On-site leakage locating of underground natural gas pipeline based on Ne tracer by miniature time-of-flight mass spectrometry.

Natural gas pipeline leakage seriously endangers people's lives and properties, and there is an urgent need for on-site, rapid, and accurate locating the leakage point of the underground natural gas pipeline. Here, we added neon gas to natural gas pipelines as a tracer gas, and used a miniature time-of-flight mass spectrometry (mini-TOFMS) to on-site detect neon gas to quickly locate the leak point of underground natural gas pipelines. The mini-TOFMS used capillary tube sampling to directly analyze the leaked neon gas without sample preparation, and the analysis time of a single sample was only 60 s, which was less than one-seventeenth that of traditional off-line gas chromatography (GC) method. The mini-TOFMS exhibited a linear response range from 69 ppmv to 3.0 × 105 ppmv with the limit of detection (LOD, S/N = 3) of 19.0 ppmv. The correlation of GC and mini-TOFMS for Ne quantitative analysis was as high as 0.98. The performance of the newly designed method with the mini-TOFMS was demonstrated by on-site locating the underground natural gas pipeline leakage point in the experimental station. And leakage point of the natural gas pipeline, especially for those pipelines with different gas pressure buried under the same road, can be found more efficiently and accurately.

Poor relationships between NEON Airborne Observation Platform data and field-based vegetation traits at a mesic grassland.

Understanding spatial and temporal variation in plant traits is needed to accurately predict how communities and ecosystems will respond to global change. The National Ecological Observatory Network's (NEON's) Airborne Observation Platform (AOP) provides hyperspectral images and associated data products at numerous field sites at 1 m spatial resolution, potentially allowing high-resolution trait mapping. We tested the accuracy of readily available data products of NEON's AOP, such as Leaf Area Index (LAI), Total Biomass, Ecosystem Structure (Canopy height model [CHM]), and Canopy Nitrogen, by comparing them to spatially extensive field measurements from a mesic tallgrass prairie. Correlations with AOP data products exhibited generally weak or no relationships with corresponding field measurements. The strongest relationships were between AOP LAI and ground-measured LAI (r = 0.32) and AOP Total Biomass and ground-measured biomass (r = 0.23). We also examined how well the full reflectance spectra (380-2,500 nm), as opposed to derived products, could predict vegetation traits using partial least-squares regression (PLSR) models. Among all the eight traits examined, only Nitrogen had a validation R2 of more than 0.25. For all vegetation traits, validation R2 ranged from 0.08 to 0.29 and the range of the root mean square error of prediction (RMSEP) was 14-64%. Our results suggest that currently available AOP-derived data products should not be used without extensive ground-based validation. Relationships using the full reflectance spectra may be more promising, although careful consideration of field and AOP data mismatches in space and/or time, biases in field-based measurements or AOP algorithms, and model uncertainty are needed. Finally, grassland sites may be especially challenging for airborne spectroscopy because of their high species diversity within a small area, mixed functional types of plant communities, and heterogeneous mosaics of disturbance and resource availability. Remote sensing observations are one of the most promising approaches to understanding ecological patterns across space and time. But the opportunity to engage a diverse community of NEON data users will depend on establishing rigorous links with in-situ field measurements across a diversity of sites.

Deep-mantle krypton reveals Earth's early accretion of carbonaceous matter.

Establishing when, and from where, carbon, nitrogen and water were delivered to Earth is a fundamental objective in understanding the origin of habitable planets such as Earth. Yet, volatile delivery to Earth remains controversial1-5. Krypton isotopes provide insights on volatile delivery owing to their substantial isotopic variations among sources6-10, although pervasive atmospheric contamination has hampered analytical efforts. Here we present the full suite of krypton isotopes from the deep mantle of the Galápagos and Iceland plumes, which have the most primitive helium, neon and tungsten isotopic compositions11-16. Except for 86Kr, the krypton isotopic compositions are similar to a mixture of chondritic and atmospheric krypton. These results suggest early accretion of carbonaceous material by proto-Earth and rule out any combination of hydrodynamic loss with outgassing of the deep or shallow mantle to explain atmospheric noble gases. Unexpectedly, the deep-mantle sources have a deficit in the neutron-rich 86Kr relative to the average composition of carbonaceous meteorites, which suggests a nucleosynthetic anomaly. Although the relative depletion of neutron-rich isotopes on Earth compared with carbonaceous meteorites has been documented for a range of refractory elements1,17,18, our observations suggest such a depletion for a volatile element. This finding indicates that accretion of volatile and refractory elements occurred simultaneously, with krypton recording concomitant accretion of non-solar volatiles from more than one type of material, possibly including outer Solar System planetesimals.

Analysis of trace impurities in neon by a customized gas chromatography.

Excimer lasers, widely used in the semiconductor industry, are crucial for analyzing the purity of premix laser gases for the purpose of controlling stable laser output power. In this study, we designed a system for analyzing impurities in pure neon (Ne) base gas by customized GC. Impurities in pure neon (H2 and He), which cannot be analyzed at the sub-µmol/mol level using commercial GC detectors, were analyzed by a customized pulsed-discharge Ne ionization detector (PDNeD) and a pressurized injection thermal conductivity detector using Ne as the carrier gas (Pres. Inj. Ne-TCD). From the results, trace species in Ne were identified with the following detection limits: H2, 0.378µmol/mol; O2, 0.119µmol/mol; CH4, 0.880µmol/mol; CO, 0.263µmol/mol; CO2, 0.162µmol/mol (PDNeD); and He, 0.190µmol/mol (Pres. Inj. Ne-TCD). This PDNeD and pressurized injection Ne-TCD technique thus developed permit the quantification of trace impurities present in high-purity Ne.

Deep fracture fluids isolated in the crust since the Precambrian era.

Fluids trapped as inclusions within minerals can be billions of years old and preserve a record of the fluid chemistry and environment at the time of mineralization. Aqueous fluids that have had a similar residence time at mineral interfaces and in fractures (fracture fluids) have not been previously identified. Expulsion of fracture fluids from basement systems with low connectivity occurs through deformation and fracturing of the brittle crust. The fractal nature of this process must, at some scale, preserve pockets of interconnected fluid from the earliest crustal history. In one such system, 2.8 kilometres below the surface in a South African gold mine, extant chemoautotrophic microbes have been identified in fluids isolated from the photosphere on timescales of tens of millions of years. Deep fracture fluids with similar chemistry have been found in a mine in the Timmins, Ontario, area of the Canadian Precambrian Shield. Here we show that excesses of (124)Xe, (126)Xe and (128)Xe in the Timmins mine fluids can be linked to xenon isotope changes in the ancient atmosphere and used to calculate a minimum mean residence time for this fluid of about 1.5 billion years. Further evidence of an ancient fluid system is found in (129)Xe excesses that, owing to the absence of any identifiable mantle input, are probably sourced in sediments and extracted by fluid migration processes operating during or shortly after mineralization at around 2.64 billion years ago. We also provide closed-system radiogenic noble-gas ((4)He, (21)Ne, (40)Ar, (136)Xe) residence times. Together, the different noble gases show that ancient pockets of water can survive the crustal fracturing process and remain in the crust for billions of years.

The Bremen mass spectrometric facility for the measurement of helium isotopes, neon, and tritium in water.

We describe the mass spectrometric facility for measuring helium isotopes, neon, and tritium that has been operative at this institute since 1989, and also the sampling and sample preparation steps that precede the mass spectrometric analysis. For water samples in a near-equilibrium with atmospheric air, the facility achieves precision for (3)He/(4)He ratios of+/-0.4% or better, and+/-0.8 % or better for helium and neon concentrations. Tritium precision is typically+/-3 % and the detection limit 10 mTU ( approximately 1.2.10(-3) Bq/kg of pure water). Sample throughputs can reach some thousands per year. These achievements are enabled, among other features, by automation of the measurement procedure and by elaborate calibration, assisted by continual development in detail. To date, we have measured more than 15,000 samples for tritium and 23,000 for helium isotopes and neon, mostly in the context of oceanographic and hydrologic work. Some results of such work are outlined. Even when atmospheric tritium concentrations have become rather uniform, tritium provides water ages if (3)He data are taken concurrently. The technique can resolve tritium concentrations in waters of the pre-nuclear era.

Transport of methane and noble gases during gas push-pull tests in dry porous media.

A field method called the gas push-pull test (GPPT) was previously developed and tested for the in situ quantification of aerobic methane (CH4) oxidation by soil microorganisms. The GPPT consists of an injection followed by extraction of reactant and tracer gases into and out of the soil. Quantification of microbial activities from GPPTs requires insight in the transport of reactant and tracer gases under diverse field conditions. We investigated how the transport of differenttracer gases (He, Ne, and Ar) compares to that of the reactant gas CH4 during GPPTs conducted in a well-defined, dry porous media that mimicked an open system. Transport of gaseous components during GPPT is mainly driven by advection resulting from injection and extraction and diffusion driven by concentration gradients. Regardless of the advective component (selected injection/ extraction, flow rates 0.2-0.8 L min(-1)), diffusion was the dominant transport mechanism for gaseous components. This resulted in dissimilar transport of CH4 and the tracers He and Ne. Numerical simulations of GPPTs showed that similar transport of these components is only achieved at very high injection/extraction rates that, in practice, are not feasible since they would imply extremely short duration times of GPPTs to allow for consumption of a measurable amount of reactant(s) by soil microorganisms. However, Ar transport was similar to that of CH4. Hence, Ar may be a good tracer provided that it is injected at high concentrations (e.g., >25% [v/v]) to overcome its background concentration in soil air. Using moderate injection/ extraction rates (e.g., 0.6 L min(-1)) with injected volumes of 10-30 L will result in GPPT durations of 1-3 h, which would suffice to attain a measurable consumption of reactant(s) in soils having relatively high (e.g., first-order rate constants >0.3 h(-1)) microbial activities.

Isotopic compositions of cometary matter returned by Stardust.

Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.

Enhanced atmospheric loss on protoplanets at the giant impact phase in the presence of oceans.

The atmospheric compositions of Venus and Earth differ significantly, with the venusian atmosphere containing about 50 times as much 36Ar as the atmosphere on Earth. The different effects of the solar wind on planet-forming materials for Earth and Venus have been proposed to account for some of this difference in atmospheric composition, but the cause of the compositional difference has not yet been fully resolved. Here we propose that the absence or presence of an ocean at the surface of a protoplanet during the giant impact phase could have determined its subsequent atmospheric amount and composition. Using numerical simulations, we demonstrate that the presence of an ocean significantly enhances the loss of atmosphere during a giant impact owing to two effects: evaporation of the ocean, and lower shock impedance of the ocean compared to the ground. Protoplanets near Earth's orbit are expected to have had oceans, whereas those near Venus' orbit are not, and we therefore suggest that remnants of the noble-gas rich proto-atmosphere survived on Venus, but not on Earth. Our proposed mechanism explains differences in the atmospheric contents of argon, krypton and xenon on Venus and Earth, but most of the neon must have escaped from both planets' atmospheres later to yield the observed ratio of neon to argon.

The response of a spherical tissue-equivalent proportional counter to different ions having similar linear energy transfer.

The response of a tissue-equivalent proportional counter (TEPC) to different ions having a similar linear energy transfer (LET) has been studied. Three ions, 14N, 20Ne and 28Si, were investigated using the HIMAC accelerator at the National Institute of Radiological Sciences at Chiba, Japan. The calculated linear energy transfer (LET( infinity )) of all ions was 44 +/- 2 keV/microm at the sensitive volume of the TEPC. A particle spectrometer was used to record the charge and position of each incident beam particle. This enabled reconstruction of the location of the track as it passed though the TEPC and ensured that the particle survived without fragmentation. The spectrum of energy deposition events in the TEPC could be evaluated as a function of trajectory through the TEPC. The data indicated that there are many events from particles that did not pass through the sensitive volume. The fraction of these events increased as the energy of the particle increased due to changes in the maximum energy of the delta rays. Even though the LET of the incident particles was nearly identical, the frequency-averaged lineal energy, y(F), as well as the dose-averaged lineal energy, y(D), varied with the velocity of the incident particle. However, both values were within 15% of LET in all cases.

On the origin of noble gases in mantle plumes.

The chemical differences between deep- and shallow-mantle sources of oceanic basalts provide evidence that several distinct components coexist within the Earth's mantle. Most of these components have been identified as recycled in origin. However, the noble-gas signature is still a matter of debate and questions the preservation of primitive regions in the convective mantle. We show that a model where the noble-gas signature observed in Hawaii and Iceland comes from a pristine homogeneous deep layer would imply a primitive (3)He content and (3)He/(22)Ne ratio that are very unlikely. On the contrary, mass balances show that the partly degassed peridotite of a marble-cake mantle can be the noble-gas end-member with an apparent 'primitive'-like composition. This component is mixed with recycled oceanic crust in different proportions in the plume sources and in the shallow mantle. A recycling model of the mantle, involving gravitational segregation of the oceanic crust at the bottom of the mantle, potentially satisfies trace-element as well as noble-gas constraints.

Application of a pulse-discharge helium detector to the determination of neon in air and water.

A pulse-discharge helium detector (Valco, PD-D2-I) is used to measure neon concentrations in air and water. The detection level is 0.5 x 10(-8) g/cm3 (0.2 ppm). Discharge gas doped with neon results in a linear response to the neon mass up to 10(-6) g. For measuring the neon concentration in water, a simple enrichment system is used.

Contributions of icy planetesimals to the Earth's early atmosphere.

Laboratory experiments on the trapping of gases by ice forming at low temperatures implicate comets as major carriers of the heavy noble gases to the inner planets. These icy planetesimals may also have brought the nitrogen compounds that ultimately produced atmospheric N2. However, if the sample of three comets analyzed so far is typical, the Earth's oceans cannot have been produced by comets alone, they require an additional source of water with low D/H. The highly fractionated neon in the Earth's atmosphere may also indicate the importance of non-icy carriers of volatiles. The most important additional carrier is probably the rocky material comprising the bulk of the mass of these planets. Venus may require a contribution from icy planetesimals formed at the low temperatures characteristic of the Kuiper Belt.

Detection of soft X-rays and a sensitive search for noble gases in comet Hale-Bopp.

An image of comet Hale-Bopp (C/1995 O1) in soft x-rays reveals a central emission offset from the nucleus, as well as an extended emission feature that does not correlate with the dust jets seen at optical wavelengths. Neon was found to be depleted in the cometary ice by more than a factor of 25 relative to solar abundance, which suggests that ices in Hale-Bopp formed at (or later experienced) temperatures higher than 25 kelvin. A helium line emission at a wavelength of 584 angstroms was detected and may be attributable to charge transfer of solar wind alpha particles in the cometary coma. Ionized oxygen and another helium line contribute to an emission observed at 538 angstroms.

Effects of absorption by Io on composition of energetic heavy ions.

The Galileo heavy ion counter is sensitive to ions with atomic numbers Z >/= 6 and energies greater than approximately 6 MeV per nucleon. During Galileo's passage through Jupiter's inner magnetosphere, the observed composition of these heavy ions was consistent with the presence of singly ionized iogenic O, Na, and S and highly ionized solar C, O, and Ne. The solar component is absorbed more strongly by Io because its gyroradius is smaller than Io's diameter.

Were micrometeorites a source of prebiotic molecules on the early Earth?

"Interplanetary Dust Particles" with sizes approximately 10 micrometers collected in the stratosphere (IDPs), as well as much larger "giant" micrometeorites retrieved from Antarctic ice melt water (AMMs), are mostly composed of unequilibrated assemblages of minerals, thus being related to primitive unequilibrated meteorites. Two independent evaluations of the mass flux of micrometeorites measuring approximately 50 micrometers to approximately 200 micrometers, recovered from either the Greenland or the Antarctic ice sheets have been reported (approximately 20,000 tons/a). A comparison with recent evaluation of the flux of meteorites reaching the Earth's surface (up to masses of 10,000 tons), indicates that micrometeorites represent about 99.5% of the extraterrestrial material falling on the Earth's surface each year. As they show carbon concentrations exceeding that of the most C-rich meteorite (Orgueil), they are the major contributors of extraterrestrial C-rich matter accreting to the Earth today. Moreover they are complex microstructured aggregates of grains. They contain not only a variety of C-rich matter, such as a new "dirty" magnetite phase enriched in P, S, and minor elements, but also a diversity of potential catalysts (hydrous silicates, oxides, sulfides and metal grains of Fe/Ni composition, etc.). They could have individually functioned on the early Earth, as "micro-chondritic-reactors" for the processing of prebiotic organic molecules in liquid water. Future progress requires the challenging development of meaningful laboratory simulation experiments, and a better understanding of the partial reprocessing of micrometeorites in the atmosphere.

In-situ polymerization PLOT columns I: divinylbenzene.

A novel method for preparation of porous-layer open-tubular (PLOT) columns is described. The method involves a simple and reproducible, straight-forward in-situ polymerization of monomer directly on the metal tube.

Composition of solar flare noble gases preserved in meteorite parent body regolith.

The isotopic composition (long-term average) of solar flare (SF) Ne has been determined by three isotope correlation techniques applied to data measured on chemically etched pyroxene separates prepared from the Kapoeta meteorite, which is known to contain implanted solar gases. The SF 20Ne/22Ne ratio obtained is 11.6 +/- 0.2 and confirms previous determinations of this SF ratio in lunar and meteoritic samples. The same SF Ne composition is also obtained by applying an ordinate intercept technique to the same data set. The ordinate intercept technique was also applied to the Ar and He data, on which the three-isotope correlation technique cannot be applied. The isotopic composition of SF Ar and SF He so obtained are SF 36Ar/38Ar = 4.9 +/- 0.1 and SF 4He/3He = 3800 +/- 200, which are significantly different from the solar wind (SW) Ar and SW He values of approximately 5.35 and approximately 2500, respectively. Correlation between 20Ne/22Ne and 36Ar/38Ar for the same data set also gives a similar SF 36Ar/38Ar ratio of 4.8 +/- 0.2. The determined SF He, Ne and Ar isotopic ratios differ from those in SW by 52%, 17% and 9%, respectively, but the elemental compositions of 4He/36Ar and 20Ne/36Ar do not show obvious differences between SF and SW. The concentration of the SF component in Kapoeta pyroxenes is approximately 20% that of the SW component, which is orders of magnitude higher than expected from SW and SF proton flux measurements. Variations in elemental and isotopic composition of He, Ne and Ar in SF relative to SW are found to correlate well with a (Z/A)2 dependence, indicating a rigidity-dependent particle spectrum in solar flares.