Modeling Single Well Injection-Withdrawal (SWIW) Tests for Characterization of Complex Fracture-Matrix Systems

The ability to reliably predict flow and transport in fractured porous rock is an essential condition for performance evaluation of geologic (underground) nuclear waste repositories. In this report, a suite of programs (TRIPOLY code) for calculating and analyzing flow and transport in two-dimensional fracture-matrix systems is used to model single-well injection-withdrawal (SWIW) tracer tests. The SWIW test, a tracer test using one well, is proposed as a useful means of collecting data for site characterization, as well as estimating parameters relevant to tracer diffusion and sorption. After some specific code adaptations, we numerically generated a complex fracture-matrix system for computation of steady-state flow and tracer advection and dispersion in the fracture network, along with solute exchange processes between the fractures and the porous matrix. We then conducted simulations for a hypothetical but workable SWIW test design and completed parameter sensitivity studies on three physical parameters of the rock matrix - namely porosity, diffusion coefficient, and retardation coefficient - in order to investigate their impact on the fracture-matrix solute exchange process. Hydraulic fracturing, or hydrofracking, is also modeled in this study, in two different ways: (1) by increasing the hydraulic aperture for flow in existing fractures and (2) by adding a new set of fractures to the field. The results of all these different tests are analyzed by studying the population of matrix blocks, the tracer spatial distribution, and the breakthrough curves (BTCs) obtained, while performing mass-balance checks and being careful to avoid some numerical mistakes that could occur. This study clearly demonstrates the importance of matrix effects in the solute transport process, with the sensitivity studies illustrating the increased importance of the matrix in providing a retardation mechanism for radionuclides as matrix porosity, diffusion coefficient, or retardation coefficient increase. Interestingly, model results before and after hydrofracking are insensitive to adding more fractures, while slightly more sensitive to aperture increase, making SWIW tests a possible means of discriminating between these two potential hydrofracking effects. Finally, we investigate the possibility of inferring relevant information regarding the fracture-matrix system physical parameters from the BTCs obtained during SWIW testing

Analysis of the iron coatings formed during marcasite and arsenopyrite oxidation at neutral-alkaline conditions

In order to study the nature of the precipitates formed on arsenopyrite and marcasite after reacting with neutral to alkaline solutions, a combination of techniques including Scanning Electron Microscope-Energy Dispersive Spectroscopy (SEM-EDS), X-ray Photoelectron Spectroscopy (XPS) and synchrotron-based techniques such as micro-X-Ray diffraction (µXRD) and Micro-X-ray Absorption Near Edge Structure (µXANES) have been used. The results showed that the oxidation of marcasite and arsenopyrite under neutral to alkaline conditions leads to the formation of an Fe rich coating which seems to prevent the oxidation of these sulphides. SEM observations confirmed the presence newly-formed phases after the sulphides reaction under the studied conditions. XPS analysis showed that iron, sulphur and arsenic in the case of the arsenopyrite are in oxidized states in the sulphide surfaces. The microscale analysis of the S and Fe speciation performed by µXANES suggested that due to the sulphide oxidation an increase in the oxidation state of those elements took place together with an increase of the sulphate content in the surface layer (grain boundary). Micro-X-ray diffraction results indicated that goethite (a-FeOOH) is the only crystalline newly-formed phase when the reaction occurs at pH 12 whereas at lower pH the products formed on the sulphide surfaces seem to be poorly crystalline and they do not contribute to the diffraction effects in the XRD diagrams

Two-step analytical procedure for the characterization and quantification of metal soaps and resinates in paint samples

Metal soaps and resinates are known to be spontaneously formed in artistic paintings, as a product of the reaction between aliphatic and terpenoid acids released by hydrolysis and oxidation of the organic media and certain cations contained in some inorganic pigments. In this paper we present an optimization and the validation of a GC/MS method for the qualitative and quantitative analysis of mixtures of terpenoid acids and aliphatic mono and dicarboxylic acids and metal carboxylates of terpenoid and aliphatic mono and dicarboxylic acids in the same paint microsample. This is based on a two-step analytical approach entailing the subsequent use of two silylating agents, N,O-bis(trimethylsilyl)trifluoroacetamide for the analysis of free acids and metal carboxylates, and 1,1,1,3,3,3-hexamethyldisilazane for the analysis of free acids. The application of this approach is possible because of the good stability at room temperature of the TMS derivatives of aliphatic and terpenoid species, characterized by high boiling points and relatively low vapour pressures. The method was then applied to the characterization of samples collected from two reference paint layers aged for 20 years, a paint sample taken from a pulpit, and sample of the varnish coating of a wooden writing desk, both from the second half of the seventeenth century

Spectroscopic techniques and the conservation of artists’ acrylic emulsion paints

Artists’ acrylic emulsion paints are used in many contexts such as paintings, murals, sculptures, works on paper and mixed media; and are forming increasing proportions of modern and contemporary art collections. Although acrylic emulsion paints have been the focus of museum-led research over the past decade, the impact of artists’ technique and conservation treatment on the upper-most surface of these paints remains essentially unexplored ; This paper summarises previous studies using vibrational (FTIR) spectroscopy and presents initial assessments of paint surfaces using X-ray spectroscopies (XPS and NEXAFS) aimed at characterising artists’ acrylic paint film surfaces after natural ageing and wet surface cleaning treatment. Both techniques were found to be well suited for surface-sensitive investigations of the organic materials associated with artists’ acrylic paints, including explorations into: (A) cleaning system residues, (B) surfactant extraction from paint surfaces, (C) the identification of migrated surfactant, and (D) monitoring pigment changes at the paint/air interface of paint films ; It has been shown is that these X-ray spectroscopic techniques can be used for the analysis of almost purely organic materials in a way that complements mass spectroscopic techniques, FTIR and XRF. This investigation forms part of broader, currently ongoing, multi-technique investigation into the properties of artists’ acrylic paints and development of conservation treatments for works-of-art made with these materials

Point of care coagulometry in prehospital emergency care: an observational study

Background: Haemostatic impairment can have a crucial impact on the outcome of emergency patients, especially in cases of concomitant antithrombotic drug treatment. In this prospective observational study we used a point of care (POC) coagulometer in a prehospital physician-based emergency medical system in order to test its validity and potential value in the treatment of emergency patients. Methods: During a study period of 12 months, patients could be included if venous access was mandatory for further treatment. The POC device CoaguChek® was used to assess international normalized ratio (INR) after ambulance arrival at the scene. Results were compared with in-hospital central laboratory assessment of INR. The gain of time was analysed as well as the potential value of POC testing through a questionnaire completed by the responsible prehospital emergency physician. Results: A total of 103 patients were included in this study. POC INR results were highly correlated with results of conventional assessment of INR (Bland-Altman-bias: 0.014). Using a cutoff value of INR >1.3, the device’s sensitivity to detect coagulopathy was 100 % with a specificity of 98.7 %. The median gain of time was 69 min. Treating emergency physicians considered the value of prehospital POC INR testing ‘high’ in 9 % and ‘medium’ in 21 % of all patients. In patients with tracer diagnosis ‘neurology’, the value of prehospital INR assessment was considered ‘high’ or ‘medium’ (63 %) significantly more often than in patients with non-neurological tracer diagnoses (24 %). Conclusions: Assessment of INR through a POC coagulometer is feasible in prehospital emergency care and provides valuable information on haemostatic parameters in patients. Questionnaire results suggest that POC INR testing may present a valuable technique in selected patients. Whether this information translates into an improved management of respective patients has to be evaluated in further studies

Postoperative ileus concealing intra-abdominal complications in enhanced recovery programs—a retrospective analysis of the GRACE database

Purpose Postoperative ileus (POI) occurrence within enhanced recovery programs (ERPs) has decreased. Also, intra-abdominal complications (IAC) such as anastomotic leakage (AL) generally present late. The aim was to characterize the link between POI and the other complications occurring after surgery. Methods This retrospective analysis of a prospective database was conducted by the Francophone Group for Enhanced Recovery after Surgery. POI was considered to be present if gastrointestinal functions had not been recovered within 3 days following surgery or if a nasogastric tube replacement was required. Results Of the 2773 patients who took part in the study, 2335 underwent colorectal resections (83.8%) for cancer, benign tumors, inflammatory bowel disease, and diverticulosis. Among the 2335 patients, 309 (13.2%) experienced POI, including 185 (59.9%) cases of secondary POI. Adjusted for well-known risk factors (male gender, need for stoma, right hemicolectomy, surgery duration, laparotomy, and conversion to open surgery), POI was associated with abdominal complications (OR = 4.55; 95% confidence interval (CI): 3.30–6.28), urinary retention (OR = 1.75; 95% CI: 1.05–2.92), pulmonary complications (OR = 4.55; 95% CI: 2.04–9.97), and cardiological complications (OR = 3.01; 95% CI: 1.15–8.02). Among the abdominal complications, AL and IAC were most strongly associated with POI (respectively, OR = 5.97; 95% CI: 3.74–8.88 and OR = 5.76; 95% CI: 3.56–10.62). Conclusion Within ERPs, POI should not be considered as usual. There is a significant link between POI and IAC. Since POI is an early-onset clinical sign, its occurrence should alert the physician and prompt them to consider performing CT scans in order to investigate other potential morbidities