Room-Temperature Monitoring of CH4 and CO2 Using a Metal-Organic Framework-Based QCM Sensor Showing Inherent Analyte Discrimination.

The detection of methane and carbon dioxide is of growing importance due to their negative impact on global warming. This is true for both environmental monitoring and leak detection in industrial processes. Although solid-state sensors are technologically mature, they have limitations that prohibit their use in certain situations, e.g., explosive atmospheres. Thus, there is a need to develop new types of sensor materials. Herein, we demonstrate a simple, low-cost, metal-organic framework (MOF)-based gas leak detection sensor. The system is based on gravimetric sensing by using a quartz crystal microbalance. The quartz crystal is functionalized by layer-by-layer growth of a thin metal-organic framework film. This film shows selective uptake of methane or carbon dioxide under atmospheric conditions. The hardware has low cost, simple operation, and theoretically high sensitivity. Overall, the sensor is characterized by simplicity and high robustness. Furthermore, by exploiting the different adsorption kinetics as measured by multiple harmonic analyses, it is possible to discriminate whether the response is due to methane or carbon dioxide. In summary, we demonstrate data relevant toward new applications of metal-organic frameworks and microporous hybrid materials in sensing.

Critical review of the OSPAR risk-based approach for offshore-produced water discharges.

The management of produced water (PW) discharges from offshore oil and gas installations in the North Atlantic is under the auspices of OSPAR (Oslo/Paris convention for Protection of the Marine Environment of the North-East Atlantic). In 2010, OSPAR introduced the risk-based approach (RBA) for PW management. The RBA includes a hazard assessment estimating PW ecotoxicity using two approaches: whole-effluent toxicity (WET) and substance-based (SB). Set against the framework of the WET and SB approach, we conducted a literature review on the magnitude and cause of PW ecotoxicity, respectively, and on the challenges of estimating these. A large variability in the reported magnitude of PW WET was found, with EC50 or LC50 values ranging from <1% to >100%, and a median of 11% (n = 301). Across the literature, metals, hydrocarbons, and production chemicals were identified as causing ecotoxicity. However, this review reveals how knowledge gaps on PW composition and high sample and species dependency of PW ecotoxicity make clear identification and generalization difficult. It also highlights how limitations regarding the availability and reliability of ecotoxicity data result in large uncertainties in the subsequent risk estimates, which is not adequately reflected in the RBA output (e.g., environmental impact factors). Thus, it is recommended to increase the focus on improving ecotoxicity data quality before further use in the RBA, and that WET should play a more pronounced role in the testing strategy. To increase the reliability of the SB approach, more attention should be paid to the actual composition of PW. Bioassay-directed chemical analysis, combining outcomes of WET and SB in toxicity identification evaluations, may hold the key to identifying drivers of ecotoxicity in PW. Finally, an uncertainty appraisal must be an integrated part of all reporting of risk estimates in the RBA, to avoid mitigation actions based on uncertainties rather than reliable ecotoxicity estimations. Integr Environ Assess Manag 2023;19:1172-1187. © 2022 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Interaction of asphaltenes with nonylphenol by microcalorimetry.

This paper shows the work performed in the study of the capability of isothermal titration calorimetry (ITC) to characterize the interaction between petroleum asphaltenes with a model molecule, namely, nonylphenol. ITC is widely used in biochemistry to study the interaction of proteins with ligands. The intention is to transfer the knowledge into the asphaltene field, with the aim of getting a better understanding of the mechanism of interaction, as well as the energies involved in this process. Calorimetric experiments show that nonylphenol has a complex mechanism of interaction with asphaltenes in toluene, including more than one process. Several models have been used to fit the experimental data. The enthalpies calculated with a model based on polymerization are in the order of -1 to -7 kJ/mol, which are very close to the hydrogen bond energies. This shows the capability of ITC to provide experimental data to the modeling of asphaltene behavior. The number of sites of interaction has been inferred by means of a model taken from protein-ligand science. The values obtained are in the range two to five sites per molecule, assuming an average Mw of 1000 units.

Thermodynamic characterization of asphaltene-resin interaction by microcalorimetry.

This paper collects the work performed by isothermal titration calorimetry (ITC) to characterize the interaction between petroleum asphaltenes and resins. The interaction between these two fractions is of great interest in order to understand the mechanism of stabilization ofasphaltenes in crude oil. To simplify the approach, this preliminary study focuses on toluene solutions of both fractions. This paper reports the experimental determination of the average number of sites in asphaltene molecules and the enthalpy of interaction between asphaltenes and resins. Two models have been used to fit the experimental data. The enthalpies calculated by ITC are in the order of -2 to -4 kJ/mol. These values are in the limit of hydrogen bonding and permanent dipole energies. Similar values have been obtained by using the enthalpy as a fitting parameter in the SAFT equation.