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This study presents a fit-for-purpose lab and field evaluation of commercially available portable sensor systems for PM, NO2, and/or BC. The main aim of the study is to identify portable sensor systems that are capable of reliably quantifying dynamic exposure gradients in urban environments. After an initial literature and market study resulting in 39 sensor systems, 10 sensor systems were ultimately purchased and benchmarked under laboratory and real-word conditions. We evaluated the comparability to reference analyzers, sensor precision, and sensitivity towards environmental confounders (temperature, humidity, and O3). Moreover, we evaluated if the sensor accuracy can be improved by applying a lab or field calibration. Because the targeted application of the sensor systems under evaluation is mobile monitoring, we conducted a mobile field test in an urban environment to evaluate the GPS accuracy and potential impacts from vibrations on the resulting sensor signals. Results of the considered sensor systems indicate that out-of-the-box performance is relatively good for PM (R2 = 0.68–0.9, Uexp = 16–66%, BSU = 0.1–0.7 µg/m3) and BC (R2 = 0.82–0.83), but maturity of the tested NO2 sensors is still low (R2 = 0.38–0.55, Uexp = 111–614%) and additional efforts are needed in terms of signal noise and calibration, as proven by the performance after multilinear calibration (R2 = 0.75–0.83, Uexp = 37–44%)). The horizontal accuracy of the built-in GPS was generally good, achieving <10 m accuracy for all sensor systems. More accurate and dynamic exposure assessments in contemporary urban environments are crucial to study real-world exposure of individuals and the resulting impacts on potential health endpoints. A greater availability of mobile monitoring systems capable of quantifying urban pollutant gradients will further boost this line of research. [ABSTRACT FROM AUTHOR]

Mobile monitoring is used as an additional tool to collect air quality data at a high spatial resolution and to complement data from fixed air quality stations. Citizens are interested in contributing to air quality monitoring, and while the availability of low-cost air quality sensors can create opportunities to measure the air quality at a high spatial resolution, the data are often of lower quality, and sensors that measure combustion-related aerosols (like black carbon) are not commonly available. Mobile monitoring using a mid-range instrument can fill this gap. We present the results of a mobile BC (black carbon) monitoring campaign performed by citizens in Mechelen as part of a local citizen observatory (CO), Meet Mee Mechelen, initiated as part of the European H2020 project, Ground Truth 2.0. The goal of the study was two-fold: (1) to propose and evaluate a mobile monitoring method (data collection and data processing) to construct pollution maps of BC concentrations and (2) to demonstrate how to organize community-based air quality monitoring to measure both the spatial and temporal variations in air pollution levels. Measurements were taken during peak hours in four campaigns characterized by different meteorological conditions: October–November 2017, February–March 2018, June–July 2018 and September 2018. The results show large spatial and temporal variabilities. Spatial variability is influenced by traffic volume, stop-and-go traffic and also the building environment and the distance of biking paths from road traffic. The four different campaigns show similar spatial patterns, but due to background and meteorological influences, the absolute concentrations differ between seasons. A rescaling method using data from fixed stations in the air quality monitoring network (AQMN) was presented to construct maps representative of longer periods. This paper shows that mobile measurements can be used by CO to assess the spatial variability of air quality in a city. The data can be used to evaluate mobility plans, carry out hot spot detection, evaluate the exposure of cyclists as a function of cycling infrastructure and perform model validation. However, it is important to use high-quality instruments and apply the correct measurement methodology (number of repetitions, season) to obtain meaningful data. [ABSTRACT FROM AUTHOR]

Advances in the field of frustrated Lewis pair (FLP) chemistry have led to the discovery of radical pairs, obtained by a single-electron transfer (SET) from the Lewis base to the Lewis acid. Radical pairs are intriguing for their potential to enable cooperative activation of challenging substrates (e.g., CH4, N2) in a homolytic fashion, as well as the exploration of novel radical reactions. In this review, we will cover the two known mechanisms of SET in FLPs—thermal and photoinduced—along with methods (i.e., CV, DFT, UV-vis) to predict the mechanism and to characterise the involved electron donors and acceptors. Furthermore, the available techniques (i.e., EPR, UV-vis, transient absorption spectroscopy) for studying the corresponding radical pairs will be discussed. Initially, two model systems (PMes3/CPh3+ and PMes3/B(C6F5)3) will be reviewed to highlight the difference between a thermal and a photoinduced SET mechanism. Additionally, three cases are analysed to provide further tools and insights into characterizing electron donors and acceptors, and the associated radical pairs. Firstly, a thermal SET process between LiHMDS and [TEMPO][BF4] is discussed. Next, the influence of Lewis acid complexation on the electron acceptor will be highlighted to facilitate a SET between (pBrPh)3N and TCNQ. Finally, an analysis of sulfonium salts as electron acceptors will demonstrate how to manage systems with rapidly decomposing radical species. This framework equips the reader with an expanded array of tools for both predicting and characterizing SET events within FLP chemistry, thereby enabling its extension and application to the broader domain of main-group (photo)redox chemistry. [ABSTRACT FROM AUTHOR]

Herein, we present the formation of transient radical ion pairs (RIPs) by single‐electron transfer (SET) in phosphine−quinone systems and explore their potential for the activation of C−H bonds. PMes3 (Mes=2,4,6‐Me3C6H2) reacts with DDQ (2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone) with formation of the P−O bonded zwitterionic adduct Mes3P−DDQ (1), while the reaction with the sterically more crowded PTip3 (Tip=2,4,6‐iPr3C6H2) afforded C−H bond activation product Tip2P(H)(2‐[CMe2(DDQ)]‐4,6‐iPr2‐C6H2) (2). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip3]⋅+[DDQ]⋅−, and subsequent homolytic C−H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip2P(H)(2‐[CMe2{TCQ−B(C6F5)3}]‐4,6‐iPr2‐C6H2) (4, TCQ=tetrachloro‐1,4‐benzoquinone) and Tip2P(H)(2‐[CMe2{oQtBu−B(C6F5)3}]‐4,6‐iPr2‐C6H2) (8, oQtBu=3,5‐di‐tert‐butyl‐1,2‐benzoquinone), from reactions of PTip3 with Lewis‐acid activated quinones, TCQ−B(C6F5)3 and oQtBu−B(C6F5)3, respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C−H bond activation by the synergistic action of radical ion pairs. [ABSTRACT FROM AUTHOR]

(1) Background: This work evaluated the usability of commercial "low-cost" air quality sensor systems to substantiate evidence-based policy making. (2) Methods: Two commercially available sensor systems (Airly, Kunak) were benchmarked at a regulatory air quality monitoring station (AQMS) and subsequently deployed in Kampenhout and Sint-Niklaas (Belgium) to address real-world policy concerns: (a) what is the pollution contribution from road traffic near a school and at a central city square and (b) do local traffic interventions result in quantifiable air quality impacts? (3) Results: The considered sensor systems performed well in terms of data capture, correlation and intra-sensor uncertainty. Their accuracy was improved via local re-calibration, up to data quality levels for indicative measurements as set in the Air Quality Directive (Uexp < 50% for PM and <25% for NO2). A methodological setup was proposed using local background and source locations, allowing for quantification of the (3.1) maximum potential impact of local policy interventions and (3.2) air quality impacts from different traffic interventions with local contribution reductions of up to 89% for NO2 and 60% for NO throughout the considered 3 month monitoring period; (4) Conclusions: Our results indicate that commercial air quality sensor systems are able to accurately quantify air quality impacts from (even short-lived) local traffic measures and contribute to evidence-based policy making under the condition of a proper methodological setup (background normalization) and data quality (recurrent calibration) procedure. The applied methodology and learnings were distilled in a blueprint for air quality sensor networks for replication actions in other cities. [ABSTRACT FROM AUTHOR]

Urban air quality mapping has been widely applied in urban planning, air pollution control and personal air pollution exposure assessment. Urban air quality maps are traditionally derived using measurements from fixed monitoring stations. Due to high cost, these stations are generally sparsely deployed in a few representative locations, leading to a highly generalized air quality map. In addition, urban air quality varies rapidly over short distances (<1 km) and is influenced by meteorological conditions, road network and traffic flow. These variations are not well represented in coarse-grained air quality maps generated by conventional fixed-site monitoring methods but have important implications for characterizing heterogeneous personal air pollution exposures and identifying localized air pollution hotspots. Therefore, fine-grained urban air quality mapping is indispensable. In this context, supplementary low-cost mobile sensors make mobile air quality monitoring a promising alternative. Using sparse air quality measurements collected by mobile sensors and various contextual factors, especially traffic flow, we propose a context-aware locally adapted deep forest (CLADF) model to infer the distribution of NO2 by 100 m and 1 h resolution for fine-grained air quality mapping. The CLADF model exploits deep forest to construct a local model for each cluster consisting of nearest neighbor measurements in contextual feature space, and considers traffic flow as an important contextual feature. Extensive validation experiments were conducted using mobile NO2 measurements collected by 17 postal vans equipped with low-cost sensors operating in Antwerp, Belgium. The experimental results demonstrate that the CLADF model achieves the lowest RMSE as well as advances in accuracy and correlation, compared with various benchmark models, including random forest, deep forest, extreme gradient boosting and support vector regression. [ABSTRACT FROM AUTHOR]

One of the most widely available technologies to clean the air in homes of particulate matter of less than 2.5 µm in diameter (PM2.5), known to have negative health impacts, are portable home air purifiers (HAPs). This paper presents research which (1) explored the effectiveness of HAPs in real-world conditions in 57 homes in three European cities; (2) examined if HAPs affect users' perceptions of the indoor air quality (IAQ) at home; and (3) considered the motivations for occupants' operation of HAPs. Results from this study found that PM2.5 concentrations in bedrooms were reduced by 45% to 69%; perceptions of IAQ were not correlated with measured high PM2.5 levels; occupants reported the HAPs to have a 'cooling' effect, which may explain why the predominant driver of HAP use was thermal comfort, rather than IAQ, in all three cities. The latter finding was supported by a statistically significant increase in the probability of HAP use with increasing indoor temperatures. If the operation of HAPs can be managed, or fully automated, to reflect indoor air pollution levels rather than thermal conditions, better pollutant reduction would be feasible and their use to reduce PM2.5 may help mitigate the negative health effects of exposure whilst at home. [ABSTRACT FROM AUTHOR]

Abstract Bacterial endotoxins are a component of particulate matter (PM) with anticipated health implications, yet we know little about how host reception of endotoxin through toll-like receptor 4 (TLR4) is affected by its association with other PM components. Subsequently, we investigated the relationship between endotoxin concentration (recombinant Factor C (rFC) assay) and host recognition (HEK Blue-TLR4 NF-kB reporter cell line based assay) in various compositions of urban PM, including road traffic, industrial and urban green land use classes. While the assays did not correlate strongly between each other, the TLR4 reporter cell line was found to be better correlated to the IL-8 response of PM. Furthermore, the ability of the quantified endotoxin (rFC assay) to stimulate the TLR4/MD-2 complex was significantly affected by the urban land use class, where traffic locations were found to be significantly higher in bioactive endotoxin than the industrial and green locations. We subsequently turned our attention to PM composition and characterized the samples based on transition metal content (through ICP-MS). The effect of nickel and cobalt – previously reported to activate the hTLR4/MD-2 complex – was found to be negligible in comparison to that of iron. Here, the addition of iron as a factor significantly improved the regression model between the two endotoxin assays, explaining 77% of the variation of the TLR4 stimulation and excluding the significant effect of land use class. Moreover, the effect of iron proved to be more than a correlation, since dosing LPS with Fe2+ led to an increase up to 64% in TLR4 stimulation, while Fe2+ without LPS was unable to stimulate a response. This study shows that endotoxin quantification assays (such as the rFC assay) may not always correspond to human biological recognition of endotoxin in urban PM, while its toxicity can be synergistically influenced by the associated PM composition. Graphical abstract Image 1 Highlights • Quantified endotoxin not strongly correlated to host recognition through hTLR4. • HEK TLR4 cell line better assay for IL8 response than rFC-quantified endotoxin. • Bioactivity of atmospheric endotoxin influenced by land-use class. • Ferrous iron modulates host endotoxin response. Although endotoxins are typically quantified in ambient air, its toxicity is significantly influenced by the associated PM composition (e.g. as shown in this study with iron, one of the most abundant transition metals found in urban PM). [ABSTRACT FROM AUTHOR]

Biomagnetic monitoring of atmospheric pollution is a growing application in the field of environmental magnetism. Particulate matter (PM) in atmospheric pollution contains readily measurable concentrations of magnetic minerals. Biological surfaces, exposed to atmospheric pollution, accumulate magnetic particles over time, providing a record of location-specific, time-integrated air quality information. This review summarizes current knowledge of biological material ("sensors") used for biomagnetic monitoring purposes. Our work addresses the following: the range of magnetic properties reported for lichens, mosses, leaves, bark, trunk wood, insects, crustaceans, mammal and human tissues; their associations with atmospheric pollutant species (PM, NOx, trace elements, PAHs); the pros and cons of biomagnetic monitoring of atmospheric pollution; current challenges for large-scale implementation of biomagnetic monitoring; and future perspectives. A summary table is presented, with the aim of aiding researchers and policy makers in selecting the most suitable biological sensor for their intended biomagnetic monitoring purpose. [ABSTRACT FROM AUTHOR]

Understanding the accumulation behaviour of atmospheric particles inside tree leaves is of great importance for the interpretation of biomagnetic monitoring results. In this study, we evaluated the temporal variation of the saturation isothermal remanent magnetisation (SIRM) of leaves of a roadside urban Platanus x acerifolia Willd. tree in Antwerp, Belgium. We hereby examined the seasonal development of the total leaf SIRM signal as well as the leaf-encapsulated fraction of the deposited dust, by washing the leaves before biomagnetic analysis. On average 38% of the leaf SIRM signal was exhibited by the leaf-encapsulated particles. Significant correlations were found between the SIRM and the cumulative daily average atmospheric PM10 and PM2.5 measurements. Moreover, a steady increase of the SIRM throughout the in-leaf season was observed endorsing the applicability of biomagnetic monitoring as a proxy for the time-integrated PM exposure of urban tree leaves. Strongest correlations were obtained for the SIRM of the leaf-encapsulated particles which confirms the dynamic nature of the leaf surface-accumulated particles. [ABSTRACT FROM AUTHOR]

Biomagnetic monitoring of tree leaf deposited particles has proven to be a good indicator of the ambient particulate concentration. The objective of this study is to apply this method to validate a local-scale air quality model (ENVI-met), using 96 tree crown sampling locations in a typical urban street canyon. To the best of our knowledge, the application of biomagnetic monitoring for the validation of pollutant dispersion modeling is hereby presented for the first time. Quantitative ENVI-met validation showed significant correlations between modeled and measured results throughout the entire in-leaf period. ENVI-met performed much better at the first half of the street canyon close to the ring road (r = 0.58-0.79, RMSE = 44-49%), compared to second part (r = 0.58-0.64, RMSE = 74-102%). The spatial model behavior was evaluated by testing effects of height, azimuthal position, tree position and distance from the main pollution source on the obtained model results and magnetic measurements. Our results demonstrate that biomagnetic monitoring seems to be a valuable method to evaluate the performance of air quality models. Due to the high spatial and temporal resolution of this technique, biomagnetic monitoring can be applied anywhere in the city (where urban green is present) to evaluate model performance at different spatial scales. [ABSTRACT FROM AUTHOR]

Biomagnetic monitoring of urban tree leaves has proven to be a good estimator of ambient particulate matter. We evaluated its relevancy by determining leaf area normalised weight (mg m-2) and SIRM (A) of leaf-deposited particles within three different size fractions (>10 μm, 3-10 μm and 0.2-3 μm) and the SIRM of the leaf-encapsulated particles. Results showed that throughout the in-leaf season, the trees accumulated on average 747 mg m-2 of dust on their leaves, of which 74 mg m-2 was within the 0.2-10 μm (~PM10) size range and 40 mg m-2 within the 0.2-3 μm (~PM3) size range. A significant correlation between the SIRM and weight of the surface-deposited particles confirms the potential of biomagnetic monitoring as a proxy for the amount of leaf-deposited particles. Spatial variation of both SIRM and weight throughout the street canyon suggests traffic and wind as key factors for respectively the source and distribution of urban particulates. [ABSTRACT FROM AUTHOR]

Biomagnetic monitoring of urban tree leaves has proven to be a good estimator of ambient particulate matter. We evaluated its relevancy by determining leaf area normalised weight (mg m−2) and SIRM (A) of leaf-deposited particles within three different size fractions (>10 μm, 3–10 μm and 0.2–3 μm) and the SIRM of the leaf-encapsulated particles. Results showed that throughout the in-leaf season, the trees accumulated on average 747 mg m−2 of dust on their leaves, of which 74 mg m−2 was within the 0.2–10 μm (∼PM10) size range and 40 mg m−2 within the 0.2–3 μm (∼PM3) size range. A significant correlation between the SIRM and weight of the surface-deposited particles confirms the potential of biomagnetic monitoring as a proxy for the amount of leaf-deposited particles. Spatial variation of both SIRM and weight throughout the street canyon suggests traffic and wind as key factors for respectively the source and distribution of urban particulates. [Copyright &y& Elsevier]

Abstract: Recently, biomagnetic monitoring of tree leaves has proven to be a good estimator for ambient particulate concentration. This paper investigates the usefulness of biomagnetic leaf monitoring of crown deposited particles to assess the spatial PM distribution inside individual tree crowns and an urban street canyon in Ghent (Belgium). Results demonstrate that biomagnetic monitoring can be used to assess spatial PM variations, even within single tree crowns. SIRM values decrease exponentially with height and azimuthal effects are obtained for wind exposed sides of the street canyon. Edge and canyon trees seem to be exposed differently. As far as we know, this study is the first to present biomagnetic monitoring results of different trees within a single street canyon. The results not only give valuable insights into the spatial distribution of particulate matter inside tree crowns and a street canyon, but also offer a great potential as validation tool for air quality modelling. [Copyright &y& Elsevier]

As real-life experimental data on natural ventilation of atmospheric pollution levels in urban street canyons is still scarce and has proven to be complex, this study, experimentally evaluated the impact of an urban street canyon opening on local atmospheric pollution levels, during a 2-week field campaign in a typical urban street canyon in Antwerp, Belgium. Besides following up on atmospheric particulate matter (PM), ultrafine particles (UFPs) and black carbon (BC) levels, the magneto-chemical PM 10 composition was quantified to identify contributions of specific elements in enclosed versus open street canyon sections. Results indicated no higher overall PM, UFP and BC concentrations at the enclosed site compared to the open site, but significant day-to-day variability between both monitoring locations, depending on the experienced wind conditions. On days with oblique wind regimes (4 out of 14), natural ventilation was observed at the open location while higher element contributions of Ca, Fe, Co, Ni, Cu, Zn and Sr were exhibited at the enclosed location. Magnetic properties correlated with the PM 10 filter loading, and elemental content of Fe, Cr, Mn and Ti. Magnetic bivariate ratios identified finel-grained magnetite carriers with grain sizes below 0.1 μm, indicating similar magnetic source contributions at both monitoring locations. Our holistic approach, combining atmospheric monitoring with magneto-chemical PM characterization has shown the complex impact of real-life wind flow regimes, different source contributions and local traffic dynamics on the resulting pollutant concentrations and contribute to a better understanding on the urban ventilation processes of atmospheric pollution. Unlabelled Image • Real-life experimental study on natural ventilation in a typical urban street canyon. • Atmospheric PM 10 concentration and analytical magneto-chemical composition. • Natural ventilation was suggested under oblique wind regimes, but net effect was negligible. • Higher contributions of Ca, Fe, Co, Ni, Cu, Zn and Sr at the enclosed location. • Holistic approach contributes to a better understanding on urban pollution ventilation. [ABSTRACT FROM AUTHOR]

Abstract: To circumvent difficulties associated with monitoring adult predatory birds, we investigated the feasibility of different non-destructive strategies for nestling white-tailed eagles (Haliaeetus albicilla). We were able to quantify polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorinated pesticides (OCPs) in body feathers (16.92, 3.37 and 7.81ngg−1 dw, respectively), blood plasma (8.37, 0.32 and 5.22ngmL−1 ww, respectively), and preen oil (1157.95, 30.92 and 440.74ngg−1 ww, respectively) of all nestlings (N=14). Strong significant correlations between blood plasma and preen oil concentrations (0.565≤r≤0.801; P<0.05) indicate that preen oil levels closely reflect the internal state of contamination. We found fewer significant correlations between body feather and blood plasma concentrations, which were almost exclusively between PCB concentrations (0.554≤r≤0.737; P<0.05). These results differ from a previous study on younger nestlings, and may indicate that the nestlings studied here, ready to fledge the nest, were possibly undergoing certain physiological changes that may have confounded the use of body feathers as biomonitor matrix. Finally, we provide an integrated discussion on the use of body feathers and preen oil as non-destructive biomonitor strategies for nestling predatory birds. [Copyright &y& Elsevier]

Humans are generally exposed to per- and polyfluoroalkyl substances (PFAS) through their diet. Whilst plenty of data are available on commercial food products, little information exists on the contribution of self-cultivated food, such as home-produced eggs (HPE), to the dietary PFAS intake in humans. The prevalence of 17 legacy and emerging PFAS in HPE (N = 70) from free-ranging laying hens was examined at 35 private gardens, situated within a 10 km radius from a fluorochemical plant in Antwerp (Belgium). Potential influences from housing conditions (feed type and number of individuals) and age of the chickens on the egg concentrations was examined, and possible human health risks were evaluated. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were detected in all samples. PFOS was the dominant compound and concentrations (range: 0.13–241 ng/g wet weight) steeply decreased with distance from the fluorochemical plant, while there was no clear distance trend for other PFAS. Laying hens receiving an obligate diet of kitchen leftovers, exhibited higher PFOS and PFOA concentrations in their eggs than hens feeding only on commercial food, suggesting that garden produce may be a relevant exposure pathway to both chickens and humans. The age of laying hens affected egg PFAS concentrations, with younger hens exhibiting significantly higher egg PFOA concentrations. Based on a modest human consumption scenario of two eggs per week, the European health guideline was exceeded in ≥67% of the locations for all age classes, both nearby and further away (till 10 km) from the plant site. These results indicate that PFAS exposure via HPE causes potential human health risks. Extensive analysis in other self-cultivated food items on a larger spatial scale is highly recommended, taking into account potential factors that may affect PFAS bioavailability to garden produce. [Display omitted] • Eight PFAS were detected in homegrown eggs of free-ranging laying hens. • PFOS was the dominant compound and concentrations decreased from the fluorochemical plant. • Diet and age of laying hens were related to PFOS and PFOA egg concentrations. • Homegrown eggs can be an important exposure pathway of PFAS to humans. • Based on exposure estimation via egg intake, health guidelines were often exceeded. [ABSTRACT FROM AUTHOR]

Herein, we present the formation of transient radical ion pairs (RIPs) by single-electron transfer (SET) in phosphine-quinone systems and explore their potential for the activation of C-H bonds. PMes 3 (Mes=2,4,6-Me 3 C 6 H 2 ) reacts with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) with formation of the P-O bonded zwitterionic adduct Mes 3 P-DDQ (1), while the reaction with the sterically more crowded PTip 3 (Tip=2,4,6-iPr 3 C 6 H 2 ) afforded C-H bond activation product Tip 2 P(H)(2-[CMe 2 (DDQ)]-4,6-iPr 2 -C 6 H 2 ) (2). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip 3 ]⋅ + [DDQ]⋅ - , and subsequent homolytic C-H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip 2 P(H)(2-[CMe 2 {TCQ-B(C 6 F 5 ) 3 }]-4,6-iPr 2 -C 6 H 2 ) (4, TCQ=tetrachloro-1,4-benzoquinone) and Tip 2 P(H)(2-[CMe 2 {oQ tBu -B(C 6 F 5 ) 3 }]-4,6-iPr 2 -C 6 H 2 ) (8, oQ tBu =3,5-di-tert-butyl-1,2-benzoquinone), from reactions of PTip 3 with Lewis-acid activated quinones, TCQ-B(C 6 F 5 ) 3 and oQ tBu -B(C 6 F 5 ) 3 , respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C-H bond activation by the synergistic action of radical ion pairs., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)