Pd-Ag膜电解浓缩氚的动力学模型及理论计算

建立了模拟Pd-Ag合金膜电解浓缩氚的过程和诸多电解参数的动力学模型。采用求解数学扩散方程的方法得到理论值,并与文献报道的实验数据进行比较。计算结果表明：氚在Pd-Ag膜上的吸附、解吸、浓缩等行为受到诸多条件的制约。在保证密封性能的前提下,对Pd-Ag膜电解槽体的要求是至少应包括有含氚水路循环、阳极气体消除和阴极扩散后氚再生3个组成部分,采取相匹配的级联技术可以提高分离效果;对电解参数的要求是采取尽可能高的电解液温度和稳定的OH^-浓度,合适的电流密度,合理的膜厚度、表面特征和Pd黑结合紧密。     

Breath water-based doubly labelled water method for the noninvasive determination of CO2 production and energy expenditure in mice

ABSTRACT

We explored a novel doubly labelled water (DLW) method based on breath water (BW-DLW) in mice to determine whole body CO₂ production and energy expenditure noninvasively. The BW-DLW method was compared to the DLW based on blood plasma. Mice (n?=?11, 43.5?±?4.6?g body mass (BM)) were administered orally a single bolus of doubly labelled water (1.2?g H₂¹⁸O kg BM^?1 and 0.4?g ²H₂O kg BM^?1, 99 atom% (AP) ¹⁸O or ²H). To sample breath water, the mice were placed into a respiration vessel. The exhaled water vapour was condensed in a cold-trap. The isotope enrichments of breath water were compared with plasma samples. The ²H/¹H and ¹⁸O/¹⁶O isotope ratios were measured by means of isotope ratio mass spectrometry. The CO₂ production (RCO₂) was calculated from the ²H and ¹⁸O enrichments in breath water and plasma over 5 days. The isotope enrichments of breath water vs. plasma were correlated (R²?=?0.89 for ²H and 0.95 for ¹⁸O) linearly. The RCO₂ determined based on breath water and plasma was not different (113.2?±?12.7 vs. 111.4?±?11.0?mmol?d^–1), respectively. In conclusion, the novel BW-DLW method is appropriate to obtain reliable estimates of RCO₂ avoiding blood sampling.     

Ultra low-level tritium measurement using electrolytic enrichment and LSC†

We describe an advanced methodology for low-level tritium measurement in regard to calibration, electrolytic tritium enrichment, liquid scintillation counting (LSC) measurement, and prevention of sample contamination. Details are given on enrichment parameters and electrode processes for optimisation of enrichment reproducibility and on optimisation of LSC stability. Intercomparison results demonstrate high accuracy of the tritium measurement system. The use of accurate tritium data for groundwater dating in the southern hemisphere is demonstrated with data from several groundwater systems of New Zealand.     

Determination of tritium concentrations in humans before the development of a nuclear power plant in Turkey

The most widely used method to determine the level of tritium in humans is testing urine. Tritium concentrations in urine samples of 100 persons aged 18–66 years selected randomly from a pilot region in Turkey were analysed. The average activity concentration of urine samples was 4.66?±?1.94?Bq?L^?1 and the maximum activity concentration was 27.91?Bq?L^?1. The minimum detectable activity was 2.38?Bq?L^?1. The annual effective dose from tritium was also evaluated on the basis of the measurement results and reference values recommended by the International Commission on Radiological Protection. The effective doses for males and females were 4.56 and 3.54?nSv, respectively. These results were lower than the permissible annual effective dose for members of the public.     

Tritium in water electrolytic enrichment and liquid scintillation counting

A batch of electrolysis cells was developed for tritium in water samples enrichment by at least a factor 10. The cell batch is controlled by a pre-programmable electronic system that interrupts the current through any cell when the planned electrolyte volume is attained. A starting and a final distillation of water samples are carried out before and after the electrolytic enrichment. Both distillations are made to dryness in order to avoid isotopic fractionation.A second electrolysis step allowed the tritium enrichment factor (EFT) to be doubled. The EFT was calculated by means of the deuterium enrichment factor (EFD) that was measured by mass spectrometry. The EFT was also measured by liquid scintillation counting. The calculated and measured EFT values were found in good agreement, especially for samples with significant tritium content.     

Increasing the performance of tritium analysis by electrolytic enrichment†

Several improvements are described for the existing tritium enrichment system at the Isotope Hydrology Laboratory of the International Atomic Energy Agency for processing natural water samples. The improvements include a simple method for pretreatment of electrolytic cells to ensure a high tritium separation factor, an improved design of the exhaust system for explosive gases, and a vacuum distillation line for faster initial preparation of water samples for electrolytic enrichment and for tritium analysis. Achievements included the reduction of variation of individual enrichment parameters of all cells to less than 1% and an improvement of 50% of the stability of the background mean. It resulted in an improved detection limit of less than 0.4 TU (at 2s), important for application of tritium measurements in the future at low concentration levels, and resulted in measurement precisions of±0.2 TU and±0.15 TU for liquid scintillation counting and for gas proportional counting, respectively.     

On the conversion of tritium units to mass fractions for hydrologic applications

We develop a general equation for converting laboratory-reported tritium levels, expressed either as concentrations (tritium isotope number fractions) or mass-based specific activities, to mass fractions in aqueous systems. Assuming that all tritium is in the form of monotritiated water simplifies the derivation and is shown to be reasonable for most environmental settings encountered in practice. The general equation is nonlinear. For tritium concentrations c less than 4.5×10¹² tritium units (TU) – i.e. specific tritium activities<5.3×10¹¹ Bq kg^?1 – the mass fraction w of tritiated water is approximated to within 1 part per million by w ≈ c×2.22293×10^?18, i.e. the conversion is linear for all practical purposes. Terrestrial abundances serve as a proxy for non-tritium isotopes in the absence of sample-specific data. Variation in the relative abundances of non-tritium isotopes in the terrestrial hydrosphere produces a minimum range for the mantissa of the conversion factor of [2.22287; 2.22300].     

Assessment of the origin and geothermal potential of the thermal waters by hydro-isotope geochemistry: Eskisehir province,Turkey

The thermal fluids vented over Eskisehir province have been investigated for their origin and to estimate the geothermal potential of the area. Thermal waters as well as bubbling and dissolved gases were collected and analysed for their chemical and isotopic features. Their isotopic composition varies in the range from ?11.5 to ?7.7?‰ for δ¹⁸O, ?84 and ?57?‰ for δ²H, and 0–7.2 TU for tritium. The gases (bubbling and dissolved) are mostly N₂-dominated with a significant amount of CO₂. The helium isotopic ratios are in the range of 0.2–0.66?R/Rac, indicate remarkable mantle-He contribution ranging between 2 and 10?% in the whole study area. Considering the estimated geothermal gradient about three times higher than the normal gradient, and the reservoir temperatures estimated to be between 50 and 100?°C using quartz and chalcedony geothermometers, a circulation model was built where possible mixing with shallow waters cool down the uprising geothermal fluids.     

Temporal and spatial distribution of isotopes in river water in Central Europe: 50 years experience with the Austrian network of isotopes in rivers

The Austrian network of isotopes in rivers comprises about 15 sampling locations and has been operated since 1976. The Danube isotope time series goes back to 1963. The isotopic composition of river water in Central Europe is mainly governed by the isotopic composition of precipitation in the catchment area; evaporation effects play only a minor role. Short-term and long-term isotope signals in precipitation are thus transmitted through the whole catchment. The influence of climatic changes has become observable in the long-term stable isotope time series of precipitation and surface waters. Environmental ³H values were around 8 TU in 2015, short-term ³H pulses up to about 80 TU in the rivers Danube and March were a consequence of releases from nuclear power plants. The complete isotope data series of this network will be included in the Global Network of Isotopes in Rivers database of the International Atomic Energy Agency (IAEA) in 2017. This article comprises a review of 50 years isotope monitoring on rivers and is also intended to provide base information on the (isotope-)hydrological conditions in Central Europe specifically for the end-users of these data, e.g. for modelling hydrological processes. Furthermore, this paper includes the 2006–2015 supplement adding to the Danube isotope set published earlier.     

Comparison of pore water samplers and cryogenic distillation under laboratory and field conditions for soil water stable isotope analysis*

We used pore water samplers (PWS) to sample for isotope analysis (1) only water, (2) soil under laboratory conditions, and (3) soil in the field comparing the results with cryogenic extraction (CE). In (1) and (2), no significant differences between source and water extracted with PWS were detected with a mean absolute difference (MAD) always lower than 2?‰ for δ²H and 1?‰ for δ¹⁸O. In (2), CE water was more enriched than PWS-extracted water, with a MAD respect to source water of roughly 8?‰ for δ²H and 4?‰ for δ¹⁸O. In (3), PWS water was enriched relative to CE water by 3?‰ for δ²H and 0.9?‰ for δ¹⁸O. The latter result may be due to the distinct water portions sampled by the two methods. Large pores, easily sampled by PWS, likely retain recent, and enriched, summer precipitation while small pores, only sampled by CE, possibly retain isotopically depleted water from previous winter precipitation or irrigation inputs. Accuracy and precision were greater for PWS relative to CE. PWS is therefore suggested as viable tool to extract soil water for stable isotope analysis, particularly for soils used in this study (sandy and silty loams).     

Studies on stable isotopic composition of daily rainfall from Kozhikode,Kerala, India

The stable isotopic compositions of all major daily rain fall samples (n?=?113) collected from Kozhikode station in Kerala, India, for the year 2010 representing the pre-monsoon, southwest and northeast monsoon seasons are examined. The isotopic variations δ¹⁸O, δ²H and d-excess in daily rainfall ranged from δ¹⁸O: ?4.4 to 2?‰, δ²H: ?25.3 to 13.8?‰, and d-excess: ?2.4 to 15.3?‰; δ¹⁸O: ?9.7 to ?0.6?‰, δ²H: ?61.7 to 5.3?‰, and d-excess 5.8 to 17.4?‰; δ¹⁸O ?11.3 to ?1.4?‰, δ²H: ?75.3 to 0.9?‰, and d-excess: 8.8 to 21.3?‰ during the pre-, southwest and northeast monsoon periods, respectively. Thus, daily rainfall events during two monsoon periods had a distinct range of isotopic variations. The daily rain events within the two monsoon seasons also exhibited periodic variations. The isotopic composition of rain events during pre-monsoon and a few low-intensity events during the southwest monsoon period had imprints of secondary evaporation. This study analysing the stable isotopic characteristics of individual rain events in southern India, which is influenced by dual monsoon rainfall, will aid in a better understanding of its mechanism.     

Isotopic composition in precipitation and groundwater in the northern mountainous region of the Central Valley of Costa Rica

The linkage between precipitation and recharge is still poorly understood in the Central America region. This study focuses on stable isotopic composition in precipitation and groundwater in the northern mountainous region of the Central Valley of Costa Rica. During the dry season, rainfall samples corresponded to enriched events with high deuterium excess. By mid-May, the Intertropical Convergence Zone poses over Costa Rica resulting in a depletion of ¹⁸O/¹⁶O and ²H/H ratios. A parsimonious four-variable regression model (r^2?=?0.52) was able to predict daily δ¹⁸O in precipitation. Air mass back trajectories indicated a combination of Caribbean Sea and Pacific Ocean sources, which is clearly depicted in groundwater isoscape. Aquifers relying on Pacific-originated recharge exhibited a more depleted pattern, whereas recharge areas relying on Caribbean parental moisture showed an enrichment trend. These results can be used to enhance modelling efforts in Central America where scarcity of long-term data limits water resources management plans.     

Sauna,sweat and science II – do we sweat what we drink?

ABSTRACT

Inspired by a previous ‘Sauna, sweat and science’ study [Zech et al. Isot Environ Health Stud. 2015;51(3):439–447] and out of curiosity and enthusiasm for stable isotope and sauna research we aimed at answering the question ‘do we sweat (isotopically) what we drink’? We, therefore, pulse-labelled five test persons in a sauna experiment with beverages that were ²H-enriched at about +25,600?‰. Sweat samples were collected during six sauna rounds and the hydrogen isotope composition δ²H_sweat was determined using an isotope ratio mass spectrometer. Before pulse labelling, δ²H_sweat – reflecting by approximation body water – ranged from –32 to –22?‰. This is ～35?‰ enriched compared to usual mid-European drinking water and can be explained with hydrogen-bearing food as well as with the respiratory loss of ²H-depleted vapour. The absence of a clearly detectable ²H pulse in sweat after pulse labelling and δ²H_sweat results of ≤+250?‰ due to a fast ²H equilibration with body water are moreover a clearly negative answer to our research question also in a short-term consideration. Given that the recovery of the tracer based on an isotope mass balance calculation is clearly below 100?%, we finally answer the question ‘where did the rest of the tracer go?’     

Seasonal variation of oxygen-18 in precipitation and surface water of the Poyang Lake Basin,China

Based on the monthly δ¹⁸O value measured over a hydrology period in precipitation, runoff of five tributaries and the main lake of the Poyang Lake Basin, combined with hydrological and meteorological data, the characteristics of δ¹⁸O in precipitation (δ¹⁸O_PPT) and runoff (δ¹⁸O_SUR) are discussed. The δ¹⁸O_PPT and δ¹⁸O_SUR values range from?2.75 to?14.12 ‰ (annual mean value=?7.13 ‰ ) and from?2.30 to?8.56 ‰, respectively. The seasonal variation of δ¹⁸O_PPT is controlled by the air mass circulation in this region, which is dominated by the Asian summer monsoon and the Siberian High during winter. The correlation between the wet seasonal averages of δ¹⁸O_SUR in runoff of the rivers and δ¹⁸O_PPT of precipitation at the corresponding stations shows that in the Poyang Lake catchment area the river water consists of 23% direct runoff (precipitation) and 77% base flow (shallow groundwater). This high proportion of groundwater in the river runoff points to the prevalence of wetland conditions in the Poyang Lake catchment during rainy season. Considering the oxygen isotopic composition of the main body of Poyang Lake, no isotopic enrichment relative to river inflow was found during the rainy season with maximum expansion of the lake. Thus, evaporation causing isotopic enrichment is a minor component of the lake water balance in the rainy period. During dry season, a slight isotopic enrichment has been observed, which suggests a certain evaporative loss of lake water in that period.     

Turnover of hydrogen isotopes in lake sturgeon blood: implications for tracking movements of wild populations

Naturally occurring deuterium (²H) in biota can be used to trace movement, migration and geographic origin of a range of organisms. However, to evaluate movements of animals using δ²H measurements of tissues, it is necessary to establish the turnover time of ²H in the tissues and the extent of isotopic discrimination from different environmental ²H sources to those tissues. We investigated the turnover of ²H in lake sturgeon (Acipenser fulvescens) blood by manipulating both environmental water δ²H and diet δ²H over a four-month period. The half-life of deuterium in lake sturgeon blood was 37.9 days after an increase in the environmental water δ²H of +714?‰. However, no clear turnover in blood ²H occurred over the same period in a separate trial following a change of ?63.8?‰ or +94.2?‰ in diet. These findings suggest that environmental water ²H exchanges much faster with blood than diets and that blood δ²H values can be used to trace movements of sturgeon and other fish moving among isotopically distinct waters.     

Soil water balance in the Lake Chad Basin using stable water isotopes and chloride of soil profiles

ABSTRACT

The Lake Chad Basin (LCB) is an endorheic transboundary catchment highly vulnerable to drought. For effective groundwater management, recharge areas need identification and replenishment quantification. At present, little research exploring unsaturated zone water flow processes and groundwater recharge are available. In this study, 12 vertical soil profiles were analysed for stable water isotopes and chloride concentration to estimate evaporation and groundwater renewal. Most δ¹⁸O and δ²H isotope profiles reveal typical arid environment patterns, with maximum enrichment at depths between 2.5 and 20?cm and depletion towards the surface (atmospheric influence) and depth (mixing and diffusion). Average annual dry season evaporation rates in Salamat and Waza Logone range from 5 to 30?mm, in Bahr el Ghazal and Northern Lake Chad from 14 to 23?mm. According to the chloride mass balance (CMB), the average annual recharge rate is estimated between 3 and 163?mm in Salamat and Waza Logone and less than 1 mm in Bahr el Ghazal and Northern Lake Chad. Based on the CMB results, potential recharge sites were identified, while estimated soil evaporation corresponds to plant water use at the initial growing stage, which is an important component in irrigation water management.     

Stable isotope composition of the meteoric precipitation in Croatia

The precipitation is the input into the water system. Its stable isotope composition has to be known for the proper use and management of water resources. Croatia is not well represented in the Global Network of Isotopes in Precipitation (GNIP) database, and the geomorphology of the country causes specific local conditions. Therefore, at the Stable Isotope Laboratory (SILab), Rijeka, we monitor the stable isotope composition (δ¹⁸O, δ²H) of precipitation. Since δ¹⁸O and δ²H are well correlated, we concentrate the discussion on the δ¹⁸O distribution. Together with GNIP, our database contains 40 stations in Croatia and in the neighbouring countries. Their different latitudes, longitudes and altitudes give information of great detail, including the influence of the topographic structure on the precipitation in the south-eastern part of Europe, as well as the complex interplay of the different climate conditions in the area. Within a few hundred kilometres, the stable isotope values display a significant change from the maritime character in the south (mean δ¹⁸O around?6 to?8%‰) to the continental behaviour in the north (mean δ¹⁸O around?8 to?11%‰). Depending on the location, the mean δ¹⁸O values vary with altitude at a rate of approximately?0.2%‰/100 m and?0.4%‰/100 m, respectively. Also the deuterium excess has been found to depend on location and altitude. The data are being used to construct a δ¹⁸O map for the entire area.     

Spring response to precipitation events using δ18O and δ2H in the Tanour catchment,NW Jordan

The Tanour spring is one of the several karst springs located in the northern part of Jordan. Water samples from the Tanour spring and precipitation were collected in the area of Ajloun in NW Jordan for the analysis of stable oxygen and hydrogen isotopes to evaluate the spring response to precipitation events. Rainwater and snow samples were collected from different elevations during winters of 2013–2014 and 2014–2015. In addition, spring samples were collected between December 2014 and March 2015. δ¹⁸O values in rainwater vary from ?3.26 to ?17.34?‰ (average: ?7.84?±?3.23?‰), while δ²H values range between ?4.4 and ?110.4?‰ (average: ?35.7?±?25.0?‰). Deuterium excess ranges from 17.8 to 34.1?‰ (average: 27.1?±?4.0?‰). The Local Meteoric Water Line for the study area was calculated to be δ²H?=?7.66*δ¹⁸O?+?24.43 (R²?=?0.98). Pre-event spring discharge showed variation in δ¹⁸O (range ?6.29 to ?7.17?‰; average ?6.58?±?0.19?‰) and δ²H values (range ?28.8 to ?32.7?‰; average: ?30.5?±?1.0?‰). In contrast, δ¹⁸O and δ²H rapidly changed to more negative values during rainfall and snowmelt events and persisted for several days before returning to background values. Spring water temperature, spring discharge, and turbidity followed the trend in isotopic composition during and after the precipitation events. The rapid change in the isotopic composition, spring discharge, water temperature, and turbidity in response to recharge events is related to fast water travel times and low storage capacity in the conduit system of the karst aquifer. Based on the changes in the isotopic composition of spring water after the precipitation events, the water travel time in the aquifer is in the order of 5–11 days.     

Estimation of groundwater recharge via deuterium labelling in the semi-arid Cuvelai-Etosha Basin,Namibia

The stable water isotope deuterium (²H) was applied as an artificial tracer (²H₂O) in order to estimate groundwater recharge through the unsaturated zone and describe soil water movement in a semi-arid region of northern central Namibia. A particular focus of this study was to assess the spatiotemporal persistence of the tracer when applied in the field on a small scale under extreme climatic conditions and to propose a method to obtain estimates of recharge in data-scarce regions. At two natural sites that differ in vegetation cover, soil and geology, 500?ml of a 70?% ²H₂O solution was irrigated onto water saturated plots. The displacement of the ²H peak was analyzed 1 and 10 days after an artificial rain event of 20 mm as well as after the rainy season. Results show that it is possible to apply the peak displacement method for the estimation of groundwater recharge rates in semi-arid environments via deuterium labelling. Potential recharge for the rainy season 2013/2014 was calculated as 45 mm a^?1 at 5.6 m depth and 40 mm a^?1 at 0.9 m depth at the two studied sites, respectively. Under saturated conditions, the artificial rain events moved 2.1 and 0.5 m downwards, respectively. The tracer at the deep sand site (site 1) was found after the rainy season at 5.6 m depth, corresponding to a displacement of 3.2 m. This equals in an average travel velocity of 2.8 cm d^?1 during the rainy season at the first site. At the second location, the tracer peak was discovered at 0.9 m depth; displacement was found to be only 0.4 m equalling an average movement of 0.2 cm d^?1 through the unsaturated zone due to an underlying calcrete formation. Tracer recovery after one rainy season was found to be as low as 3.6?% at site 1 and 1.9?% at site 2. With an in situ measuring technique, a three-dimensional distribution of ²H after the rainy season could be measured and visualized. This study comprises the first application of the peak displacement method using a deuterium labelling technique for the estimation of groundwater recharge in semi-arid regions. Deuterium proved to be a suitable tracer for studies within the soil–vegetation–atmosphere interface. The results of this study are relevant for the design of labelling experiments in the unsaturated zone of dry areas using ²H₂O as a tracer and obtaining estimations of groundwater recharge on a local scale. The presented methodology is particularly beneficial in data-scarce environments, where recharge pathways and mechanisms are poorly understood.     

Distribution of stable isotopes in surface water along the Danube River in Serbia†

Stable hydrogen and oxygen isotopes were analysed in water samples from the River Danube and its tributaries during a longitudinal survey performed in August 2005 on Serbian territory. Danube river water data ranged from?80‰ to?66‰ for δ²H, and from?11.2‰ to?9.3‰ for δ¹⁸O with δ values increasing downstream. The isotopic signatures of the adjacent tributaries (the Tisza, the Sava and the Velika Morava) sampled at the locations close to their confluence with the Danube (Titel, Ostru?nica and Ljubi?evski most, respectively) just about the time of the campaign were enriched (?67‰ and?63‰ for δ²H, and?9.3‰ and?8.9‰ for δ¹⁸O) with respect to the Danube water because of their catchment effects. Hydrogen and oxygen stable isotope values were used in combination with measured physico-chemical and biological parameters to trace hydrological and transport processes in these river systems. The mixing relationships between the Danube main stream and its tributaries were estimated using the mass balance for isotopic composition and electrical conductivity as conservative parameters. Evidence of an incomplete mixing process at the ?enta location, 8 km below the confluence of the Tisza river, with its participation of 88% was shown by its oxygen-18 content. The correlations between river water isotope composition and physico-chemical and biological parameters are discussed.