Hydrostratigraphic Interpretation of Test-hole and Surface Geophysical Data, Elkhorn and Loup River Basins, Nebraska, 2008 to 2011

The Elkhorn-Loup Model (ELM) was begun in 2006 to understand the effect of various groundwater-management scenarios on surface-water resources. During phase one of the ELM study, a lack of subsurface geological information was identified as a data gap. Test holes drilled to the base of the aquifer in the ELM study area are spaced as much as 25 miles apart, especially in areas of the western Sand Hills. Given the variable character of the hydrostratigraphic units that compose the High Plains aquifer system, substantial variation in aquifer thickness and characteristics can exist between test holes. To improve the hydrogeologic understanding of the ELM study area, the U.S. Geological Survey, in cooperation with the Nebraska Department of Natural Resources, multiple Natural Resources Districts participating in the ELM study, and the University of Nebraska-Lincoln Conservation and Survey Division, described the subsurface lithology at six test holes drilled in 2010 and concurrently collected borehole geophysical data to identify the base of the High Plains aquifer system. A total of 124 time-domain electromagnetic (TDEM) soundings of resistivity were collected at and between selected test-hole locations during 2008-11 as a quick, non-invasive means of identifying the base of the High Plains aquifer system. Test-hole drilling and geophysical logging indicated the base-of-aquifer elevation was less variable in the central ELM area than in previously reported results from the western part of the ELM study area, where deeper paleochannels were eroded into the Brule Formation. In total, more than 435 test holes were examined and compared with the modeled-TDEM soundings. Even where present, individual stratigraphic units could not always be identified in modeled-TDEM sounding results if sufficient resistivity contrast was not evident; however, in general, the base of aquifer [top of the aquifer confining unit (ACU)] is one of the best-resolved results from the TDEM-based models, and estimates of the base-of-aquifer elevation are in good accordance with those from existing test-hole data. Differences between ACU elevations based on modeled-TDEM and test-hole data ranged from 2 to 113 feet (0.6 to 34 meters). The modeled resistivity results reflect the eastward thinning of Miocene-age and older stratigraphic units, and generally allowed confident identification of the accompanying change in the stratigraphic unit forming the ACU. The differences in elevation of the top of the Ogallala, estimated on the basis of the modeled-TDEM resistivity, and the test-hole data ranged from 11 to 251 feet (3.4 to 77 meters), with two-thirds of model results being within 60 feet of the test-hole contact elevation. The modeled-TDEM soundings also provided information regarding the distribution of Plio-Pleistocene gravel deposits, which had an average thickness of 100 feet (30 meters) in the study area; however, in many cases the contact between the Plio-Pleistocene deposits and the overlying Quaternary deposits cannot be reliably distinguished using TDEM soundings alone because of insufficient thickness or resistivity contrast

A uniform treatment of order of evaluation and aggregate update

The article presents an algorithm for the destructive update optimization in first-order lazy functional languages. The main component of the method is a new static analysis of the order of evaluation of expressions which, compared to other published work, has a much lower complexity and is not restricted to pure lazy evaluation. The other component, which we call reduction to variables, is a method of detecting the variables which denote locations where the result of an expression might be stored.Starting with the operational semantics of the language, we introduce some markers for the values in the basic domain. By choosing appropriately the set of markers M and the method of propagating them during evaluation, we can extract some property of the evaluation in which an expression can participate by looking at the marker of its value. We then define an equivalent denotational semantics and derive the above analyses, in a uniform way, by abstract interpretation over a subdomain of P(M[perpendicular]).Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/30571/1/0000206.pd

In-vehicle exposure to NO2 and PM2.5:A comprehensive assessment of controlling parameters and reduction strategies to minimise personal exposure

Vehicles are the third most occupied microenvironment, other than home and workplace, in developed urban areas. Vehicle cabins are confined spaces where occupants can mitigate their exposure to on-road nitrogen dioxide (NO2) and fine particulate matter (PM2.5) concentrations. Understanding which parameters exert the greatest influence on in-vehicle exposure underpins advice to drivers and vehicle occupants in general. This study assessed the in-vehicle NO2 and PM2.5 levels and developed stepwise general additive mixed models (sGAMM) to investigate comprehensively the combined and individual influences of factors that influence the in-vehicle exposures. The mean in-vehicle levels were 19 ± 18 and 6.4 ± 2.7 μg/m3 for NO2 and PM2.5, respectively. sGAMM model identified significant factors explaining a large fraction of in-vehicle NO2 and PM2.5 variability, R2 = 0.645 and 0.723, respectively. From the model's explained variability on-road air pollution was the most important predictor accounting for 22.3 and 30 % of NO2 and PM2.5 variability, respectively. Vehicle-based predictors included manufacturing year, cabin size, odometer reading, type of cabin filter, ventilation fan speed power, window setting, and use of air recirculation, and together explained 48.7 % and 61.3 % of NO2 and PM2.5 variability, respectively, with 41.4 % and 51.9 %, related to ventilation preference and type of filtration media, respectively. Driving-based parameters included driving speed, traffic conditions, traffic lights, roundabouts, and following high emitters and accounted for 22 and 7.4 % of in-vehicle NO2 and PM2.5 exposure variability, respectively. Vehicle occupants can significantly reduce their in-vehicle exposure by moderating vehicle ventilation settings and by choosing an appropriate cabin air filter

Evaluation of detailed aromatic mechanisms (MCMv3 and MCMv3.1) against environmental chamber data

International audienceA high quality dataset on the photo-oxidation of benzene, toluene, p-xylene and 1,3,5-trimethylbenzene has been obtained from experiments in the European Photoreactor (EUPHORE), a large outdoor environmental reaction chamber. The experiments were designed to test sensitive features of detailed aromatic mechanisms, and the dataset has been used to evaluate the performance of the Master Chemical Mechanism Version 3 (MCMv3). An updated version (MCMv3.1) was constructed based on recent experimental data, and details of its development are described in a companion paper. The MCMv3.1 aromatic mechanisms have also been evaluated using the EUPHORE dataset. Significant deficiencies have been identified in the mechanisms, in particular: 1) an over-estimation of the ozone concentration, 2) an under-estimation of the NO oxidation rate, 3) an under-estimation of OH. The use of MCMv3.1 improves the model-measurement agreement in some areas but significant discrepancies remain

NO2 levels inside vehicle cabins with pollen and activated carbon filters::A real world targeted intervention to estimate NO2 exposure reduction potential

Traffic related nitrogen dioxide (NO2) poses a serious environmental and health risk factor in the urban environment. Drivers and vehicle occupants in general may have acute exposure to NO2 levels. In order to identify key controllable measures to reduce vehicle occupant's exposure, this study measures NO2 exposure inside ten different vehicles under real world driving conditions and applies a targeted intervention by replacing previously used filters with new standard pollen and new activated carbon cabin filters. The study also evaluates the efficiency of the latter as a function of duration of use. The mean in-vehicle NO2 exposure across the tested vehicles, driving the same route under comparable traffic and ambient air quality conditions, was 50.8 ± 32.7 μg/m3 for the new standard pollen filter tests and 9.2 ± 8.6 μg/m3 for the new activated carbon filter tests. When implementing the new activated carbon filters, overall we observed significant (p < 0.05) reductions by 87 % on average (range 80 - 94.2 %) in the in-vehicle NO2 levels compared to the on-road concentrations. We further found that the activated carbon filter NO2 removal efficiency drops by 6.8 ± 0.6 % per month; showing a faster decay in removal efficiency after the first 6 months of use. These results offer novel insights into how the general population can control and reduce their exposure to traffic related NO2. The use and regular replacement of activated carbon cabin air filters represents a relatively inexpensive method to significantly reduce in-vehicle NO2 exposure

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO₂, H₂O and dimethyl sulfide

Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting sulfate aerosol) and NO2 processing (affecting NOx levels) depends critically upon the fate of the SCIs with respect to reaction with water and decomposition. Here, we have investigated the removal of SO2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene-derived SCIs with H2O. Under excess SO2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (+/-0.03). The observed SO2 removal kinetics are consistent with a relative rate constant, k (SCI + H2O) = k (SCI + SO2), of 3.1 (+/-0.5) x 10(-5) for isoprene-derived SCIs. The relative rate constant for k (SCI decomposition) = k (SCI + SO2) is 3.0 (+/-3.2) x 10(11) cm(-3). Uncertainties are +/-2 sigma and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprenederived SCIs are unlikely to make a substantial contribution to gas-phase SO2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO2 removal in the isopreneozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCIs and dimethyl sulfide (DMS); the observed SO2 removal kinetics are consistent with a relative rate constant, k (SCI + DMS) = k (SCI + SO2), of 3.5 (+/-1.8). This result suggests that SCIs may contribute to the oxidation of DMS in the atmosphere and that this process could therefore influence new particle formation in regions impacted by emissions of unsaturated hydrocarbons and DMS

Chemically-Mediated Roostmate Recognition and Roost Selection by Brazilian Free-Tailed Bats (Tadarida brasiliensis)

BACKGROUND: The Brazilian free-tailed bat (Tadarida brasiliensis) is an exceptionally social and gregarious species of chiropteran known to roost in assemblages that can number in the millions. Chemical recognition of roostmates within these assemblages has not been extensively studied despite the fact that an ability to chemically recognize individuals could play an important role in forming and stabilizing complex suites of social interactions. METHODOLOGY/PRINCIPAL FINDINGS: Individual bats were given a choice between three roosting pouches: one permeated with the scent of a group of roostmates, one permeated with the scent of non-roostmates, and a clean control. Subjects rejected non-roostmate pouches with greater frequency than roostmate pouches or blank control pouches. Also, bats chose to roost in the roostmate scented pouches more often than the non-roostmate or control pouches. CONCLUSIONS/SIGNIFICANCE: We demonstrated that T. brasiliensis has the ability to chemically recognize roostmates from non-roostmates and a preference for roosting in areas occupied by roostmates. It is important to investigate these behaviors because of their potential importance in colony dynamics and roost choice

Measurements of photo-oxidation products from the reaction of a series of alkyl-benzenes with hydroxyl radicals during EXACT using comprehensive gas chromatography

Photo-oxidation products from the reaction of a series of alkyl-benzenes, (benzene, toluene, <i>p</i>-xylene and 1,3,5-trimethyl-benzene) with hydroxyl radicals in the presence of NO_x have been investigated using comprehensive gas chromatography (GCxGC). A GCxGC system has been developed which utilises valve modulation and independent separations as a function of both volatility and polarity. A number of carbonyl-type compounds were identified during a series of reactions carried out at the European Photoreactor (EUPHORE), a large volume outdoor reaction chamber in Valencia, Spain. Experiments were carried as part of the EXACT project (<b>E</b>ffects of the o<b>X</b>idation of <b>A</b>romatic <b>C</b>ompounds in the <b>T</b>roposphere). Two litre chamber air samples were cryo-focused, with a sampling frequency of 30 minutes, allowing the evolution of species to be followed over oxidation periods of 3-6 hours. To facilitate product identification, several carbonyl compounds, which were possible products of the photo-oxidation, were synthesised and used as reference standards.<br> <br> For toluene reactions, observed oxygenated intermediates found included the co-eluting pair <font face='Symbol'>a</font>-angelicalactone/4-oxo-2-pentenal, maleic anhydride, citraconic anhydride, benzaldehyde and <i>p</i>-methyl benzoquinone. In the <i>p</i>-xylene experiment, the products identified were E/Z-hex-3-en-2,5-dione and citraconic anhydride. For 1,3,5-TMB reactions, the products identified were 3,5-dimethylbenzaldehyde, 3,5-dimethyl-3H-furan-2-one and 3-methyl-5-methylene-5H-furan-2-one. Preliminary quantification was carried out on identified compounds using liquid standards. Comparison of FTIR and GCxGC for the measurement of the parent aromatics generally showed good agreement. Comparison of the concentrations observed by GCxGC to concentration-time profiles simulated using the Master Chemical Mechanism, MCMv3, demonstrates that this mechanism significantly over-predicts the concentrations of many product compounds and highlights the uncertainties which exist in our understanding of the atmospheric oxidation of aromatics

The atmospheric impacts of monoterpene ozonolysis on global stabilised Criegee intermediate budgets and SO2 oxidation : experiment, theory and modelling

The gas-phase reaction of alkenes with ozone is known to produce stabilised Criegee intermediates (SCIs). These biradical/zwitterionic species have the potential to act as atmospheric oxidants for trace pollutants such as SO₂, enhancing the formation of sulfate aerosol with impacts on air quality and health, radiative transfer and climate. However, the importance of this chemistry is uncertain as a consequence of limited understanding of the abundance and atmospheric fate of SCIs. In this work we apply experimental, theoretical and numerical modelling methods to quantify the atmospheric impacts, abundance and fate of the structurally diverse SCIs derived from the ozonolysis of monoterpenes, the second most abundant group of unsaturated hydrocarbons in the atmosphere. We have investigated the removal of SO₂ by SCIs formed from the ozonolysis of three atmospherically important monoterpenes (<i>α</i>-pinene, <i>β</i>-pinene and limonene) in the presence of varying amounts of water vapour in large-scale simulation chamber experiments that are representative of boundary layer conditions. The SO₂ removal displays a clear dependence on water vapour concentration, but this dependence is not linear across the range of [H₂O] explored. At low [H₂O] a strong dependence of SO₂ removal on [H₂O] is observed, while at higher [H₂O] this dependence becomes much weaker. This is interpreted as being caused by the production of a variety of structurally (and hence chemically) different SCIs in each of the systems studied, which displayed different rates of reaction with water and of unimolecular rearrangement or decomposition. The determined rate constants, <i>k</i>(SCI+H₂O), for those SCIs that react primarily with H₂O range from 4 to 310  ×  10⁻¹⁵ cm³ s⁻¹. For those SCIs that predominantly react unimolecularly, determined rates range from 130 to 240 s⁻¹. These values are in line with previous results for the (analogous) stereo-specific SCI system of <i>syn</i>-/<i>anti</i>-CH₃CHOO. The experimental results are interpreted through theoretical studies of the SCI unimolecular reactions and bimolecular reactions with H₂O, characterised for <i>α</i>-pinene and <i>β</i>-pinene at the M06-2X/aug-cc-pVTZ level of theory. The theoretically derived rates agree with the experimental results within the uncertainties. A global modelling study, applying the experimental results within the GEOS-Chem chemical transport model, suggests that &gt; 97 % of the total monoterpene-derived global SCI burden is comprised of SCIs with a structure that determines that they react slowly with water and that their atmospheric fate is dominated by unimolecular reactions. Seasonally averaged boundary layer concentrations of monoterpene-derived SCIs reach up to 1.4  ×  10⁴ cm⁻³ in regions of elevated monoterpene emissions in the tropics. Reactions of monoterpene-derived SCIs with SO₂ account for &lt; 1 % globally but may account for up to 60 % of the gas-phase SO₂ removal over areas of tropical forests, with significant localised impacts on the formation of sulfate aerosol and hence the lifetime and distribution of SO₂