Assessment of alternative adsorption models and global sensitivity analysis to characterize hexavalent chromium loss from soil to surface runoff

We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AIC_C] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.     

Comparative Study of the Three-Dimensional Thermodynamical Structure of the Inner Corona of Solar Minimum Carrington Rotations 1915 and 2081

Using differential emission measure tomography (DEMT) based on time series of EUV images, we carry out a quantitative comparative analysis of the three-dimensional (3D) structure of the electron density and temperature of the inner corona (\(r<1.25\,\mathrm{R}_{\odot}\)) between two specific rotations selected from the last two solar minima, namely Carrington Rotations (CR)1915 and CR-2081. The analysis places error bars on the results because of the systematic uncertainty of the sources. While the results for CR-2081 are characterized by a remarkable north–south symmetry, the southern hemisphere for CR-1915 exhibits higher densities and temperatures than the northern hemisphere. The core region of the streamer belt in both rotations is found to be populated by structures whose temperature decreases with height (called “down loops” in our previous articles). They are characterized by plasma \(\beta\gtrsim1\), and may be the result of the efficient dissipation of Alfvén waves at low coronal heights. The comparative analysis reveals that the low latitudes of the equatorial streamer belt of CR-1915 exhibit higher densities than for CR-2081. This cannot be explained by the systematic uncertainties. In addition, the southern hemisphere of the streamer belt of CR-1915 is characterized by higher temperatures and density scale heights than for CR-2081. On the other hand, the coronal hole region of CR-1915 shows lower temperatures than for CR-2081. The reported differences are in the range \({\approx}\,10\,\mbox{--}\,25\%\), depending on the specific physical quantity and region that is compared, as fully detailed in the analysis. For other regions and/or physical quantities, the uncertainties do not allow assessing the thermodynamical differences between the two rotations. Future investigation will involve a DEMT analysis of other Carrington rotations selected from both epochs, and also a comparison of their tomographic reconstructions with magnetohydrodynamical simulations of the inner corona.     

Orbital Elements of 2004 Perseid Meteoroids Perturbed by Jupiter

Jupiter and Saturn produce important gravitational impulses on meteoroids released by comet 109P/Swift-Tuttle. The meteoroids from this comet once released follow retrograde orbits that during their periodic approaches to these planets (within 1.6 and 0.9 A.U., respectively) are impulsed gaining orbital energy. This perturbation effect is translated into a net inward shift in the node of the perturbed meteoroids. Such geometry with Jupiter occurred in 2004 over a meteoroid trail ejected by this comet during the 1862 A.D. return of the comet to perihelion. In order to study the predicted outburst produced by one-revolution meteoroids, the Spanish Photographic Meteor Network (SPMN) performed an extensive campaign. As a part of this observational effort here are presented 10 accurate meteoroid orbits. We discuss their origin by comparing them with the theoretical orbital elements of the dust trails intercepting the Earth during the 2004 Perseid return.     

Site Effects Study in the Serravalle Village (NE Italy) by Means of Spectral Ratios Analyses Relatively to Multiple Reference Sites

The area of Serravalle, sited in the northern part of the town of Vittorio Veneto (TV), NE Italy, has been the target of a seismic microzonation campaign. 10 seismic stations have been deployed for a 7 months period to record in continuous mode. Three stations were installed on bedrock outcrops and seven on sedimentary sites with variable cover thickness. Spectral analyses have been performed on the collected data-set using the Generalized Inversion Technique (GIT, e.g. Andrews, 1986). In particular, spectral ratios have been calculated for each station relatively to the average of the three reference, bedrock sites. The spectral ratios provide quantitative estimates of the seismic motion amplifications which occur in each of the monitored sites. Two sites show high values of amplification, 5 times larger than signal amplitude at the reference sites, in correspondence of well discernible peak frequencies of 5 Hz. Results for the other stations show smaller amounts of site amplification spreading over a broad range of frequencies. Sites where the highest amplifications were recorded all lie on the left bank of the Meschio River and in areas farther away from its outlet into the plain correlating with the presence of thick layers of Quaternary deposits.     

Paleoecology and radiocarbon dating of the Pleistocene megafauna of the Brazilian Intertropical Region

During the Pleistocene a fauna composed of large (biomass > 44 kg) and giant mammals (biomass > 1000 kg) that are usually associated with open environments lived in the Brazilian Intertropical Region. We present here new information concerning the paleoecology and chronology of some species of this megafauna. Carbon isotope analyses were performed for a better understanding of the paleoecology of the species Eremotherium laurillardi (Lund, 1842), Notiomastodon platensis (Ameghino, 1888) and Toxodon platensis (Owen, 1849). The δ¹³C data allow attributing a generalist diet to these species, which varied according to the kind of habitat in which they lived. In more open habitats all species were grazers; in mixed habitats E. laurillardi and T. platensis were mixed feeders, and N. platensis was grazer; and in more closed habitats all species were mixed feeders.     

A DNA tracer used in column tests for hydrogeology applications

Tracing techniques are commonly used to investigate groundwater quality and dynamics, as well as to measure the hydrogeological parameters of aquifers. The last decade has seen a growing interest in environmentally friendly tracers, including single-stranded DNA molecules. In this study, an electrolytic tracer and a synthetic DNA tracer are comparatively evaluated in laboratory scale tests to assess their potential application in field studies aimed at investigating groundwater environments. A real-time quantitative Polymerase Chain Reaction assay was developed and optimized to detect and quantify the DNA tracer, while tracer column tests were performed to investigate the DNA tracer behavior and to compare it to the electrolytic tracer. The results show that the DNA tracer has an almost pure convective flow, while the KCl tracer experiences dispersive behavior. The tracing method proposed can be applied in hydrogeological field studies involving calcareous fractured rock systems, with the DNA tracer particularly suitable in tracing karst systems, which are often characterized by several conduits of flow. To test the DNA tracer in operation, a preliminary test was conducted in the field.     

Groundwater flow model, recharge estimation and sustainability in an arid region of Patagonia, Argentina

The Península Valdés, in northeastern Patagonia, Argentina, is characterised by its arid climate and the lack of perennial watercourses; thus, all economic activities depend on the groundwater resources. Water demand is mainly associated with tourism, which is centralised in Puerto Pirámides and supplied by a water desalination plant, and to sheep farming, supplied by the local aquifer. Due to the exponential growth of tourism, the government is planning to exploit groundwater and convey it by aqueduct to the abovementioned locality. The objectives of this study were to corroborate the conceptual geohydrological model, to develop a mathematical model to simulate the response of the aquifer to different scenarios, and to assess the incidence of water input into the system as a variable—a function that poses difficulties in the models for arid regions. The Visual Modflow 4.1 code was used, calibrating it in trial-and-error mode, changing the recharge and hydraulic conductivity parameters with different variants in the recharge zone and in the inclusion or exclusion of the evapotranspiration module. Results indicate the importance of the recharge analysis by treating rainfall at daily time steps. The adjusted model was exposed to four scenarios with variations in water input and in output by pumping. It can be concluded that under different input conditions, but with a controlled extraction, the system responds in a sustainable manner.     

Using distributed temperature sensing (DTS) technology in acid gas injection design

The use of slickline distributed temperature sensing (SL-DTS) technology is becoming widespread due to its ease of operation and ability to acquire real-time multiple temperature traces inside the wellbore. Injection of treated acid gas (TAG)—a mixture of CO₂ and H₂S—into geologic formations has become an attractive technical and economic option for oil and gas producers and processors who are faced with regulations concerning excess sulfur and greenhouse gas emissions. Acid gas injection (AGI) into geologic formations is more economical and more flexible in dealing with varying TAG compositions than sulfur recovery units (SRUs) using the Claus process. SRUs do not achieve air quality standards and have high operation and maintenance costs. In addition, there is low demand for sulfur and sulfur disposal costs are high. The results of the analysis of SL-DTS data acquired in conjunction with step rate and pressure falloff (PFO) tests are presented in this paper. These tests were conducted to evaluate the injection potential of geologic formations. The injection zone consisted of a carbonate formation characterized by Karst features, vugs, and natural fractures. The SL-DTS data during the initial injection flow rate for the step rate test (SRT) indicated that high permeability zones accepted fluid at lower injection rates. An increasing number of discrete zones began to accept fluid as the injection rate was increased. The results of the SRT provided the fracture pressure of the formation. This information was used to design an AGI program that would avoid fracturing the formation while allowing for the required volume of TAG to be injected. The results of the PFO test provided information on the reservoir pressure and permeability and also indicated the presence of one or more hydraulic fractures. This case study of SL-DTS measurements made during a SRT and a PFO test for the design of an AGI well provides valuable insights into the potential of DTS technology and its use in AGI and carbon capture/sequestration (CCS) operations. Its findings could be applied to analyze injection potential of geological formations not only for AGI projects but also for CCS, and CO₂ enhanced oil recovery opportunities.     

Temperature induced decoupling of enzymatic hydrolysis and carbon remineralization in long-term incubations of Arctic and temperate sediments

Extracellular enzymatic hydrolysis of high-molecular weight organic matter is the initial step in sedimentary organic carbon degradation and is often regarded as the rate-limiting step. Temperature effects on enzyme activities may therefore exert an indirect control on carbon mineralization. We explored the temperature sensitivity of enzymatic hydrolysis and its connection to subsequent steps in anoxic organic carbon degradation in long-term incubations of sediments from the Arctic and the North Sea. These sediments were incubated under anaerobic conditions for 24 months at temperatures of 0, 10, and 20 °C. The short-term temperature response of the active microbial community was tested in temperature gradient block incubations. The temperature optimum of extracellular enzymatic hydrolysis, as measured with a polysaccharide (chondroitin sulfate), differed between Arctic and temperate habitats by about 8-13 °C in fresh sediments and in sediments incubated for 24 months. In both Arctic and temperate sediments, the temperature response of chondroitin sulfate hydrolysis was initially similar to that of sulfate reduction. After 24 months, however, hydrolysis outpaced sulfate reduction rates, as demonstrated by increased concentrations of dissolved organic carbon (DOC) and total dissolved carbohydrates. This effect was stronger at higher incubation temperatures, particularly in the Arctic sediments. In all experiments, concentrations of volatile fatty acids (VFA) were low, indicating tight coupling between VFA production and consumption. Together, these data indicate that long-term incubation at elevated temperatures led to increased decoupling of hydrolytic DOC production relative to fermentation. Temperature increases in marine sedimentary environments may thus significantly affect the downstream carbon mineralization and lead to the increased formation of refractory DOC.