DyeLIF™: A New Direct‐Push Laser‐Induced Fluorescence Sensor System for Chlorinated Solvent DNAPL and Other Non‐Naturally Fluorescing NAPLs

DyeLIF? is a new version of laser‐induced fluorescence (LIF) for high‐resolution three‐dimensional subsurface mapping of nonaqueous phase liquids (NAPLs) in the subsurface. DyeLIF eliminates the requirement that the NAPL contains native fluorophores (such as those that occur in compounds like polynuclear aromatic hydrocarbons [PAHs]) and can therefore be used to detect chlorinated solvents and other nonfluorescing NAPLs that had previously been undetectable with conventional LIF tools. With DyeLIF, an aqueous solution of water and nontoxic hydrophobic dye is continuously injected ahead of the sapphire detection window while the LIF probe is being advanced in the subsurface. If soil containing NAPL is penetrated, the injected dye solvates into the NAPL within a few milliseconds, creating strong fluorescence that is transmitted via fiber‐optic filaments to aboveground optical sensors. A detailed field evaluation of the novel DyeLIF technology was performed at a contaminated industrial site in Lowell, Massachusetts, USA where chlorinated solvent dense nonaqueous phase liquid (DNAPL) persists below the water table in sandy sediments. Continuously cored boreholes were drilled adjacent to 5 of 30 DyeLIF probes that were advanced at that site. The cores were subsampled in high resolution to generate discrete‐depth soil samples as splits at the same depths where DNAPL was detected in the colocated DyeLIF probes. The cores were analyzed above ground using (1) colorimetric screening using hydrophobic dye tests, (2) laboratory extraction and quantitative chemical analysis, (3) “Benchtop” DyeLIF, and (4) volumetric moisture content. Correlation between DyeLIF and aboveground analyses of the soil cores was excellent: 98% agreement with positive DNAPL detections in samples where DNAPL pore saturations were >0.7% (based on quantitative soil analyses) and the ex situ tests. DyeLIF produced the equivalent of one aboveground colorimetric dye test every 0.2 inch (0.5 cm) of probing. With average daily probing of 395 linear feet (120.4 m), this was the equivalent of 12,039 discrete‐depth colorimetric dye tests/day. Because DyeLIF is an in situ measurement, there are no issues with soil core recovery like there would be for conventional ex situ colorimetric dye tests and 100% characterization of the probed intervals is achieved. Tracking the injection rate and pressure of the dye solution provides simultaneous data regarding relative soil permeability, similar to other direct push (DP) hydraulic profiling tools. Conventional LIF is considered the premier DP tool to identify and map NAPL containing PAHs in the subsurface or confirm its absence. While chlorinated solvent DNAPLs at some field sites contain impurities (e.g., solvated greases or oils) that make them detectable with conventional LIF techniques, at other sites, the DNAPL cannot be detected with conventional LIF. At such sites, the injection of a hydrophobic dye ahead of the sapphire window with the DyeLIF system now makes the LIF technology applicable to the many types of NAPLs that were previously invisible using conventional LIF techniques.     

On Methods for In‐Well Nitrate Monitoring Using Optical Sensors

Optical sensors are promising for collecting high resolution in‐well groundwater nitrate monitoring data. Traditional well purging methods are labor intensive, can disturb ambient conditions and yield an unknown blend of groundwater in the samples collected, and obtain samples at a limited temporal resolution (i.e., monthly or seasonally). This study evaluated the Submersible Ultraviolet Nitrate Analyzer (SUNA) for in‐well nitrate monitoring through new applications in shallow overburden and fractured bedrock environments. Results indicated that SUNA nitrate‐N concentration measurements during flow cell testing were strongly correlated (R ² = 0.99) to purged sample concentrations. Vertical profiling of the water column identified distinct zones having different nitrate‐N concentrations in conventional long‐screened overburden wells and open bedrock boreholes. Real‐time remote monitoring revealed dynamic responses in nitrate‐N concentrations following recharge events. The monitoring platform significantly reduced labor requirements for the large amount of data produced. Practitioners should consider using optical sensors for real‐time monitoring if nitrate concentrations are expected to change rapidly, or if a site's physical constraints make traditional sampling programs challenging. This study demonstrates the feasibility of applying the SUNA in shallow overburden and fractured bedrock environments to obtain reliable data, identifies operational challenges encountered, and discusses the range of insights available to groundwater professionals so they will seek to gather high resolution in‐well monitoring data wherever possible.     

Improved Method for Estimating Reaction Rates During Push-Pull Tests

The breakthrough curve obtained from a single-well push-pull test can be adjusted to account for dilution of the injection fluid in the aquifer fluid. The dilution-adjusted breakthrough curve can be analyzed to estimate the reaction rate of a solute. The conventional dilution-adjusted method assumes that the ratios of the concentrations of the nonreactive and reactive solutes in the injection fluid vs. the aquifer fluid are equal. If this assumption is invalid, the conventional method will generate inaccurate breakthrough curves and may lead to erroneous conclusions regarding the reactivity of a solute. In this study, a new method that generates a dilution-adjusted breakthrough curve was theoretically developed to account for any possible combination of nonreactive and reactive solute concentrations in the injection and aquifer fluids. The newly developed method was applied to a field-based data set and was shown to generate more accurate dilution-adjusted breakthrough curves. The improved dilution-adjusted method presented here is simple, makes no assumptions regarding the concentrations of the nonreactive and reactive solutes in the injection and aquifer fluids, and easily allows for estimating reaction rates during push-pull tests.     

Extraterrestrial organic compounds and cyanide in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

Evaluating the water‐soluble organic composition of carbonaceous chondrites is key to understanding the inventory of organic matter present at the origins of the solar system and the subsequent processes that took place inside asteroid parent bodies. Here, we present a side‐by‐side analysis and comparison of the abundance and molecular distribution of aliphatic amines, aldehydes, ketones, mono‐ and dicarboxylic acids, and free and acid‐releasable cyanide species in the CM2 chondrites Aguas Zarcas and Murchison. The Aguas Zarcas meteorite is a recent fall that occurred in central Costa Rica and constitutes the largest recovered mass of a CM‐type meteorite after Murchison. The overall content of organic species we investigated was systematically higher in Murchison than in Aguas Zarcas. Similar to previous meteoritic organic studies, carboxylic acids were one to two orders of magnitude more abundant than other soluble organic compound classes investigated in both meteorite samples. We did not identify free cyanide in Aguas Zarcas and Murchison; however, cyanide species analyzed after acid digestion of the water‐extracted meteorite mineral matrix were detected and quantified at slightly higher abundances in Aguas Zarcas compared to Murchison. Although there were differences in the total abundances of specific compound classes, these two carbonaceous chondrites showed similar isomeric distributions of aliphatic amines and carboxylic acids, with common traits such as a complete suite of structural isomers that decreases in concentration with increasing molecular weight. These observations agree with their petrologic CM type‐2 classification, suggesting that these meteorites experienced similar organic formation processes and/or conditions during parent body aqueous alteration.     

Ballistic capture into distant retrograde orbits around Phobos: an approach to entering orbit around Phobos without a critical maneuver near the moon

This paper discusses an approach for designing missions to Phobos that do not require a critical maneuver in proximity of the moon. A low-energy transfer is designed that utilizes the aspherical mass distribution of Phobos to capture a spacecraft into a distant retrograde orbit (DRO) for the mission duration. The process for generating stable DROs in the Mars–Phobos system is discussed along with the method for generating and surveying a set of ballistic capture trajectories (BCTs) for DROs with altitudes between 0.5 and 14 km above Phobos. Statistical analysis of the BCT set reveals options for designing a mission to the desired DRO. This approach can be used in any three-body system when a significant perturbation is present, such as Phobos’ aspherical co-rotating gravity field.     

Atomistic simulation of the effect of impurities on vacancy migration at the {4 1 0}/[0 0 1] tilt grain boundary of MgO

We present the results of atomistic simulations to calculate the effect of impurities on vacancy migration at the {4 1 0} tilt grain boundary of MgO. We show that impurities within the mantle could significantly modify vacancy migration within the mantle due to segregation to grain boundaries. This segregation increases with increasing impurity size and with increasing pressure. The impurities have little effect on vacancy migration at 0 GPa but at higher pressures the impurities alter the activation energies such that the vacancies prefer to migrate towards them. This suggests that at mantle conditions the vacancies will be pinned both by the compression of the boundary and also the impurities, slowing diffusion. Received: 22 February 1999 / Revised, accepted: 1 June 1999     

Large-scale structure of galaxies in the Ophiuchus region

The large-scale structure around the Ophiuchus cluster of galaxies in the vicinity of the Galactic Centre ( l =05, b =95, cz =8500 km s⁻¹) is investigated on the basis of a galaxy survey and spectroscopic observations made for a 12°×17° area. The galaxy survey was performed using six ESO/SERC Sky Survey Atlas films, and 4021 galaxies were detected in total. Recession velocities were newly obtained for 179 galaxies to make the total number of galaxies in the survey area with known velocities 219.
In the distribution of bright galaxies, we identified seven new clumps of galaxies. Comparing the surface number density of bright galaxies with the Galactic extinction, which is estimated from the 100‐μm flux density in the IRAS Sky Survey Atlas, we demonstrate that the seven clumps are not spurious as a result of the inhomogeneity of the Galactic extinction. Among the seven clumps, two are found to be clusters and four to be groups on the basis of the histogram of recession velocities and the number of member galaxies. The Ophiuchus cluster, two newly identified clusters, and four groups are all concentrated at 9000 km s⁻¹. Field galaxies are also distributed centred at 8500 km s⁻¹. Hence field galaxies occupy a common three-dimensional region with galaxies in the clusters and groups, and altogether they form a large-scale structure of supercluster size. As opposed to the overdensity in the supercluster region, the mean number density of galaxies in the velocity range 0–5000 km s⁻¹ is only 25 per cent of the mean number density of the Universe, comparable with the density of the well-known Böotes void. Hence this nearby three-dimensional region in Ophiuchus is a void of galaxies also.     

Sensitivity experiments for polar low forecasting with the CMC mesoscale finite‐element model

Abstract

High‐resolution versions of the Canadian operational regional finite‐element model (RFE) have been developed to assess their potential in simulating mesoscale, difficult‐to‐forecast and potentially dangerous weather systems commonly referred to as polar lows. The operational (1989) 100‐km version and a 50‐km version of the model have been run for two different polar low cases: one over Hudson Bay and one over Davis Strait. More integrations have also been performed on the Hudson Bay event both at 50 and 25 km to assess the model sensitivity to ice cover. As expected, the reduction in spatial truncation errors provided by the increase in resolution results in a better simulation of the systems. Moreover, when run at higher resolutions the model shows a significant sensitivity to ice cover. The results of the ice‐cover experiments also put into perspective the interaction between the heat and moisture fluxes at the surface, the low‐level wind structure, and the relation of these to the development of the polar low. This study suggests that the improved forecast accuracy obtained from increased resolution is limited by the correctness of the analysis of the ice cover, which acts as a stationary forcing for the entire forecast period.     

Shifts in the thermal niche of almond under climate change

Delineating geographic shifts in crop cultivation under future climate conditions provides information for land use and water management planning, and insights to meeting future demand. A suitability modeling approach was used to map the thermal niche of almond cultivation and phenological development across the Western United States (US) through the mid-21st century. The Central Valley of California remains thermally suitable for almond cultivation through the mid-21st century, and opportunities for expansion appear in the Willamette Valley of western Oregon, which is currently limited by insufficient heat accumulation. Modeled almond phenology shows a compression in reproductive development under future climate. By the mid-21st century, almond phenology in the Central Valley showed ~?2-week delay in chill accumulation and ~?1- and ~?2.5-week advance in the timing of bloom and harvest, respectively. Although other climatic and non-climatic restrictions to almond cultivation may exist, these results highlight opportunities for shifts in the geography of high-value cropping systems, which may influence growers’ long-term land use decisions, and shape regional water and agricultural industry discussions regarding climate change adaptation options.