.     

Analysis of emerging organic contaminants in environmental solid samples

Spreading sewage sludge on agricultural lands has been actively promoted by national authorities as an economic way of recycling. However, as by-product of wastewater treatment, sewage sludge may contain toxic substances, which could be incorporated into agricultural products or be distributed in the environment. Moreover, sediments can be contaminated by the discharge of wastewater effluents into rivers. This article reviews the determination of emerging contaminants (surfactants, flame retardants, pharmaceuticals and personal care products) in environmental solid samples (sludge, soil and sediment). Sample preparation, including extraction and clean-up, as well as the subsequent instrumental determination of contaminants are discussed. Recent applications of extraction techniques, such as Soxhlet extraction, ultrasound assisted extraction, pressurised liquid extraction, microwave assisted extraction and matrix solid-phase dispersion to the analysis of emerging contaminants in environmental solid samples are reviewed. Determination of these contaminants, generally carried out by gas chromatography and liquid chromatography coupled with different detectors, especially mass spectrometry for the identification and quantification of residues, is also summarised and discussed.      

A method for the determination of tritium in environmental water samples by electrolytic enrichment

In order to determine the tritium concentration in environmental water samples, the electrolytic enrichment was carried out with (St) and without (S) addition of tritiated water of a certain concentration (deuterium-free) to the samples. With the use of the fundamental formulas on electrolytic enrichment, the deuterium concentration (Dit) before electrolysis for an environmental water sample is determined by liquid scintillation counting and densitometry for the sample St. Furthermore, the tritium concentration in the environmental water sample is determined by the above methods for the sample S, and by the substitution of Dit for Di in the formulas. Tritium concentrations in environmental water samples were found to be determined within an accuracy of 10% by this method when Vi/Vf was 14-25. It is considered that this method dispenses with the direct measurement of low deuterium concentrations (Di) before electrolysis, a special technique on the purification of water for densitometry, and moreover, excludes the possibility of cross contamination in the electrolytic enrichment by the spike cell method.     

Determination of tritium levels in environmental samples around NIPNE,Romania from 2007 to 2017

National Institute for Physics and Nuclear Engineering (NIPNE) Romania is located in Măgurele and approximately 10 km from Bucharest. A continued surveillance over the past 10 years offers the opportunity to verify the tritium releases, but also for development of monitoring methods. The determined levels are well below the maximum admissible limits for environmental samples. Dose values have no impact on the environment and have an insignificant contribution to the cumulative annual dose. Comparison with global, regional and zonal levels highlights the role played by its emissions in the Lower Danube Basin, the Romanian Plain and the Danube Meadow.

     

A new adsorbent for trace organic analysis in environmental samples

Summary Graphite fluoride has been evaluated as an adsorbent for use in concentrating organic impurities in air and water samples. This material has been shown to yield large breakthrough volumes for most organics and should be useful for trace analysis in environmental chemistry.     

Assessment of natural radioactivity in soil samples and comparison of direct and indirect measurement of environmental air kerma rate

This study presents the high purity germanium (HPGe) gamma spectrometric measurement of natural radioactivity mainly due to ²²⁶Ra, ²³²Th and ⁴⁰K in soil samples collected in Ferozepur and Faridkot district of Punjab, India. ²²⁶Ra activity varied from 28.6 to 51.1 Bq kg⁻¹ with the mean of 39.7 Bq kg⁻¹. The range and mean activity of ²³²Th were 42.9–73.2 and 58.2 Bq kg⁻¹, respectively. ⁴⁰K activity was in the range of 470.9–754.9 Bq kg⁻¹ with the mean of 595.2 Bq kg⁻¹. The air kerma rate (AKR) at 1 m height from the ground was also measured using gamma survey meter in all the sampling locations, which was ranging from 92.1 to 122.8 nGy h⁻¹ with the mean of 110.6 nGy h⁻¹. The radiological parameters such as Ra_eq and activity index of the soil samples were also evaluated, which are the tools to assess the external radiation hazard due to building materials. The mean and range of the Ra_eq values were 168.7 and 132.9–210.4 Bq kg⁻¹, respectively, whereas the activity index varied from 0.5 to 0.8 with the mean value of 0.62. These indices show that the indoor external dose due to natural radioactivity in the soil used for the construction will not exceed the dose criteria. The AKR was also evaluated from soil activity concentration and altitude correction of cosmic radiation contribution. The statistical tests such as Pearson correlation, spearman rank correlation, box and whisker plot, the Wilcoxon/Mann–Whitney test and chi-square test, were used to compare the measured AKR with evaluated AKR, which indicates good correlation.     

Interlaboratory comparison for the determination of five residual organochlorine pesticides in ginseng root samples by gas chromatography

An interlaboratory comparison study for the determination of 5 residual organochlorine pesticides (hexachlorobenzene and 4 hexachlorocyclohexane isomers) in ginseng root was performed. This program [Asia Pacific Laboratory Accreditation Cooperation (APLAC) T049] was the first of its kind for an herbal matrix and involved the participation of 70 laboratories from 26 countries worldwide. Consensus mean values were computed statistically from the reported results, which were eventually used to assess the performance of individual laboratories in terms of the z-scores. The distribution of analytical data was found to be widespread, with standard deviation ranging from 43.9 to 55.9%, and the result patterns obtained were similar to those residue pesticide programs using other matrixes. Although the estimation of measurement uncertainty is a crucial requirement for all quantitative tests for laboratories that meet the requirements of International Organization for Standardization/International Electrotechnical Commisssion (ISO/IEC) 17025, some laboratories in this program had difficulties and showed unfamiliarity with respect to that quality criterion. It was recommended that laboratories review and rectify the situation promptly so that they would have a better understanding of measurement uncertainty or the test service provided.     

Rapid measurement of 241Pu activity at environmental levels using low-level liquid scintillation analysis

A straightforward and rapid method has been developed for the determination of ²⁴¹Pu activities. Pu is chemically separated from the sample, purified and electrodeposited to produce a source for alpha spectrometric determination of ²³⁸Pu and ^239,240Pu. Pu is stripped from the disc with concentrated nitric acid and extracted into tri-octylphosphine oxide (TOPO)/toluene. The organic extract is then mixed directly with commercial liquid scintillation cocktail without any further purification procedures and the sample counted on a Wallac 1220 Quantulus liquid scintillation counter (LSC). ²⁴¹Pu activity is estimated via the ²⁴²Pu yield monitor acquired by alpha spectrometry measurement. Experimental results for the performance testing of a low-level liquid scintillation spectrometer and the data for the evaluation of the method using standard reference materials are presented.     

Analysis of organic compounds in environmental samples by headspace solid phase microextraction

The analysis of samples contaminated by organic compounds is an important aspect of environmental monitoring. Because of the complex nature of these samples, isolating target organic compounds from their matrices is a major challenge. A new isolation technique, solid phase microextraction, or SPME, has recently been developed in our laboratory. This technique combines the extraction and concentration processes into one step; a fused silica fiber coated with a polymer is used to extract analytes and transfer them into a GC injector for thermal desorption and analysis. It is simple, rapid, inexpensive, completely solvent-free, and easily automated. To minimize matrix interferences in environmental samples, SPME can be used to extract analytes from the headspace above the sample. The combination of headspace sampling with SPME separates volatile and semi-volatile analytes from non-volatile compounds, thus greatly reducing the interferences from non-target compounds. This paper reports the use of headspace SPME to isolate volatile organic compounds from various matrices such as water, sand, clay, and sludge. By use of the technique, benzene, toluene, ethyl-benzene, and xylene isomers (commonly known as BTEX), and volatile chlorinated compounds can be efficiently isolated from various matrices with good precision and low limits of detection. This study has found that the sensitivity of the method can be greatly improved by the addition of salt to water samples, water to soil samples, or by heating. Headspace SPME can also be used to sample semi-volatile compounds, such as PAHs, from complex matrices.     

Interlaboratory comparison of INAA of semiconductor silicon

In an interlaboratory comparison four samples of monocrystalline silicon were analyzed sequentially by INAA in four laboratories. The results obtained demonstrate the possiblity of repeated use of silicion samples for interlaboratory comparisons. *** DIRECT SUPPORT *** A0653052 00003     

Occurrence of residual water within disk-based solid-phase extraction and its effect on GC-MS measurement of organic extracts of environmental samples

Solid-phase extraction (SPE) is a widespread and powerful sample preparation technique in many analytical areas. Many of the used methods reduce residual water during sample preparation by drying the phase material. Despite the importance of this step, hardly any study deals specifically with the drying process, and if so, only few aspects are mentioned. The present study is the first systematic investigation of the drying process using SPE disks, including the influence of process parameters on the amount of residual water and its consequences for subsequent elution and gas chromatography-mass spectrometry (GC-MS) analysis. The following points were investigated in detail: (1) the change of pressure and volume flow during the drying process, (2) the remaining amount of water at different drying times for different SPE materials, (3) the influence of suspended particulate matter on the drying process and (4) the effects of the residual water on the elution step by using different organic solvents. The study shows that the volume of residual water in the SPE disk is affected by the fixation of the sorbent, the phase material, the amount of sorbent, the pumping settings and the duration of the drying process. Furthermore, systematic investigations demonstrate the influence of residual water on the GC-MS analysis and show analytical interferences only for a few of the investigated analytes. All results suggest that more problems in SPE GC-MS methods are caused by residual water than previously assumed.     

Uncertainty assessment of environmental tritium measurements in water

The method most widely used nowadays to measure environmental tritium levels in water is electrolytic enrichment followed by liquid scintillation spectrometry. Although these techniques have been in use for many years, there is a gap in systematic analysis of the sources of uncertainty associated with this particular application. The paper presents a comprehensive assessment of the individual uncertainty components of the entire analytical process, starting from sample preparation to radioactivity measurement. Examples of the complete uncertainty budget for typical tritium levels in the analysed water samples are included. The relative importance of individual uncertainty components is given and possible ways of improving the overall quality of analyses are discussed.