Chemical Surrogate Research Articles

Cigarette Smoke Constituents and Nicotine Differentially Affect Cytokine Production by Human Macrophages Stimulated by TLR Ligands In Vitro: Considerations for a Standardised Protocol.

Chronic obstructive pulmonary disease (COPD) is an inflammatory lung condition associated with cigarette (tobacco) smoking. Numerous in vivo animal studies have been conducted to investigate the links between cigarette smoke, nicotine and infection in lung pathology. As an alternative to animal experiments, we used an in vitro system to investigate the effects of cigarette smoke extract (CSE) or nicotine on TNF-α and IL-10 production by monocyte-derived human macrophages. The macrophages were simultaneously stimulated with either poly-IC (as a chemical surrogate for viral infection) or lipopolysaccharide (as a chemical surrogate for Gram-negative bacterial infection). CSE enhanced TNF-α production, whereas nicotine inhibited IL-10 production by the macrophages, particularly when co-stimulated with the microbial chemical surrogates. A system of this type may help to further our understanding of the immunological and inflammatory effects of smoking, without recourse to in vivo studies. Requirements for the optimisation and standardisation of such an in vitro system are also discussed.

Establishing performance metrics for quantitative non-targeted analysis: a demonstration using per- and polyfluoroalkyl substances

Non-targeted analysis (NTA) is an increasingly popular technique for characterizing undefined chemical analytes. Generating quantitative NTA (qNTA) concentration estimates requires the use of training data from calibration “surrogates,” which can yield diminished predictive performance relative to targeted analysis. To evaluate performance differences between targeted and qNTA approaches, we defined new metrics that convey predictive accuracy, uncertainty (using 95% inverse confidence intervals), and reliability (the extent to which confidence intervals contain true values). We calculated and examined these newly defined metrics across five quantitative approaches applied to a mixture of 29 per- and polyfluoroalkyl substances (PFAS). The quantitative approaches spanned a traditional targeted design using chemical-specific calibration curves to a generalizable qNTA design using bootstrap-sampled calibration values from “global” chemical surrogates. As expected, the targeted approaches performed best, with major benefits realized from matched calibration curves and internal standard correction. In comparison to the benchmark targeted approach, the most generalizable qNTA approach (using “global” surrogates) showed a decrease in accuracy by a factor of ~4, an increase in uncertainty by a factor of ~1000, and a decrease in reliability by ~5%, on average. Using “expert-selected” surrogates (n = 3) instead of “global” surrogates (n = 25) for qNTA yielded improvements in predictive accuracy (by ~1.5×) and uncertainty (by ~70×) but at the cost of further-reduced reliability (by ~5%). Overall, our results illustrate the utility of qNTA approaches for a subclass of emerging contaminants and present a framework on which to develop new approaches for more complex use cases.Graphical

First detection of deuterated methylidyne (CD) in the interstellar medium

While the abundance of elemental deuterium is relatively low (D/H ~ a few ×10−5), orders of magnitude higher D/H abundance ratios have been found for many interstellar molecules, enhanced by deuterium fractionation. In cold molecular clouds (T < 20 K), deuterium fractionation is driven by the H2D+ ion, whereas at higher temperatures (T ≥ 20–30 K) gas-phase deuteration is controlled by reactions with CH2D+ and C2HD+. While the role of H2D+ in driving cold interstellar deuterium chemistry is well understood, thanks to observational constraints from direct measurements of H2D+, deuteration stemming from CH2D+ is far less understood as a result of the absence of direct observational constraints of its key ions. Therefore, making use of chemical surrogates is imperative in order to explore deuterium chemistry at intermediate temperatures. Formed at an early stage of ion-molecule chemistry directly from the dissociative recombination of CH3+ (CH2D+), CH (CD) is an ideal tracer for investigating deuterium substitution initiated by reactions with CH2D+. This paper reports the first detection of CD in the interstellar medium (ISM), carried out using the APEX 12 m telescope toward the widely studied low-mass protostellar system IRAS 16293–2422. Observed in absorption towards the envelope of the central protostar, the D/H ratio derived from the column densities of CD and CH is found to be 0.016 ± 0.003. This is an order of magnitude lower than the values found for other small molecules like C2H and H2CO observed in emission but whose formation, which is similar to that of CH, is also initiated via pathways involving warm deuterium chemistry. Gas-phase chemical models reproducing the CD/CH abundance ratio suggest that it reflects ‘warm deuterium chemistry’ (which ensues in moderately warm conditions of the ISM) and illustrates the potential use of the CD/CH ratio in constraining the gas temperatures of the envelope gas clouds it probes.

Survey of 226Ra/228Ra and inorganic constituents in Iowa private drinking water wells

AbstractRadium is a naturally‐occurring radioactive element found in Upper Midwest aquifers, yet exposure risks for unregulated water sources in this region are unknown. A survey of 226/228Ra and other inorganic constituents in 94 private wells was conducted in 2019 across 10 Iowa counties. Within private wells, 53% measured below minimum detectable activity whereas 6.3% have 226/228Ra levels above the United States Environmental Protection Agency Maximum Contaminant Level. 226/228Ra occurrence was not associated with well‐depth or chemical surrogates, but were generally consistent with the lithology and historical water quality trends for aquifers. In 2020, 11 of the 226/228Ra‐impacted wells were re‐sampled to assess the efficacy of in‐home water treatment. Water softeners reduced 226/228Ra to non‐detectable activities, but other inorganic constituents persisted and their removal required more advanced treatment. This study suggests that 226/228Ra occurrence in private wells can reasonably be anticipated from public water supply data if reliable information is available to identify the source aquifer.

Identification of bio-active food compounds as potential SARS-CoV-2 PLpro inhibitors-modulators via negative image-based screening and computational simulations

Despite significant studies on the COVID-19 pandemic, scientists around the world are still battling to find a definitive therapy against the ongoing severe global health crisis. In this study, advanced computational approaches have been employed to identify bioactive food constituents as potential SARS-CoV-2 PLpro inhibitors-modulators. As a validated antiviral drug target, PLpro has gained tremendous attention for therapeutics developments. Therefore, targeting the multifunctional SARS-CoV-2 PLpro protein, ∼1039 bioactive dietary compounds have been screened extensively through novel techniques like negative image-based (NIB) screening and molecular docking approaches. In particular, the three different models of NIB screening have been generated and used to re-score the dietary compounds based on the negative image which is created by reversing the shape and electrostatics features of PLpro protein's ligand-binding cavity. Further, 100 ns molecular dynamics simulation has been performed and MM-GBSA based binding free energies have been estimated for the final proposed four dietary compounds (PC000550, PC000361, PC000558, and PC000573) as potential inhibitors/modulators of SARS-CoV-2 PLpro protein. Employed computational study outcome also has been compared with respect to the earlier experimentally investigated compound GRL0617 against SARS-CoV-2 PLpro protein, which suggests much greater interaction potential in terms of binding affinity and other energetic contributions for the proposed dietary compounds. Hence, the present study suggests that proposed dietary compounds can be suitable chemical entities for modulating the activity of PLpro protein or can be further utilized for optimizing or screening of novel chemical surrogates, however also needs experimental evaluation for entry in clinical studies for better assessment.

Numerical investigations of low load diesel-methane dual fuel combustion at early diesel injection timings

The present work focuses on the development and validation of a CFD simulation setup of diesel-methane dual fuel combustion in a single-cylinder research engine (SCRE). The validated setup is used to provide insight about dual fuel combustion at low-load operation. The computational campaign consisted of evaluating three different diesel injection timings of 310, 320, and 330 CAD at a methane percent energy substitution (PES) of 80%, 5.1 bar gross IMEP, 500 bar diesel injection pressure, and 1.5 bar manifold air pressure where 360 CAD corresponds to firing top dead center. The computational setup ability to capture combustion, performance, and emissions trends accurately is demonstrated by good agreement with experimental data. The validated setup is further utilized to provide insights into the nature of dual fuel combustion, particularly, the effect of methane on diesel autoignition. Analysis of the computational results showed that the onset of both low-temperature heat release and high-temperature heat release of n-dodecane (the chemical surrogate used for diesel) is delayed by the presence of methane in the system. For early diesel injection in a dual-fuel engine at low-load, initial high-temperature combustion arises from the burning of n-dodecane followed by methane combustion. Most of the methane present in the piston compression ring crevices, areas near the piston top and the liner, remained unreacted after combustion is done. The effect of diesel and methane fuel amount on engine performance at low-load was also explored.

Development of diesel surrogates for reproducing the effect of fuel properties on engine combustion and emissions using an optimized decoupling physical–chemical surrogate (DPCS) model

An optimized decoupling physical–chemical surrogate (DPCS) model was carried out to formulate different diesel surrogates effectively. In the optimized DPCS model, the physical candidates of ten components and the chemical candidates of four components are coupled by the rule of hydrocarbon type to match the physical–chemical properties of diesel fuel. The composition of the physical components is determined using genetic algorithm (GA), and then the coupling rule is applied to derive the composition of the chemical components. To validate the robustness of the optimized DPCS model, the prediction results are compared with the experimental results containing vapor penetration distance in a constant volume bomb (CVB) and the combustion and emission characteristics in a convention diesel combustion (CDC) engine utilizing different diesel fuels. The results show that the predictions of the diesel surrogates formulated by the optimized DPCS model accurately fit the experimental results, and the impacts of diesel fuel properties on the spray and combustion behaviors can be well reproduced. Besides, the factors that dominate the spray and combustion features of different diesel fuels are identified.

Adsorptive Behaviour of a Novel Ag-4,4-bipyridine Metal Organic Framework Thin Film Tethered to a Quartz Crystal Microbalance

We report on the development of a Quartz Crystal Microbalance-based sensor targeting the monitoring of the pertechnetate ion (TcO4 –) in groundwater exploiting the anion-specific adsorptive behaviour of a novel Ag-4,4-bipyridine metal-organic framework (MOF) thin film. This MOF was first reported by Zhu et al. [Environ. Sci. Technol. Lett., 4, 316, (2017)] to selectively and irreversibly adsorb ReO4 –, a non-radioactive chemical surrogate for TcO4 −, in the form of bulk crystals. The structure of our film was characterised by XRD and SEM and its response and selectivity were evaluated by monitoring the changes in the resonant frequency of the QCM as a function of the concentration of ReO4 – and other interferents. Finally, the interaction of all the analytes with the film was modelled with adsorption isotherms including Langmuir, Freundlich and Sips. We show that the behaviour of the thin film is substantially different from that of the bulk crystals.

Monitoring of Technetium in Groundwater:Development of a Novel QCM Based Sensor

99Tc, a pure β-emitter with Emax =294 keV, is one of the most significant (t1/2 =2.1×105 y) nuclear waste isotopes, produced by the fission of U with a yield of 6%. Under normal environmental conditions, it is mostly encountered as the pertechnetate ion, TcO4 -, which is highly soluble and consequently mobile in water. For this reason, and because it often is the first contaminant to be present in detectable levels, its monitoring into groundwater is a statutory requirement for every nuclear license site. Because of its relatively low concentration in environmental samples, current determination methods of 99Tc involve several steps, such as chemical separation from the matrix, purification and source preparation, prior to radiometric (e.g. liquid scintillation counting) or mass spectroscopic (e.g. inductively coupled plasma mass spectroscopy) determination. The detection of 99Tc may take up to several days, thus making these techniques inappropriate for an emergency situation. Hence, We report on the development of a sensor for the real time monitoring of 99Tc in groundwater based on the Quartz Crystal Microbalance (QCM). The QCM is a piezoelectric resonator, which oscillates in a resonant frequency fs when an electric potential is applied across its body. It is capable of measuring very small changes in mass at its surface, through the change of the resonant frequency. We modify it to respond exclusively to the presence of TcO4 -, by application of a novel Ag-4,4bipyridine metal-organic framework thin film built layer-by-layer on a self-assembled monolayer of 4-mercaptopyridine on the gold surface. The film’s structure is characterised by several techniques such as XPS, AFM and XRD and we evaluate its response and selectivity by monitoring the changes in the resonant frequency as a function of the concentration of ReO4 -, which is a non-radioactive chemical surrogate for TcO4 -. Finally, we model the adsorption of ReO4 - and other interferences with adsorption isotherms such as Langmuir, Freundlich and Sips.

Lanthanide (Ce, Nd, Eu) environments and leaching behavior in borosilicate glasses

Borosilicate glasses will be used to stabilize the high-level radioactive wastes for disposal in a geological repository. Understanding the effects of actinide addition to a borosilicate glass matrix is of great importance in view of waste immobilization. Lanthanides were considered as chemical surrogates for actinides. The local structures of Ce3+, Nd3+ and Eu3+ ions in borosilicate glass, have been investigated by synchrotron radiation based techniques. The atomic parameters, such as bond lengths and coordination environments derived from X-ray diffraction, in combined with Reverse Monte Carlo simulations show correlation with X-ray absorption fine structure data. The lanthanide ions are in the common network with the tetrahedral SiO4 and with the mixed trigonal BO3 and tetrahedral BO4 units. Second neighbor atomic pair correlations reveal that the Ce3+, Nd3+ and Eu3+ ions are accommodated in both Si and B sites, supporting that the lanthanide-ions are stabilized in the glass-matrix network. Microscopy and microanalysis provided information on the amorphous state and on the major elemental composition of the high lanthanide-concentration samples. The release of matrix components (Si, B, Na, Ba, Zr) is higher than that of lanthanides (Ce, Nd, Eu). Both types of elements show a decreasing release tendency with time.

Monitoring of Technetium in Groundwater: Development of a Novel QCN Based Sensor

Technetium-99, a pure β-emitter with Emax =294 keV, is one of the most significant (t1/2 =2.1×105 y) nuclear waste isotopes, produced by the fission of U with a yield of 6%. Under normal environmental conditions, it is mostly encountered as the pertechnetate ion, TcO4 -, which is highly soluble and consequently mobile in water. For this reason, its monitoring into groundwater is a statutory requirement for every nuclear license site. Because of its relatively low concentration in environmental samples, current determination methods of 99Tc involve several steps, such as chemical separation from the matrix, purification and source preparation, prior to radiometric (e.g. liquid scintillation counting) or mass spectroscopic (e.g. inductively coupled plasma mass spectroscopy) determination. The detection of 99Tc may take up to several days, thus making these techniques inappropriate for an emergency situation. Hence, We report on the development of a sensor for the real time monitoring of 99Tc in groundwater based on the Quartz Crystal Nanobalance (QCN). The QCN is a piezoelectric resonator, which oscillates in a resonant frequency fs when an electric potential is applied across its body. It is capable of measuring very small changes in mass at its surface, through the change of the resonant frequency. We modify it to respond exclusively to the presence of TcO4 -, by application of a novel Ag-4,4bipyridine metal-organic framework thin film built layer-by-layer on a self-assembled monolayer of 4-mercaptopyridine on the gold surface. The film’s structure is characterised by several techniques such as XPS, AFM and XRD and we evaluate its response and selectivity by monitoring the changes in the resonant frequency as a function of the concentration of ReO4 -, which is a non-radioactive chemical surrogate for TcO4 -. Finally, we model the adsorption of ReO4 - and other interferences with adsorption isotherms such as Langmuir, Freundlich and Sips.

A cell-based screening method using an intracellular antibody for discovering small molecules targeting the translocation protein LMO2.

Intracellular antibodies are tools that can be used directly for target validation by interfering with properties like protein-protein interactions. An alternative use of intracellular antibodies in drug discovery is developing small-molecule surrogates using antibody-derived (Abd) technology. We previously used this strategy with an in vitro competitive surface plasmon resonance method that relied on high-affinity antibody fragments to obtain RAS-binding compounds. We now describe a novel implementation of the Abd method with a cell-based intracellular antibody-guided screening method that we have applied to the chromosomal translocation protein LMO2. We have identified a chemical series of anti-LMO2 Abd compounds that bind at the same LMO2 location as the inhibitory anti-LMO2 intracellular antibody combining site. Intracellular antibodies could therefore be used in cell-based screens to identify chemical surrogates of their binding sites and potentially be applied to any challenging proteins, such as transcription factors that have been considered undruggable.

A combustion model for multi-component fuels based on relative reactivity and molecular structure

A reliable multi-component surrogate fuel model needs to be able to represent both physical properties and chemical kinetics of a real fuel. However, enhancing the fidelity of a model with detailed description of physical and chemical behavior of all fuel components found in real fuels is limited by the prohibitive computational load to calculate the combustion chemistry of the fuel. Hence, it is desirable to achieve computational efficiency by reducing the number of chemical surrogates at the minimum expense of prediction accuracy. The objective of this work is to develop a model that can simulate the oxidation of multi-component fuels by representing the ignition characteristics of physical surrogate components with fewer chemical surrogates and achieve both computational efficiency and prediction accuracy. The main advantage of the model, called the Reactivity-Adjustment (ReAd) combustion model, is to accurately predict the reactivity of the physical surrogate components that the reaction mechanisms of which are not included in the reaction kinetics model employed in the simulation. The reactivity variation of local mixtures with different compositions is modeled by adjusting the reaction rate constants of selected control-reactions in the reaction mechanism of the representative chemical surrogates. An initial version of the model has been developed employing a single chemical surrogate to represent the combustion of diesel fuel which is modeled as multiple surrogate components to capture the physical properties of the real fuel. The model was extended to consider two more chemical surrogate components to represent the ignition characteristics of other chemical families than n-alkanes. This enabled to avoid the excessive adjustment of reaction rate constants that were necessary when a single chemical surrogate is used to represent the oxidation kinetics of entire multi-component fuels. The model was extensively tested for simulating oxidation processes of many fuels with a variety of fuel reactivity and in various combustion regimes. The results demonstrated that excellent accuracy of the ignition/combustion prediction was achieved while ensuring computational efficiency.

Pan RAS-binding compounds selected from a chemical library by inhibiting interaction between RAS and a reduced affinity intracellular antibody

Intracellular antibodies are valuable tools for target validation studies for clinical situations such as cancer. Recently we have shown that antibodies can be used for drug discovery in screening for chemical compounds surrogates by showing that compounds could be developed to the so-called undruggable RAS protein family. This method, called Antibody-derived compound (Abd) technology, employed intracellular antibodies binding to RAS in a competitive surface plasmon resonance chemical library screen. Success with this method requires a high affinity interaction between the antibody and the target. We now show that reduction in the affinity (dematuration) of the anti-active RAS antibody facilitates the screening of a chemical library using an in vitro AlphaScreen method. This identified active RAS specific-binding Abd compounds that inhibit the RAS-antibody interaction. One compound is shown to be a pan-RAS binder to KRAS, HRAS and NRAS-GTP proteins with a Kd of average 37 mM, offering the possibility of a new chemical series that interacts with RAS in the switch region where the intracellular antibody binds. This simple approach shows the druggability of RAS and is generally applicable to antibody-derived chemical library screening by affording flexibility through simple antibody affinity variation. This approach can be applied to find Abd compounds as surrogates of antibody-combining sites for novel drug development in a range of human diseases.

Influence of torrefaction intensities on bamboo (Acidosasa longiligula) shoot shell-derived biochar and its application for Tc(VII) reductive immobilization

In this study, the torrefaction biochar from bamboo (Acidosasa longiligula) shoot shell under different torrefaction intensities (TI) were prepared and characterized. Nonradioactive Cr(VI), a chemical surrogate for radioactive Tc(VII), was used to evaluate Tc(VII) reductive immobilization of torrefaction biochar. Batch adsorption experiments indicated that torrefaction biochar had strong adsorption ability to Cr(VI) with the best uptake capacity of 63.11 mg/g. The adsorption kinetic was well fitted by pseudo-second-order model and Park model. The adsorption equilibrium was considerably fitted by Freundlich and Temkin isotherm The adsorption-reduction mechanism during the whole Cr(VI) immobilization process was confirmed by the Raman spectrum analysis and the nice fitting of Park model. This study demonstrates that torrefaction biochar deserves to be a low-cost and effective immobilization material for Tc(VII).

Hydrolysis of Dimethyl Methylphosphonate (DMMP) in Hot-Compressed Water.

Dimethyl methylphosphonate (DMMP) is often used as a chemical surrogate for organophosphate nerve agents, as it exhibits similar physiochemical properties while having significantly lower toxicity. Continuous hydrolysis of DMMP in hot-compressed water is performed at temperatures from 200 to 300 °C, pressures of 20 and 30 MPa, and residence times from 30 to 80 s to evaluate the effects of pressure and temperature on reaction kinetics. DMMP hydrolysis is observed to follow pseudo-first-order reaction behavior, producing methylphosphonic acid and methanol as the only detectable reaction products. This is significant for the practical implementation of a continuous hydrothermal reactor for chemical warfare agent neutralization, as the process only yields stable, less-toxic compounds. Pressure has no discernible effect on the hydrolysis rate in compressed liquid water. Pseudo-first-order Arrhenius parameters are determined, with an activation energy of 90.17 ± 5.68 kJ/mol and a pre-exponential factor of 107.51±0.58 s-1.

Refining Fuel Composition of RP-3 Chemical Surrogate Models by Reactive Molecular Dynamics and Machine Learning

A simple chemical surrogate fuel model may not be able to fully reproduce the chemical behavior in real fuel combustion. A structure–chemical reactivity relationship at the molecular level is believed to be useful in tuning the chemical composition of reported surrogate fuel models. This work proposes an approach to predict a component fraction of a RP-3 surrogate fuel model with a combined method of ReaxFF molecular dynamics (MD) simulations and machine learning. There are four major steps to get a refined surrogate fuel model on the basis of parent RP-3 fuel models with two, three, or four components. Step 1 helps to prepare chemical reactivity data as the input of machine learning. The chemical reactivity data are described by the oxidation reactions in terms of dynamic species concentration with time that were prepared with ReaxFF MD simulations for each derived fuel model generated from the RP-3 parent fuel model by randomly changing its component fraction. Step 2 fits a component fraction prediction model between a single surrogate component fraction and its chemical reactivity data among the common reaction space in oxidation of possible RP-3 surrogates and a 45-component RP-3 fuel with the machine-learning method. The best performance model of LightGBM was selected among the machine-learning models of linear regression, support vector regression, and LightGBM based on the training error evaluation. Each refined component fraction of RP-3 surrogate models was predicted one by one using the trained LightGBM model with the input of dynamic species concentration data of the 45-component RP-3 fuel model better representing real RP-3 fuel. Step 3 helps to select one refined surrogate model among the predicted surrogate models with two, three, or four components by comparing the chemical reactivity deviation of important species with additional ReaxFF MD simulations under the conditions of heat-up, isothermal oxidation, and isothermal pyrolysis. The optimal model of the refined three-component RP-3 surrogate is validated in step 4 where its predicted ignition delay time is found to be closer to the reported experimental data of the real RP-3 fuel than to its parent surrogate fuel model. This work suggests that the proposed computational approach by combining ReaxFF MD simulations and machine learning should be potentially useful in search for refined RP-3 chemical surrogate fuel models directly on the basis of chemical reactivity data in oxidation at the molecular level.

Structural investigation of borosilicate glasses containing lanthanide ions

High level radioactive actinides are produced as a side product in reprocessing spent nuclear fuel, for which safe long-term-inert immobilizer matrices are needed. Borosilicate glasses are of great potential amongst the candidates of suitable inert materials for radioactive waste immobilization. Understanding the effects of actinide addition to a borosilicate glass matrix is of great importance in view of waste immobilization. Here we present structural studies of a simplified glass-matrix, − 55SiO2·10B2O3·25Na2O·5BaO·5ZrO2 - upon adding lanthanide (Ln-)oxides: CeO2, Nd2O3, Eu2O3, in two different concentrations 10% and 30w% each, to investigate the effects of lanthanides (Ln) taken as chemical surrogates for actinides. Neutron diffraction combined with of Reverse Monte Carlo simulations show that all investigated glass structures comprise tetrahedral SiO4, trigonal BO3 and tetrahedral BO4 units, forming mixed [4]Si-O-[3]B and [4]Si-O-[4]B linkages. 11B Magic Angle Spinning Nuclear Magnetic Resonance is indicative of simultaneous presence of trigonal BO3 and tetrahedral BO4 units, with spectral fractions strongly dependent on the Ln addition. Ln-addition promote the BO3 + O-→[BO4]– isomerization resulting in lower fraction of boron in BO3, as compared to BO4 units. Raman spectra, in full agreement with neutron diffraction, confirm that the basic network structure consists of BO3/trigonal and SiO4/BO4 tetrahedral units. Second neighbour atomic pair correlations reveal Ce, Nd, Eu to be accommodated in both Si and B sites, supporting that the borosilicate-matrix well incorporates Ln-ions and is likely to similarly incorporate actinides, opening a way to radioactive nuclear waste immobilization of this group of elements in a borosilicate glass matrix.

Monitoring of Technetium in Groundwater:Development of a Novel Qcn Based Sensor

99Tc, a pure β-emitter with Emax =294 keV, is one of the most significant (t1/2 =2.1×105 y) nuclear waste isotopes, produced by the fission of U with a yield of 6%. Under normal environmental conditions, it is mostly encountered as the pertechnetate ion, TcO4 -, which is highly soluble and consequently mobile in water. For this reason, and because it often is the first contaminant to be present in detectable levels, its monitoring into groundwater is a statutory requirement for every nuclear license site. Because of its relatively low concentration in environmental samples, current determination methods of 99Tc involve several steps, such as chemical separation from the matrix, purification and source preparation, prior to radiometric (e.g. liquid scintillation counting) or mass spectroscopic (e.g. inductively coupled plasma mass spectroscopy) determination. The detection of 99Tc may take up to several days, thus making these techniques inappropriate for an emergency situation. Hence, We report on the development of a sensor for the real time monitoring of 99Tc in groundwater based on the Quartz Crystal Nanobalance (QCN). The QCN is a piezoelectric resonator, which oscillates at a resonant frequency fs when an electric potential is applied across its body. It is capable of measuring very small changes in mass at its surface, through the change of the resonant frequency. We modify it to respond exclusively to the presence of TcO4 -, by application of a novel Ag-4,4bipyridine metal-organic framework thin film built layer-by-layer on a self-assembled monolayer of 4-mercaptopyridine on the gold surface. The film’s structure is characterised by several techniques such as XPS, AFM and XRD and we evaluate its response and selectivity by monitoring the changes in the resonant frequency as a function of the concentration of ReO4 -, which is a non-radioactive chemical surrogate for TcO4 -.

Hot Isostatically Pressed Zirconolite Wasteforms for Actinide Immobilisation

In order to demonstrate the deployment of Hot Isostatic Pressing (HIP) for the immobilisation of Pu stocks and residues, a series of active and inactive zirconolite formulations have been processed and characterised. In this instance, Ce, U, and Th have been applied as chemical surrogates for Pu4+. A range of formulations targeting isovalent Zr4+ site substitution (i.e. to simulate CaZr1-xPuxTi2O7) have been processed by HIP and characterised by powder X-ray diffraction, and scanning electron microscopy, in order to determine surrogate partitioning between the host zirconolite phase, and accessory phases that may have formed during the HIP process.