Noble gas, CFC and other geochemical evidence for the age and origin of the Bath thermal waters, UK

The city of Bath is a World Heritage site and its thermal waters, the Roman Baths and new spa development rely on undisturbed flow of the springs (45 °C). The current investigations provide an improved understanding of the residence times and flow regime as basis for the source protection. Trace gas indicators including the noble gases (helium, neon, argon, krypton and xenon) and chlorofluorocarbons (CFCs), together with a more comprehensive examination of chemical and stable isotope tracers are used to characterise the sources of the thermal water and any modern components. It is shown conclusively by the use of 39Ar that the bulk of the thermal water has been in circulation within the Carboniferous Limestone for at least 1000 years. Other stable isotope and noble gas measurements confirm previous findings and strongly suggest recharge within the Holocene time period (i.e. the last 12 kyr). Measurements of dissolved 85Kr and chlorofluorocarbons constrain previous indications from tritium that a small proportion (<5%) of the thermal water originates from modern leakage into the spring pipe passing through Mesozoic valley fill underlying Bath. This introduces small amounts of O2 into the system, resulting in the Fe precipitation seen in the King’s Spring. Silica geothermometry indicates that the water is likely to have reached a maximum temperature of between 69–99 °C, indicating a most probable maximum circulation depth of ∼3 km, which is in line with recent geological models. The rise to the surface of the water is sufficiently indirect that a temperature loss of >20 °C is incurred. There is overwhelming evidence that the water has evolved within the Carboniferous Limestone formation, although the chemistry alone cannot pinpoint the geometry of the recharge area or circulation route. For a likely residence time of 1–12 kyr, volumetric calculations imply a large storage volume and circulation pathway if typical porosities of the limestone at depth are used, indicating that much of the Bath-Bristol basin must be involved in the water storage.

Groundwater age distributions at a public drinking water supply well field derived from multiple age tracers (⁸⁵Kr, ³H/³He, and ³⁹Ar)

Groundwater age is a key aspect of production well vulnerability. Public drinking water supply wells typically have long screens and are expected to produce a mixture of groundwater ages. The groundwater age distributions of seven production wells of the Holten well field (Netherlands) were estimated from tritium-helium (3H/3He), krypton-85 (85Kr), and argon-39 (39Ar), using a new application of a discrete age distribution model and existing mathematical models, by minimizing the uncertainty-weighted squared differences of modeled and measured tracer concentrations. The observed tracer concentrations fitted well to a 4-bin discrete age distribution model or a dispersion model with a fraction of old groundwater. Our results show that more than 75 of the water pumped by four shallow production wells has a groundwater age of less than 20 years and these wells are very vulnerable to recent surface contamination. More than 50 of the water pumped by three deep production wells is older than 60 years. 3H/3He samples from short screened monitoring wells surrounding the well field constrained the age stratification in the aquifer. The discrepancy between the age stratification with depth and the groundwater age distribution of the production wells showed that the well field preferentially pumps from the shallow part of the aquifer. The discrete groundwater age distribution model appears to be a suitable approach in settings where the shape of the age distribution cannot be assumed to follow a simple mathematical model, such as a production well field where wells compete for capture area.

Analysis of ⁸⁵Kr: a comparison at the 10-14 level using micro-liter samples

The isotopic abundance of 85Kr in the atmosphere, currently at the level of 10−11, has increased by orders of magnitude since the dawn of nuclear age. With a half-life of 10.76 years, 85Kr is of great interest as tracers for environmental samples such as air, groundwater and ice. Atom Trap Trace Analysis (ATTA) is an emerging method for the analysis of rare krypton isotopes at isotopic abundance levels as low as 10−14 using krypton gas samples of a few micro-liters. Both the reliability and reproducibility of the method are examined in the present study by an inter-comparison among different instruments. The 85Kr/Kr ratios of 12 samples, in the range of 10−13 to 10−10, are measured independently in three laboratories: a low-level counting laboratory in Bern, Switzerland, and two ATTA laboratories, one in Hefei, China, and another in Argonne, USA. The results are in agreement at the precision level of 5%.

Multiple inert gas elimination technique by micropore membrane inlet mass spectrometry--a comparison with reference gas chromatography.

The mismatching of alveolar ventilation and perfusion (VA/Q) is the major determinant of impaired gas exchange. The gold standard for measuring VA/Q distributions is based on measurements of the elimination and retention of infused inert gases. Conventional multiple inert gas elimination technique (MIGET) uses gas chromatography (GC) to measure the inert gas partial pressures, which requires tonometry of blood samples with a gas that can then be injected into the chromatograph. The method is laborious and requires meticulous care. A new technique based on micropore membrane inlet mass spectrometry (MMIMS) facilitates the handling of blood and gas samples and provides nearly real-time analysis. In this study we compared MIGET by GC and MMIMS in 10 piglets: 1) 3 with healthy lungs; 2) 4 with oleic acid injury; and 3) 3 with isolated left lower lobe ventilation. The different protocols ensured a large range of normal and abnormal VA/Q distributions. Eight inert gases (SF6, krypton, ethane, cyclopropane, desflurane, enflurane, diethyl ether, and acetone) were infused; six of these gases were measured with MMIMS, and six were measured with GC. We found close agreement of retention and excretion of the gases and the constructed VA/Q distributions between GC and MMIMS, and predicted PaO2 from both methods compared well with measured PaO2. VA/Q by GC produced more widely dispersed modes than MMIMS, explained in part by differences in the algorithms used to calculate VA/Q distributions. In conclusion, MMIMS enables faster measurement of VA/Q, is less demanding than GC, and produces comparable results.

Improving accuracy and precision of ice core δD(CH4) analyses using methane pre-pyrolysis and hydrogen post-pyrolysis trapping and subsequent chromatographic separation

Firn and polar ice cores offer the only direct palaeoatmospheric archive. Analyses of past greenhouse gas concentrations and their isotopic compositions in air bubbles in the ice can help to constrain changes in global biogeochemical cycles in the past. For the analysis of the hydrogen isotopic composition of methane (δD(CH4) or δ2H(CH4)) 0.5 to 1.5 kg of ice was hitherto used. Here we present a method to improve precision and reduce the sample amount for δD(CH4) measurements in (ice core) air. Pre-concentrated methane is focused in front of a high temperature oven (pre-pyrolysis trapping), and molecular hydrogen formed by pyrolysis is trapped afterwards (post-pyrolysis trapping), both on a carbon-PLOT capillary at −196 °C. Argon, oxygen, nitrogen, carbon monoxide, unpyrolysed methane and krypton are trapped together with H2 and must be separated using a second short, cooled chromatographic column to ensure accurate results. Pre- and post-pyrolysis trapping largely removes the isotopic fractionation induced during chromatographic separation and results in a narrow peak in the mass spectrometer. Air standards can be measured with a precision better than 1‰. For polar ice samples from glacial periods, we estimate a precision of 2.3‰ for 350 g of ice (or roughly 30 mL – at standard temperature and pressure (STP) – of air) with 350 ppb of methane. This corresponds to recent tropospheric air samples (about 1900 ppb CH4) of about 6 mL (STP) or about 500 pmol of pure CH4.

On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

Stable carbon isotope analysis of methane (delta C-13 of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton (Kr) can severely interfere during the mass spectrometric measurement, leading to significant biases in delta C-13 of CH4, if krypton is not sufficiently separated during the analysis. According to our experiments, the krypton interference is likely composed of two individual effects, with the lateral tailing of the doubly charged Kr-86 peak affecting the neighbouring m/z 44 and partially the m/z 45 Faraday cups. Additionally, a broad signal affecting m/z 45 and especially m/z 46 is assumed to result from scattered ions of singly charged krypton. The introduced bias in the measured isotope ratios is dependent on the chromatographic separation, the krypton-to-CH4 mixing ratio in the sample, the focusing of the mass spectrometer as well as the detector configuration and can amount to up to several per mil in delta C-13. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias.

Radiometric 81Kr dating identifies 120,000-year-old ice at Taylor Glacier, Antarctica

We present successful 81 Kr-Kr radiometric dating of ancient polarice. Krypton was extracted from the air bubbles in four∼350-kg polar ice samples from Taylor Glacier in the McMurdo Dry Valleys, Antarctica, and dated using Atom Trap Trace Analysis (ATTA). The 81 Kr radiometric ages agree with independent age estimates obtained from stratigraphic dating techniques with a mean abso-lute age offset of 6±2.5 ka. Our experimental methods and sampling strategy are validated by (i) 85 Kr and 39 Ar analyses that show the samples to be free of modern air contamination and (ii)air content measurements that show the ice did not experience gas loss. We estimate the error in the 81 Kr ages due to past geomagnetic variability to be below 3 ka. We show that ice from the previous interglacial period (Marine Isotope Stage 5e, 130–115 ka before present) can be found in abundance near the surface of Taylor Glacier. Our study paves the way for reliable radiometric dating of ancient ice in blue ice areas and margin sites where large samples are available, greatly enhancing their scientific value as archives of old ice and meteorites. At present, ATTA 81Kr analysis requires a 40–80-kg ice sample; as sample requirements continue to decrease, 81 Kr dating of ice cores is a future possibility.

Cool Glacial Temperatures and Changes in Moisture Source Recorded in Oman Groundwaters

Concentrations of atmospheric noble gases (neon, argon, krypton, and xenon) dissolved in groundwaters from northern Oman indicate that the average ground temperature during the Late Pleistocene (15,000 to 24,000 years before present) was 6.5° ± 0.6°C lower than that of today. Stable oxygen and hydrogen isotopic groundwater data show that the origin of atmospheric water vapor changed from a primarily southern, Indian Ocean source during the Late Pleistocene to a dominantly northern, Mediterranean source today. The reduced northern water vapor source is consistent with a drier Last Glacial Maximum through much of northern Africa and Arabia.

Calibration of cosmogenic noble gas production based on ³⁶Cl-³⁶Ar ages. Part 2. The ⁸¹Kr-Kr dating technique

We calibrated the ⁸¹Kr-Kr dating system for ordinary chondrites of different sizes using independent shielding-corrected ³⁶Cl-³⁶Ar ages. Krypton concentrations and isotopic compositions were measured in bulk samples from 14 ordinary chondrites of high petrologic type and the cosmogenic Kr component was obtained by subtracting trapped Kr from phase Q. The thus-determined average cosmogenic ⁷⁸Kr/⁸³Kr, ⁸⁰Kr/⁸³Kr, ⁸²Kr/⁸³Kr, and ⁸4Kr/⁸³Kr ratiC(Lavielle and Marti 1988; Wieler 2002). The cosmogenic ⁷⁸Kr/⁸³Kr ratio is correlated with the cosmogenic 22Ne/21Ne ratio, confirming that ⁷⁸Kr/⁸³Kr is a reliable shielding indicator. Previously, ⁸¹Kr-Kr ages have been determined by assuming the cosmogenic production rate of ⁸¹Kr, P(⁸¹Kr)c, to be 0.95 times the average of the cosmogenic production rates of ⁸⁰Kr and ⁸²Kr; the factor Y = 0.95 therefore accounts for the unequal production of the various Kr isotopes (Marti 1967a). However, Y should be regarded as an empirical adjustment. For samples whose ⁸⁰Kr and ⁸²Kr concentrations may be affected by neutron-capture reactions, the shielding-dependent cosmogenic (⁷⁸Kr/⁸³Kr)c ratio has been used instead to calculate P(⁸¹Kr)/P(⁸³Kr), as for some lunar samples, this ratio has been shown to linearly increase with (⁷⁸Kr/⁸³Kr)c (Marti and Lugmair 1971). However, the ⁸¹Kr-Kr ages of our samples calculated with these methods are on average ~30% higher than their ³⁶Cl-³⁶Ar ages, indicating that most if not all the ⁸¹Kr-Kr ages determined so far are significantly too high. We therefore re-evaluated both methods to determine P(⁸¹Kr)c/P(⁸³Kr)c. Our new Y value of 0.70 ± 0.04 is more than 25% lower than the value of 0.95 used so far. Furthermore, together with literature data, our data indicate that for chondrites, P(⁸¹Kr)c/P(⁸³Kr)c is rather constant at 0.43 ± 0.02, at least for the shielding range covered by our samples ([⁷⁸Kr/⁸³Kr]c = 0.119–0.185; [22Ne/21Ne]c = 1.083–1.144), in contrast to the observations on lunar samples. As expected considering the method used, ⁸¹Kr-Kr ages calculated either directly with this new P(⁸¹Kr)c/P(⁸³Kr)c value or with our new Y value both agree with the corresponding ³⁶Cl-³⁶Ar ages. However, the average deviation of 2% indicates the accuracy of both new ⁸¹Kr-Kr dating methods and the precision of the new dating systems of ~10% is demonstrated by the low scatter in the data. Consequently, this study indicates that the ⁸¹Kr-Kr ages published so far are up to 30% too high.