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Long-term distributed temperature sensing monitoring for near-wellbore gas migration and gas hydrate formation

Well integrity monitoring has always been a critical component of subsurface oil and gas operations. Distributed fiber-optic sensing is an emerging technology that shows great promise for monitoring processes, both in boreholes and in other settings. In this study, we present a case study of using distributed temperature sensing (DTS) technology to monitor a cemented and plugged well in the Alaska North Slope (ANS). The well was drilled as part of a long-term gas hydrate study, and the downhole DTS data were recorded over a period of approximately 2 years. By applying a temporal gradient and removing instrument instability noise, we reveal subtle (<0.001°C/h) thermal anomalies, which are characterized by brief warming periods followed by longer cooling periods at discrete depths along the borehole. The observed coherent events show an upward trajectory from deeper formations into the overlying permafrost interval, with the thermal anomalies concentrated in relatively coarse-grained sandstone layers. We also observe that the upward migration rate of the DTS anomalies varies with formation lithology and that there is a spatial and temporal correlation between the subsurface events and measured wellhead annular pressures. We interpret that the observed warming events represent the exothermic process of gas hydrate formation that is occurring in association with the upward migration of gas outside the well casing, and this interpretation is confirmed by numerical simulations. These observations demonstrate the ability of suitably processed DTS data to detect subtle processes and highlight the value of DTS technologies for wellbore integrity monitoring.

Alaska

Development and evaluation of a gas chromatographic method for the determination of triazine herbicides in natural water samples

A multi-residue method is described for the determination o triazine herbicides in natural water samples. The technique uses solvent extraction followed by gas chromatographic separation and detection employing nitrogen-selective devices. Seven compounds can be determined simultaneously at a nominal detection limit of 0.1 μg/L in a 1-litre sample. Three different natural water samples were used for error analysis via evaluation of recovery efficiencies and estimation of overall method precision. As an alternative to liquid-liquid partition (solvent extraction) for removal of compounds of interest from water, solid-phase extraction (SPE) techniques employing chromatographic grade silicas with chemically modified surfaces have been examined. SPE is found to provide rapid and efficient concentration with quantitative recovery of some triazine herbicides from natural water samples. Concentration factors of 500 to 1000 times are obtained readily by the SPE technique.

International Journal of Environmental Analytical

Determination of Antimycin-A in water by liquid chromatographic/mass spectrometry: single-laboratory validation

An LC/MS method was developed and validated for the quantitative determination and confirmation of antimycin-A (ANT-A) in water from lakes or streams. Three different water sample volumes (25, 50, and 250 mL) were evaluated. ANT-A was stabilized in the field by immediately extracting it from water into anhydrous acetone using SPE. The stabilized concentrated samples were then transported to a laboratory and analyzed by LC/MS using negative electrospray ionization. The method was determined to have adequate accuracy (78 to 113% recovery), precision (0.77 to 7.5% RSD with samples &ge;500 ng/L and 4.8 to 17% RSD with samples &le;100 ng/L), linearity, and robustness over an LOQ range from 8 to 51 600 ng/L.

Journal of AOAC International

On the size of the flare associated with the solar proton event in 774 AD

The 774 AD solar proton event (SPE) detected in cosmogenic nuclides had an inferred >1 GV (>430 MeV) fluence estimated to have been ~30–70 times larger than that of the 1956 February 23 ground level event (GLE). The 1956 GLE was itself ~2.5 times larger at >430 MeV than the episode of strong GLE activity from 1989 August–October. We use an inferred soft X-ray (SXR) class of X20 ± 10 for the 1956 February 23 eruptive flare as a bridge to the source flare for the 774 SPE. A correlation of the >200 MeV proton fluences of hard-spectra post-1975 GLEs with the SXR peak fluxes of their associated flares yields an SXR flare class of X285 ± 140 (bolometric energy of ~(1.9 ± 0.7) × 10 33 erg) for the 774 flare. This estimate is within theoretical determinations of the largest flare the Sun could produce based on the largest spot group yet observed. Assuming a single eruptive flare source for the 774 SPE, the above estimate indicates that the Sun can produce a threshold-level 10 33 erg superflare. If the 774 event originated in two closely timed, equal-fluence SPEs, the inferred flare size drops to X180 ± 90 (~(1.4 ± 0.5) × 10 33 erg). We speculate on favorable solar conditions that can lead to enhanced shock acceleration of high-energy protons in eruptive flares.

Astrophysical Journal

Simplified method for detecting tritium contamination in plants and soil

Cost-effective methods are needed to identify the presence and distribution of tritium near radioactive waste disposal and other contaminated sites. The objectives of this study were to (i) develop a simplified sample preparation method for determining tritium contamination in plants and (ii) determine if plant data could be used as an indicator of soil contamination. The method entailed collection and solar distillation of plant water from foliage, followed by filtration and adsorption of scintillation-interfering constituents on a graphite-based solid phase extraction (SPE) column. The method was evaluated using samples of creosote bush [ Larrea tridentata (Sessé & Moc. ex DC.) Coville], an evergreen shrub, near a radioactive disposal area in the Mojave Desert. Laboratory tests showed that a 2-g SPE column was necessary and sufficient for accurate determination of known tritium concentrations in plant water. Comparisons of tritium concentrations in plant water determined with the solar distillation–SPE method and the standard (and more laborious) toluene-extraction method showed no significant difference between methods. Tritium concentrations in plant water and in water vapor of root-zone soil also showed no significant difference between methods. Thus, the solar distillation–SPE method provides a simple and cost-effective way to identify plant and soil contamination. The method is of sufficient accuracy to facilitate collection of plume-scale data and optimize placement of more sophisticated (and costly) monitoring equipment at contaminated sites. Although work to date has focused on one desert plant, the approach may be transferable to other species and environments after site-specific experiments.

Journal of Environmental Quality

Monitoring sea lamprey pheromones and their degradation using rapid stream-side extraction coupled with UPLC-MS/MS

Pheromones guide adult sea lamprey (Petromyzon marinus) to suitable spawning streams and mates, and therefore, when quantified, can be used to assess population size and guide management. Here, we present an efficient sample preparation method where 100 mL of river water was spiked with deuterated pheromone as an internal standard and underwent rapid field-based SPE and elution in the field. The combination of field extraction with laboratory UPLC-MS/MS reduced the sample consumption from 1 to 0.1 L, decreased the sample process time from more than 1 h to 10 min, and increased the precision and accuracy. The sensitivity was improved more than one order of magnitude compared with the previous method. The influences of experimental conditions were assessed to optimize the separation and peak shapes. The analytical method has been validated by studies of stability, selectivity, precision, and linearity and by the determination of the limits of detection and quantification. The method was used to quantify pheromone concentration from five streams tributary to Lake Ontario and to estimate that the environmental half-life of 3kPZS is about 26 h.

Journal of Separation Science

Phylogenetic conservatism in plant phenology

Phenological events – defined points in the life cycle of a plant or animal – have been regarded as highly plastic traits, reflecting flexible responses to various environmental cues. The ability of a species to track, via shifts in phenological events, the abiotic environment through time might dictate its vulnerability to future climate change. Understanding the predictors and drivers of phenological change is therefore critical. Here, we evaluated evidence for phylogenetic conservatism – the tendency for closely related spe-cies to share similar ecological and biological attributes – in phenological traits across flowering plants. We aggregated published and unpublished data on timing of first flower and first leaf, encompassing ~4000 species at 23 sites across the Northern Hemisphere. We reconstructed the phylogeny for the setof included species, first, using the software program Phylomatic, and second, from DNA data. We then quantified phylogenetic conservatism in plant phenology within and across sites. We show that more closely related species tend to flower and leaf at similar times. By contrastingmean flowering times within and across sites, however, we illustrate that it is not the time of yearthat is conserved, but rather the phenological responses to a common set of abiotic cues. Our findings suggest that species cannot be treated as statistically independent when modelling phenological responses. Synthesis. Closely related species tend to resemble each other in the timing of their life-history events, a likely product of evolutionarily conser ved responses to environmental cues. The search for the underlying drivers of phenology must therefore account for species’ shared evolutionary histories.

Journal of Ecology