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Background and Purpose: Safe reirradiation relies on assessment of cumulative doses to organs at risk (OARs) across multiple treatments. Different clinical pathways can result in inconsistent estimates. Here, we quantified the consistency of cumulative dose to OARs across multi-centre clinical pathways., Material and Methods: We provided DICOM planning CT, structures and doses for two reirradiation cases: head & neck (HN) and lung. Participants followed their standard pathway to assess the cumulative physical and EQD2 doses (with provided α/β values), and submitted DVH metrics and a description of their pathways. Participants could also submit physical dose distributions from Course 1 mapped onto the CT of Course 2 using their best available tools. To assess isolated impact of image registrations, a single observer accumulated each submitted spatially mapped physical dose for every participating centre., Results: Cumulative dose assessment was performed by 24 participants. Pathways included rigid (n = 15), or deformable (n = 5) image registration-based 3D dose summation, visual inspection of isodose line contours (n = 1), or summation of dose metrics extracted from each course (n = 3). Largest variations were observed in near-maximum cumulative doses (25.4 - 41.8 Gy for HN, 2.4 - 33.8 Gy for lung OARs), with lower variations in volume/dose metrics to large organs. A standardised process involving spatial mapping of the first course dose to the second course CT followed by summation improved consistency for most near-maximum dose metrics in both cases., Conclusion: Large variations highlight the uncertainty in reporting cumulative doses in reirradiation scenarios, with implications for outcome analysis and understanding of published doses. Using a standardised workflow potentially including spatially mapped doses improves consistency in determination of accumulated dose in reirradiation scenarios., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: [Nicholas Hardcastle receives research grant funding from Varian Medical Systems and Reflexion Medical for work unrelated to the current project. Nicholas Hardcastle receives consultancy fees from SeeTreat Medical. Theresa Hemminger is an employee of Brainlab AG.]., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Tobacco product waste poses a global environmental issue, affecting urban and coastal areas alike. The present studies report, for the first time, the total and bioavailable polycyclic aromatic hydrocarbons (PAHs) concentrations in unused and operated heat-not-burn (HnBs) tobacco products. To enable direct comparisons, identical sets of studies were conducted using conventional cigarettes (CCs). Five low-molecular PAHs were determined in HnBs at total concentrations that were of the same order before and after operation (Σ 5 PAH = 47.37 ± 3.44 ng unit -1 and Σ 5 PAH = 69.36 ± 5.78 ng unit -1 in unused and used HnBs, respectively). The incomplete combustion of organics during smoking of CCs, yielded substantially higher amounts of PAHs with their sum (Σ 10 PAHs = 1449 ± 113 ng unit -1 ) being >20 times larger than those in HnBs. The tobacco and filter were the most contaminated parts in HnBs. In unused CCs, tobacco had the highest PAHs load and after smoking, the spent filter was the most contaminated part, containing ∼80% of the total amount of PAHs. Naphthalene was the most abundant PAH detected in all tobacco products. Despite the high total PAH concentrations found in smoked CCs, the sums of the bioavailable PAH concentrations were of the same order in all tested tobacco products (Σ 5 PAH = 61.38 ± 1.79 ng unit -1 in unused HnBs, Σ 5 PAH = 70.87 ± 7.67 ng unit -1 in used HnBs, Σ 4 PAH = 66.92 ± 5.95 ng unit -1 in unused CCs, and Σ 6 PAH = 47.94 ± 1.26 ng unit -1 in smoked CCs). This finding was related to smoking affecting PAHs' leachability from CCs and delaying their desorption from the solid matrix. Adjusting the pH, salt and humic acids content at environmentally relevant values did not affect PAHs leaching at 24 h of soaking. Finally, the leaching behavior of PAHs in natural waters (river water, rainwater, and seawater) was found similar to that in ultrapure water, experimentally verifying the ability of tobacco product waste to leach PAHs into the aquatic environment., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: This research was funded by an Investigator-Initiated Study award by Philip Morris Products SA (IIS.PMI.2017.30). The study protocol was written by Professor E. Psillakis who was also the principal investigator of the study. Philip Morris Products SA had no involvement in the study conduct, data analysis and writing of the manuscript., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This work reports for the first time the UVC photodegradation of cilastatin, a renal dehydropeptidase inhibitor co-adminstered with the imipenem antibiotic. Initially, solutions of cilastatin at varying concentrations were prepared in ultra-pure water and the direct photolysis of cilastatin was monitored under 254-nm irradiation. Degradation was slower at higher initial cilastatin concentrations, due to absorption saturation. Of the different eluting photoproducts, only one was tentatively identified as oxidized cilastatin bearing a sulfoxide group. UV-254 photolysis occurred faster at lower pH values, because the protonated forms of the molecule (H 3 A + , H 2 A) have both higher absorption coefficients and higher photolysis quantum yields than the non-protonated ones (HA - , A 2- ). The direct photolysis of cilastatin does not involve • OH, as excluded by experiments in which t-butanol was added as • OH scavenger, whereas the presence of humic acids inhibited photolysis due to competition for radiation absorption. The same explanation partially accounts for the observation that the photolysis kinetics of cilastatin was slower in tap water, river water and treated wastewater samples compared to ultra-pure water. Moreover, the direct photolysis quantum yield was also lower in water matrices compared to ultra-pure water. Similar findings reported for triclosan and the herbicide 2-methyl-4-chlorophenoxyacetic acid in previous studies might suggest that the water matrix components could carry out either physical quenching of cilastatin's excited states or back-reduction to cilastatin of the partially oxidized degradation intermediates. Overall, the present results demonstrate that UVC irradiation is a fast and efficient process for the degradation of cilastatin in natural water and treated wastewater., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Nicotine is an important emerging contaminant widely detected in water resources. The main nicotine sources are human excretions from users and leaching from discarded tobacco product waste, which represents the most commonly littered item in urban areas and coasts. In this study, the UV 254 photolytical fate of nicotine in natural water and leachates produced from conventional cigarettes (CCs) and the new generation heat-not-burn (HnBs) tobacco products is examined for the first time. The effect of UV 254 irradiation on nicotine depletion in ultrapure water was initially studied. The reaction was pseudo first-order with respect to nicotine concentration at low concentrations and shifted to lower order at higher concentrations, an effect associated to absorption saturation. Although nicotine removal was fast, only 9.5% of the total organic carbon was removed after irradiation due to the formation of by-products. The chemical structures of six photo-products were derived by means of liquid and gas chromatography coupled to mass spectrometry. The photodegradation kinetics was found to depend on pH and faster kinetics were recorded when the monoprotonated form of nicotine was dominant (pH = 5-8). The presence of humic acids was found to slightly delay kinetics as they competed with nicotine for lamp irradiance, whereas the presence of salt had no effect on the direct photolysis of nicotine. Direct photolysis studies were also performed using natural waters. Compared to ultra-pure water, photodegradation was found to proceed slightly slower in river water, in similar kinetics in seawater, and relatively faster in rain water. The later was assumed to be due to the lower pH compared to the rest of the natural water tested. Leachates from used HnBs and smoked CCs were also submitted to UV 254 irradiation and direct photolysis was found to proceed fast despite the high complexity of these matrices. Nonetheless, the total organic carbon in the system remained the same after irradiation due to the abundance of organics and photo-products formed. We take advantage of the present investigations and report the leaching behavior of nicotine from HnBs and CCs. Among others, we found that in HnBs ~70% of the total and bioavailable nicotine content remains in the tobacco sticks after operation and this percentage drops to 15% in CCs due to the reduction in mass after smoking. This finding demonstrated the importance of properly disposing tobacco product waste to prevent nicotine leaching in water bodies., (Copyright © 2020 The Author(s). Published by Elsevier Inc. All rights reserved.)

The use of a thick sorbent coating in headspace sorptive extraction (HSSE) increases the amount of analytes extracted at equilibrium as well as the time needed to reach it. In this work we propose HSSE sampling under vacuum conditions to reduce equilibration times. A theoretical model is presented that describes the pressure dependence of the so-called vacuum-assisted HSSE (Vac-HSSE) method, and predicts the reduction in equilibration times when lowering the sampling pressure. We take advantage of the theoretical formulation to reach some general conclusions for HSSE on the relationship between the physical characteristics of the stir bar, uptake rates and equilibration times. The theoretical predictions were experimentally verified using water solutions spiked with naphthalene, acenaphthene and fluoranthene as model compounds. The effects of sampling temperature and extraction time under vacuum and regular pressure conditions were thoroughly investigated. The positive combined effect of heating the sample under low sampling pressure pointed that high humidity did not affect the performance of the extraction phase; an effect commonly recorded in headspace solid-phase microextraction. The extraction time profiles built at 25 and 55 °C visualized the substantial improvement in extraction kinetics with Vac-HSSE compared to the regular HSSE method. The results on naphthalene (assumed to evaporate relatively fast from the water sample) provided evidence that at 1 atm gas-sided resistance limited analyte uptake by the stir-bar and that this limitation could be effectively reduced by adopting the vacuum sampling approach. The accelerations of acenaphthene and fluoranthene suggested that gas-phase constraints limited both the evaporation and analyte uptake processes. Independent method optimization of HSSE under each pressure condition yielded a shorter sampling time for Vac-HSSE compared to the regular HSSE procedure (30 min vs. 60 min respectively). The analytical performances of the two optimized methods were evaluated and it was concluded that Vac-HSSE was performing similar (naphthalene and acenaphthene) or better (fluoranthene) than regular HSSE in half the sampling time needed., (Copyright © 2019 Elsevier B.V. All rights reserved.)