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Abstract The resonant excitation of electronic transitions with coherent laser sources creates quantum coherent superpositions of the involved electronic states. Most time-resolved studies have focused on gases or isolated subsystems embedded in insulating solids, aiming for applications in quantum information. Here, we focus on the coherent control of orbital wavefunctions in the correlated quantum material Tb2Ti2O7, which forms an interacting spin liquid ground state. We show that resonant excitation with a strong THz pulse creates a coherent superposition of the lowest energy Tb 4f states. The coherence manifests itself as a macroscopic oscillating magnetic dipole, which is detected by ultrafast resonant x-ray diffraction. We envision the coherent control of orbital wavefunctions demonstrated here to become a new tool for the ultrafast manipulation and investigation of quantum materials.

Condensed particulate polycyclic aromatic hydrocarbons (PAHs) are a group of toxic organic compounds that are produced by the incomplete combustion of organic material, for example, via biomass burning or traffic emissions. Even at low long-term exposure levels, such as 1 ng m−3 of benzo(a)pyrene, PAHs are recognized to be detrimental to human health. Therefore, a quantitative characterization of PAHs at sub-nanogram-per-cubic-meter levels is important to examine precise long-term exposure. A new ultrasensitive generation of proton transfer reaction mass spectrometry (PTR-MS) instruments coupled to the CHARON particle inlet are capable of quantitatively detecting this toxic class of compounds at a molecular composition level while also offering a high temporal resolution of < 1 min and sub-nanogram-per-cubic-meter limits of detection. To demonstrate the capabilities of this new CHARON FUSION PTR-TOF 10k instrument, we present a thorough characterization of summertime ambient condensed PAHs in Innsbruck, Austria. With a mass resolution of > 14 000 (m Δm−1 at full width at half maximum) and sensitivities of up to 40 cps ng−1 m3 (where cps represents counts per second), a series of nine condensed PAHs of four (C16H10) to six aromatic rings (C26H16) are identified among a plethora of organic compounds in ambient organic aerosol. With 1 min limits of detection between 19 and 46 pg m−3, quantitative time series of these PAHs at the lowermost mass concentrations are determined. To understand the sources and processes associated with these condensed summertime PAHs in greater detail, a matrix factorization including the ∼ 4000 ionic signals detected by the CHARON FUSION PTR-TOF 10k is performed, representing the vast majority of the mass concentration of ambient organic aerosol. A total of 10 factors and their corresponding time series can be identified. Known tracer compounds like levoglucosan, pinonic acid or nicotine consequently allow the assignment to individual organic aerosol sources and physicochemical processes. PAH emissions from traffic are found to be minor contributors during this summertime sampling period. The highest concentrations of PAHs are identified in a mixed aged oxygenated organic aerosol, followed by a biomass burning and a cigarette smoke organic aerosol.

Reliable short-term sea ice forecasts are needed to support maritime operations in polar regions. While sea ice forecasts produced by physically based models still have limited accuracy, statistical post-processing techniques can be applied to reduce forecast errors. In this study, post-processing methods based on supervised machine learning have been developed for improving the skill of sea ice concentration forecasts from the TOPAZ4 prediction system for lead times from 1 to 10 d. The deep learning models use predictors from TOPAZ4 sea ice forecasts, weather forecasts, and sea ice concentration observations. Predicting the sea ice concentration for the next 10 d takes about 4 min (including data preparation), which is reasonable in an operational context. On average, the forecasts from the deep learning models have a root mean square error 41 % lower than TOPAZ4 forecasts and 29 % lower than forecasts based on persistence of sea ice concentration observations. They also significantly improve the forecasts for the location of the ice edges, with similar improvements as for the root mean square error. Furthermore, the impact of different types of predictors (observations, sea ice, and weather forecasts) on the predictions has been evaluated. Sea ice observations are the most important type of predictors, and the weather forecasts have a much stronger impact on the predictions than sea ice forecasts.

Background and Aims: Data on the prevalence and characteristics of so-called rare HCV genotypes (GTs) in larger cohorts is limited. This study investigates the frequency of rare GT and resistance-associated substitutions and the efficacy of retreatment in a European cohort. Methods: A total of 129 patients with rare GT1-6 were included from the European resistance database. NS3, NS5A, and NS5B were sequenced and clinical parameters and retreatment efficacies were collected retrospectively. Results: Overall 1.5% (69/4,656) of direct-acting antiviral (DAA)-naive and 4.4% (60/1,376) of DAA-failure patients were infected with rare GT. Although rare GTs were almost equally distributed throughout GT1-6 in DAA-naive patients, we detected mainly rare GT4 (47%, 28/60 GT4; of these n = 17, subtype 4r) and GT3 (25%, 15/60 GT3, of these n = 8, subtype 3b) among DAA-failures. A total of 62% (37/60) of DAA failures had not responded to first-generation regimes and the majority was infected with rare GT4 (57%, 21/37). In contrast, among patients with failure to pangenotypic DAA regimens (38%, 23/60), infections with rare GT3 were overrepresented (57%, 13/23). Although NS5A RASs were uncommon in rare GT2, GT5a, and GT6, we observed combined RASs in rare GT1, GT3, and GT4 at positions 28, 30, 31, which can be considered as inherent. DAA failures with completed follow-up of retreatment, achieved a high SVR rate (94%, 45/48 modified intention-to-treat analysis; 92%, 45/49 intention-to-treat). Three patients with GT4f, 4r, or 3b, respectively, had virological treatment failure. Conclusions: In this European cohort, rare HCV GT were uncommon. Accumulation of specific rare GT in DAA-failure patients suggests reduced antiviral activities of DAA regimens. The limited global availability of pangenotypic regimens for first line therapy as well as multiple targeted regimens for retreatment could result in HCV elimination targets being delayed. Impact and implications: Data on the prevalence and characteristics of rare HCV genotypes (GT) in larger cohorts are still scarce. This study found low rates of rare HCV GTs among European HCV-infected patients. In direct-acting antiviral (DAA)-failure patients, rare GT3 subtypes accumulated after pangenotypic DAA treatment and rare GT4 after first generation DAA failure and viral resistance was detected at NS5A positions 28, 30, and 31. The limited global availability of pangenotypic DAA regimens for first line therapy as well as multiple targeted regimens for retreatment could result in HCV elimination targets being delayed.

Ammonia is a significant precursor of PM2.5 particles and thus contributes to poor air quality in many regions. Furthermore, ammonia concentrations are rising due to the increase of large-scale, intensive agricultural activities, which are often accompanied by greater use of fertilizers and concentrated animal feedlots. Ammonia is highly reactive and thus highly variable and difficult to measure. Satellite-based instruments, such as the Atmospheric Infrared Sounder (AIRS) and the Cross-Track Infrared Sounder (CrIS), have been shown to provide much greater temporal and spatial coverage of ammonia distribution and variability than is possible with in situ networks or aircraft campaigns, but the validation of these data is limited. Here we evaluate MUSES (multi-spectra, multi-species, multi-sensors) ammonia retrievals from AIRS and CrIS against ammonia measurements from aircraft in the California Central Valley and in the Colorado Front Range. These are small datasets taken over high-source regions under very different conditions: winter in California and summer in Colorado. Direct comparisons of the surface values of the retrieved profiles are biased very low in California (∼ 40 ppbv) and slightly high in Colorado (∼ 4 ppbv). This bias appears to be primarily due to smoothing error, since applying the instrument operator effectively reduces the bias to zero; even after the smoothing error is accounted for, the average uncertainty at the surface is in the 20 %–30 % range. We also compare 3 years of CrIS ammonia against an in situ network in the Magic Valley in Idaho We show that CrIS ammonia captures both the seasonal signal and the spatial variability in the Magic Valley, although it is biased low here also. In summary, this analysis substantially adds to the validation record but also points to the need for more validation under many different conditions and at higher altitudes.

Toluene represents a large fraction of anthropogenic emissions and significantly contributes to tropospheric ozone and secondary organic aerosol (SOA) formation. Despite the fact that toluene is one of the most studied aromatic compounds, detailed chemical mechanisms still fail to correctly reproduce the speciation of toluene gaseous and condensed oxidation products. This study aims to elucidate the role of initial experimental conditions in toluene SOA mass loadings and to investigate gas–particle partitioning of its reaction products at different relevant temperatures. Gaseous and particulate reaction products were identified and quantified using a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) coupled to a CHemical Analysis of aeRosol ONline (CHARON) inlet. The chemical system exhibited a volatility distribution mostly in the semi-volatile regime. Temperature decrease caused a shift of saturation concentration towards lower values. The CHARON–PTR-ToF-MS instrument identified and quantified approximately 60 %–80 % of the total organic mass measured by an aerosol mass spectrometer. A detailed mechanism for toluene gaseous oxidation was developed based on the Master Chemical Mechanism (MCM) and Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) deterministic mechanisms, modified following the literature. The new mechanism showed improvements in modeling oxidation product speciation with more observed species represented and more representative concentrations compared to the MCM–GECKO-A reference. Tests on partitioning processes, nonideality, and wall losses highlighted the high dependency of SOA formation on the considered processes. Our results underline the fact that volatility is not sufficient to explain the gas–particle partitioning: the organic and the aqueous phases need to be considered as well as the interactions between compounds in the particle phase.

We study sub-micron Y3Fe5O12 (YIG) flakes that we produce via mechanical cleaving and exfoliation of YIG single crystals. By characterizing their structural and magnetic properties, we find that these YIG flakes have surfaces oriented along unusual crystallographic axes and uniaxial in-plane magnetic anisotropy due to their shape, both of which are not commonly available in YIG thin films. These physical properties, combined with the possibility of picking up the YIG flakes and stacking them onto flakes of other van der Waals materials or pre-patterned electrodes or waveguides, open unexplored possibilities for magnonics and for the realization of novel YIG-based heterostructures and spintronic devices.

With an atmospheric concentration of approximately 2000 parts per billion (ppbV, 10−9), methane (CH4) is the second most abundant greenhouse gas (GHG) in the atmosphere after carbon dioxide (CO2). The task of long-term and spatially resolved GHG monitoring to verify whether climate policy actions are effective is becoming more crucial as climate change progresses. In this paper we report the CH4 concentration readings of our photoacoustic (PA) sensor over a 5 d period at Hohenpeißenberg, Germany. As a reference device, a calibrated cavity ring-down spectrometer, Picarro G2301, from the meteorological observatory of the German Weather Service (DWD) was employed. Trace gas measurements with photoacoustic instruments promise to provide low detection limits at comparably low costs. However, PA devices are often susceptible to cross-sensitivities related to fluctuating environmental conditions, e.g. ambient humidity. The obtained results show that for PA sensor systems non-radiative relaxation effects induced by varying humidity are a non-negligible factor. Applying algorithm compensation techniques, which are capable of calculating the influence of non-radiative relaxation effects on the photoacoustic signal, increase the accuracy of the photoacoustic sensor significantly. With an average relative deviation of 1.11 % from the G2301, the photoacoustic sensor shows good agreement with the reference instrument.

The heterogeneous chemistry of atmospheric aerosols involves multiphase chemical kinetics that can be described by kinetic multi-layer models (KMs) that explicitly resolve mass transport and chemical reactions. However, KMs are computationally too expensive to be used as sub-modules in large-scale atmospheric models, and the computational costs also limit their utility in inverse-modeling approaches commonly used to infer aerosol kinetic parameters from laboratory studies. In this study, we show how machine learning methods can generate inexpensive surrogate models for the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB) to predict reaction times in multiphase chemical systems. We apply and compare two common and openly available methods for the generation of surrogate models, polynomial chaos expansion (PCE) with UQLab and neural networks (NNs) through the Python package Keras. We show that the PCE method is well suited to determining global sensitivity indices of the KMs, and we demonstrate how inverse-modeling applications can be enabled or accelerated with NN-suggested sampling. These qualities make them suitable supporting tools for laboratory work in the interpretation of data and the design of future experiments. Overall, the KM surrogate models investigated in this study are fast, accurate, and robust, which suggests their applicability as sub-modules in large-scale atmospheric models.

Quality assessments of horticultural products are still often carried out manually in breeding contexts, although computer vision systems have been reported to be able to overcome the limitations of manual assessments, e.g. in automated food processing. Here, a new computer vision workflow for quality trait assessment of bush bean pods (Phaseolus vulgaris) is introduced to replace physical measurements and visual scorings of expert breeders, while increasing consistency, accuracy, and objectivity of the measurements. A closed imaging box was used to take images of bean pods from 40 different varieties to develop and validate computer vision workflows to assess breeding relevant shape and color traits of bean pods. For the detection of beaks and peduncles via a neural network approach (Mask R-CNN) accuracies of 95.5% were reached. Computer vision estimations and manual reference measurements of length and caliber were highly correlated (R=0.99). Also, curvature and brightness of green bean pods well- correlated with visual scorings of expert breeders (R=0.81, R=-0.87). A Random Forest Classifier was trained to distinguish yellow and extremely rare bicolored pods and a cross validation accuracy of 83 ±7% was reached. An additional backlight LED panel enabled non-destructive analysis of seed formation inside the pod and promising results were achieved using a Faster R-CNN model. This new computer vision workflow provides the opportunity to replace well-established manual workflows for quality trait assessment of bush bean pods as it is more objective, reliable, and considerably faster.

High-quality ocean colour observations are increasingly accessible to support various monitoring and research activities for water quality measurements. In this paper, we present a newly developed regional total suspended solids (TSSs) empirical model using MODIS Aqua's Rrs(530) and Rrs(666) reflectance bands to investigate the spatial and temporal variation in TSS dynamics along the southwest coast of Sarawak, Borneo, with the application of the Open Data Cube (ODC) platform. The performance of this TSS retrieval model was evaluated using error metrics (bias = 1.0, MAE = 1.47, and RMSE = 0.22, in milligrams per litre) with a log10 transformation prior to calculation as well as using a k-fold cross-validation technique. The temporally averaged map of the TSS distribution, using daily MODIS Aqua satellite datasets from 2003 until 2019, revealed that large TSS plumes were detected – particularly in the Lupar and Rajang coastal areas – on a yearly basis. The average TSS concentration in these coastal waters was in the range of 15–20 mg L−1. Moreover, the spatial map of the TSS coefficient of variation (CV) indicated strong TSS variability (approximately 90 %) in the Samunsam–Sematan coastal areas, which could potentially impact nearby coral reef habitats in this region. Study of the temporal TSS variation provides further evidence that monsoonal patterns drive the TSS release in these tropical water systems, with distinct and widespread TSS plume variations observed between the northeast and southwest monsoon periods. A map of relative TSS distribution anomalies revealed strong spatial TSS variations in the Samunsam–Sematan coastal areas, while 2010 recorded a major increase (approximately 100 %) and widespread TSS distribution with respect to the long-term mean. Furthermore, study of the contribution of river discharge to the TSS distribution showed a weak correlation across time at both the Lupar and Rajang river mouth points. The variability in the TSS distribution across coastal river points was studied by investigating the variation in the TSS pixels at three transect points, stretching from the river mouth into territorial and open-water zones, for eight main rivers. The results showed a progressively decreasing pattern of nearly 50 % in relation to the distance from shore, with exceptions in the northeast regions of the study area. Essentially, our findings demonstrate that the TSS levels on the southwest coast of Sarawak are within local water quality standards, promoting various marine and socio-economic activities. This study presents the first observation of TSS distributions in Sarawak coastal systems with the application of remote sensing technologies and aims at enhancing coastal sediment management strategies for the sustainable use of coastal waters and their resources.

Abstract Communication for the Internet of things (IoT) currently is predominantly narrowband and cannot always guarantee low latency and high reliability. Future IoT applications such as flexible manufacturing, augmented reality and self-driving vehicles rely on sophisticated real-time processing in the cloud to which mobile IoT devices are connected. High-capacity links that meet the requirements of the upcoming 6G systems cannot easily be provided by the current radio-based communication infrastructure. Light communication, which is also denoted as LiFi, offers huge amounts of spectrum, extra security and low-latency transmission free of interference even in dense reuse settings. We present the current state-of-the-art of LiFi systems and introduce new features needed for future IoT applications. We discuss results from a distributed multiple-input multiple-output topology with a fronthaul using plastic optical fibre. We evaluate seamless mobility between the light access points and also handovers to 5G, besides low-power transmission and integrated positioning. Future LiFi development, implementation and efforts towards standardization are addressed in the EU ELIoT project which is presented here.

Deep coastal inlets are sites of high sedimentation and organic carbon deposition that account for 11 % of the world's organic carbon burial. Australasia's mid- to high-latitude regions have many such systems. It is important to understand the role of climate forcings in influencing hypoxia and organic matter cycling in these systems, but many such systems, especially in Australasia, remain poorly described. We analysed a decade of in situ water quality data from Macquarie Harbour, Tasmania, a deep coastal inlet with more than 180 000 t of organic carbon loading per annum. Monthly dissolved oxygen, total Kjeldahl nitrogen, dissolved organic carbon, and dissolved inorganic nitrogen concentrations were significantly affected by rainfall patterns. Increased rainfall was correlated to higher organic carbon and nitrogen loading, lower oxygen concentrations in deep basins, and greater oxygen concentrations in surface waters. Most notably, the Southern Annular Mode (SAM) significantly influenced oxygen distribution in the system. High river flow (associated with low SAM index values) impedes deep water renewal as the primary mechanism driving basin water hypoxia. Climate forecasting predicts increased winter rainfall and decreased summer rainfall, which may further exacerbate hypoxia in this system. Currently, Macquarie Harbour's basins experience frequent (up to 36 % of the time) and prolonged (up to 2 years) oxygen-poor conditions that may promote greenhouse gas (CH4, N2O) production altering the processing of organic matter entering the system. The increased winter rainfall predicted for the area will likely promote the increased spread and duration of hypoxia in the basins. Further understanding of these systems and how they respond to climate change will improve our estimates of future organic matter cycling (burial vs. export).

Abstract Background Pain is one of the most common, yet challenging problems leading to emergency department (ED) presentation, despite the availability of a wide range of pharmacological therapies. Virtual reality (VR) simulations are well studied in a wide variety of clinical settings, including acute and chronic pain management, as well as anxiety disorders. However, studies in the busy environment of an adult ED are scarce. The aim of this study is to explore the feasibility and effectiveness of a VR simulation for pain and anxiety control in a convenience sample of adult ED patients presenting with traumatic and non-traumatic pain triaged 2–5 (i.e., urgent to non-urgent) with a pain rating of ≥ 3 on a numeric rating scale (NRS 0–10). Methods Prospective within-subject, repeated measures interventional feasibility pilot study at a Swiss University ED. The intervention consisted of a virtual reality simulation in addition to usual care. Pain and anxiety levels were measured using a verbally administered numeric rating scale (NRS) before and after the intervention. Information on patient experience was collected using established rating scales. Results Fifty-two patients were enrolled. The most common pain localisations were extremities (n = 15, 28.8%) and abdomen (n = 12, 23.1%). About one third of patients presented with trauma-associated pain (n = 16, 30.8%). Duration of pain was mainly acute ( 24 h) (n = 32, 61.5%). The majority of patients were triage category 3, i.e. semi-urgent (n = 48, 92.3%). Significant reduction in pain (NRS median pre-VR simulation 4.5 (IQR 3–7) vs. median post-VR simulation 3 (IQR 2–5), p

Southeast Asian peatlands represent a globally significant carbon store that is destabilized by land-use changes like deforestation and the conversion into plantations, causing high carbon dioxide (CO2) emissions from peat soils and increased leaching of peat carbon into rivers. While this high carbon leaching and consequentially high DOC concentrations suggest that CO2 emissions from peat-draining rivers would be high, estimates based on field data suggest they are only moderate. In this study, we offer an explanation for this phenomenon by showing that carbon decomposition is hampered by the low pH in peat-draining rivers. This limits CO2 production in and emissions from these rivers. We find an exponential pH limitation that shows good agreement with laboratory measurements from high-latitude peat soils. Additionally, our results suggest that enhanced input of carbonate minerals increases CO2 emissions from peat-draining rivers by counteracting the pH limitation. As such inputs of carbonate minerals can occur due to human activities like deforestation of river catchments, liming in plantations, and enhanced weathering application, our study points out an important feedback mechanism of those practices.

IntroductionAlthough distal radius fractures (DRFs) are the most common fractures of the human body, there are still ongoing debates concerning the treatment for type A fractures, especially in elderly patients. In spite of good clinical outcomes, it remains unclear whether elderly patients, especially, could regain the preoperative functional level of the wrist. Therefore, we have quantified wrist function within a retrospective study design using patient-reported outcome measures (PROM) and we have analyzed the influence of age between control and patient collective and young vs. old, respectively.Patients and methodsThe retrospective study included all patients with a surgically treated DRF type A and a control group of healthy patients, age and gender matched. The function of the wrist was examined by using a self-assessment questionnaire called the Munich Wrist Questionnaire (MWQ) according to the patient-related outcome measurements PROM.ResultsWe could enroll 110 patients and controls, and the average follow-up was 66 months. Subgroup matching induced similar age group distribution: in both groups, 7 individuals 80 years, were enrolled, respectively. In the fracture group, women were significantly older than men (59 ± 15 vs. 47 ± 17 (M ± SD). There was no significant difference between the control and the patient groups (96 ± 6 vs. 95 ± 7). The function was significantly different between controls and patients 80 and in the age group 30–64 compared with 65–79 and >80. In the control group, the function was found to be significantly decreasing with advancing age, whereas in the patient group, this influence was absent. A correlation analysis showed a worse function with increasing age in the control group and therefore a negative correlation. In the fracture group, a similar result could not be obtained.DiscussionAge has a relevant influence on wrist function. Although the wrist function decreases significantly with aging, in the patient group, this influence is absent, and the functional results after surgery are excellent. Even elderly patients can regain their preoperative functional level.

Low-cost sensors are considered to exhibit great potential to complement classical air quality measurements in existing monitoring networks. However, the use of low-cost sensors poses some challenges. In this study, the behavior and performance of electrochemical sensors for NO and NO2 were determined over a longer operating period in a real-world deployment. After careful calibration of the sensors, based on co-location with reference instruments at a rural traffic site during 6 months and by using robust linear regression and random forest regression, the coefficient of determination of both types of sensors was high (R2 > 0.9), and the root mean square error (RMSE) of NO and NO2 sensors was about 6.8 and 3.5 ppb, respectively, for 10 min mean concentrations. The RMSE of the NO2 sensors, however, more than doubled when the sensors were deployed without recalibration for a 1-year period at other site types (including urban background locations), where the range and the variability of air pollutant concentrations differed from the calibration site. This indicates a significant effect of relocation of the sensors on the quality of their data. During deployment, we found that the NO2 sensors are capable of distinguishing general pollution levels, but they proved unsuitable for accurate measurements, mainly due to significant biases. In order to investigate the long-term stability of the original calibration, the sensors were reinstalled at the calibration site after deployment. Surprisingly, the coefficient of determination and the RMSE of the NO sensor remained almost unchanged after more than 1 year of operation. In contrast, the performance of the NO2 sensors clearly deteriorated as indicated by a higher RMSE (about 7.5 ppb, 10 min mean concentrations) and a lower coefficient of determination (R2 = 0.59).

Oblique imaging sensor systems are becoming a standard for photogrammetric applications such as city modeling, with increasing need for frequently updated geospatial data in urban areas. The ground processing software has to consider and support this develop-ment, providing a highly performant workflow for projects that can consist of tens or hundreds of thousands of images in different view angles: nadir (vertical), left, right, backward, forward. This is a challenge also for the oblique aerial triangulation (AT), both the large number of images to process and the high amount of overlap in-between them, where more than 50 image measurements for a given ground point are common.At the same time, the large overlap even in a single view generally provides stable sub-blocks for each viewing direction and, therefore, allows for separating the oblique AT by view and performing a hierarchical approach: The nadir block is triangulated first, updating the exterior orientation parameters of all nadir images and providing adjusted ground points. This nadir reference can be used to tie the oblique views’ sub-blocks in subsequent AT runs to eventually provide adjusted exterior orientations for all images, with comparable accuracy to an integrated AT – but providing a significant performance gain. The hierarchical AT is a three-step approach: 1. adjust-ment of the nadir imagery, 2. adjustment of each oblique views independently by cardinal direction (East, West, North, South) while tying it to the nadir reference, and 3. computation of combined statistics and report.The paper details our AT approach and evaluates its parameterization for different oblique data sets, comparing results and performance to a fully integrated AT.

Abstract High latitude organic soils form a significant carbon storage and deposition of these soils is largely driven by climate. Svalbard, Norway, has experienced millennial-scale climate variations and in general organic soil processes have benefitted from warm and humid climate phases while cool late Holocene has been unfavourable. In addition to direct effect of cool climate, the advancing glaciers have restricted the vegetation growth, thus soil accumulation. Since the early 1900’s climate has been warming at unprecedented rate, assumingly promoting organic soil establishment. Here we present results of multiple organic soil profiles collected from Svalbard. The profiles have robust chronologies accompanied by soil property analyses, carbon stock estimations and testate amoeba data as a proxy for soil moisture. Our results reveal relatively recent initiation of organic soils across the Isfjorden area. The initiation processes could be linked to glacier retreat, and improvement of growing conditions and soil stabilization. Carbon stock analyses suggested that our sites are hot spots for organic matter accumulation. Testate amoebae data suggested drying of soil surfaces, but the reason remained unresolved. If continued, such a process may lead to carbon release. Our data suggest that detailed palaeoecological data from the Arctic is needed to depict the on-going processes and to estimate future trajectories.

Several severe flood events hit Germany in recent years, with events in 2013 and 2016 being the most destructive ones, although dynamics and flood processes were very different. While the 2013 event was a slowly rising widespread fluvial flood accompanied by some severe dike breaches, the events in 2016 were fast-onset pluvial floods, which resulted in surface water flooding in some places due to limited capacities of the drainage systems and in destructive flash floods with high sediment loads and clogging in others, particularly in small steep catchments. Hence, different pathways, i.e. different routes that the water takes to reach (and potentially damage) receptors, in our case private households, can be identified in both events. They can thus be regarded as spatially compound flood events or compound inland floods. This paper analyses how differently affected residents coped with these different flood types (fluvial and pluvial) and their impacts while accounting for the different pathways (river flood, dike breach, surface water flooding and flash flood) within the compound events. The analyses are based on two data sets with 1652 (for the 2013 flood) and 601 (for the 2016 flood) affected residents who were surveyed around 9 months after each flood, revealing little socio-economic differences – except for income – between the two samples. The four pathways showed significant differences with regard to their hydraulic and financial impacts, recovery, warning processes, and coping and adaptive behaviour. There are just small differences with regard to perceived self-efficacy and responsibility, offering entry points for tailored risk communication and support to improve property-level adaptation.

Abstract Background Antithrombin deficiency (ATD) is an autosomal dominant thrombophilia presenting with varying phenotypes. In pediatric patients with ATD, thrombosis typically develops during the neonatal period or adolescence. However, to date there are no consistent recommendations on the therapeutic management of children with ATD. Inferior vena cava atresia (IVCA) belongs to a range of congenital or acquired vena cava malformations and is described as an independent risk factor for thrombosis. The present case report explores two cases of combined ATD and IVCA in an adolescent and his mother. Case presentation A 14-year-old male presented with extensive deep venous thromboses (DVTs) of both lower extremities as well as an IVCA. The patient had previously been diagnosed with an asymptomatic ATD without therapeutic consequences at that time. His mother was suffering from an ATD and had herself just been diagnosed with IVCA, too. The DVTs in the adolescent were treated by systemic anticoagulation and catheter-directed local thrombolysis causing favourable results. Yet, despite adequate oral anticoagulation the DVTs in both lower extremities reoccurred within 1 week after the patient was discharged from hospital. This time, thrombolysis could not be fully achieved. Surprisingly, probing and stenting of the IVCA was achieved, indicating an acquired IVCA which could have occurred after undetected thrombosis in early childhood. Genetic analyses showed the same mutation causing ATD in both son and mother: heterozygote missense mutation c.248 T > C, p.(Leu83Pro), within the heparin binding domain of antithrombin. This mutation was never reported in mutation databases before. Conclusions To our knowledge this is the first case report discussing combined ATD and IVCA in two family members. Since ATDs present with clinical heterogeneity, taking a thorough family history is crucial for the anticipation of possible complications in affected children and decisions on targeted diagnostics and therapeutic interventions. Affected families must be educated on risk factors and clinical signs of thrombosis and need an immediate diagnostic workup in case of clinical symptoms. IVCA in patients with ATD could occur due to thrombotic occlusion at a very early age. Therefore, in case of family members with IVCA and ATD ultrasound screening in newborns should be considered.

Abstract Peri-implantitis may result in the loss of dental implants. Cold atmospheric pressure plasma (CAP) was suggested to promote re-osseointegration, decrease antimicrobial burden, and support wound healing. However, the long-term risk assessment of CAP treatment in the oral cavity has not been addressed. Treatment with two different CAP devices was compared against UV radiation, carcinogen administration, and untreated conditions over 12 months. Histological analysis of 406 animals revealed that repeated CAP exposure did not foster non-invasive lesions or squamous cell carcinoma (SCCs). Carcinogen administration promoted non-invasive lesions and SCCs. Molecular analysis by a qPCR screening of 144 transcripts revealed distinct inflammatory profiles associated with each treatment regimen. Interestingly, CAP treatment of carcinogen-challenged mucosa did not promote but instead left unchanged or reduced the proportion of non-invasive lesions and SCC formation. In conclusion, repeated CAP exposure of murine oral mucosa was well tolerated, and carcinogenic effects did not occur, motivating CAP applications in patients for dental and implant treatments in the future.

A re-evaluated data set of nitrogen dioxide (NO2) column densities over Rome for the years 1996 to 2017 is here presented. This long-term record is obtained from ground-based direct sun measurements with a MkIV Brewer spectrophotometer (serial number #067) and further reprocessed using a novel algorithm. Compared to the original Brewer algorithm, the new method includes updated NO2 absorption cross sections and Rayleigh scattering coefficients, and it accounts for additional atmospheric compounds and instrumental artefacts, such as the spectral transmittance of the filters, the alignment of the wavelength scale, and internal temperature. Moreover, long-term changes in the Brewer radiometric sensitivity are tracked using statistical methods for in-field calibration. The resulting series presents only a few (about 30) periods with missing data longer than 1 week and features NO2 retrievals for more than 6100 d, covering nearly 80 % of the considered 20-year period. The high quality of the data is demonstrated by two independent comparisons. In the first intensive campaign, Brewer #067 is compared against another Brewer (#066), recently calibrated at the Izaña Atmospheric Observatory through the Langley method and there compared to reference instrumentation from the Network for the Detection of Atmospheric Composition Change (NDACC). Data from this campaign show a highly significant Pearson's correlation coefficient of 0.90 between the two series of slant column densities (SCDs), slope 0.98 and offset 0.05 DU (Dobson units; 1.3×1015 molec.cm-2). The average bias between the vertical column densities is 0.03 DU (8.1×1014 molec.cm-2), well within the combined uncertainty of both instruments. Brewer #067 is also independently compared with new-generation instrumentation, a co-located Pandora spectrometer (#117), over a 1-year-long period (2016–2017) at Sapienza University of Rome, showing linear correlation indices above 0.96 between slant column densities, slope of 0.97, and offset of 0.02 DU (5.4×1014 molec.cm-2). The average bias between vertical column densities is negligible (−0.002 DU or -5.4×1013 molec.cm-2). This, incidentally, represents the first intercomparison of NO2 retrievals between a MkIV Brewer and a Pandora instrument. Owing to its accuracy and length, the Brewer data set collected in Rome can be useful for satellite calibration/validation exercises, comparison with photochemical models, and better aerosol optical depth estimates (NO2 optical depth climatology). In addition, it can be employed to identify long-term trends in NO2 column densities in a metropolitan environment, over two decades witnessing important changes in environmental policies, emission loads and composition, and the effect of a worldwide economic recession, to offer just a few examples. The method can be replicated on the more than 80 MkIV spectrophotometers operating worldwide in the frame of the international Brewer network. The NO2 data set described in this paper can be freely accessed at https://doi.org/10.5281/zenodo.4715219 (Diémoz and Siani, 2021).

Aims: Hospitalization for heart failure treatment (HHF) is an incisive event in the course of HF. Today, the large majority of HHF patients is ≥ 65 years and discharge HF drugs are most often not applied at dose levels acknowledged to provide prognostic benefit. This study therefore aims to investigate the treatment effect size of discharge HF drugs in old HHF patients. Methods: Drugs are analyzed according to pharmacological class. Individual discharge HF drug dose is reported as percentage of guidelines-recommended target dose. Primary endpoint was 1-year all-cause mortality (ACM) after discharge; the secondary endpoint combined 1-year ACM and first cardiovascular hospitalization within 1 year after discharge. Comparison between 65–80 years and > 80 years old study participants tested the relative treatment effect size as a function of respective age group. Results: The 875 consecutive HHF patients had a median age of 82 years [76–87 years]; 48.6 % were females. Betablocker and diuretic treatment did not change the incidence of endpoints. Inhibition of the renin-angiotensin system (RASi), when compared to no treatment, decreased the incidence of endpoints both at the 1–25 % and the > 25 % target dose level. Antagonists of the mineralocorticoid receptor (MRA), when compared to no treatment, decreased the secondary endpoint at the 1–25 % target dose level but not at the > 25 % target dose level. The relative treatment effect size of RASi or MRA corresponded between the age strata for both endpoints. Conclusion: Low-dose RASi and MRA had beneficial effects in these old HHF patients.

Developing accurate sea ice drift forecasts is essential to support the decision-making of maritime end-users operating in the Arctic. In this study, two calibration methods have been developed for improving 10 d sea ice drift forecasts from an operational sea ice prediction system (TOPAZ4). The methods are based on random forest models (supervised machine learning) which were trained using target variables either from drifting buoy or synthetic-aperture radar (SAR) observations. Depending on the calibration method, the mean absolute error is reduced, on average, between 3.3 % and 8.0 % for the direction and between 2.5 % and 7.1 % for the speed of sea ice drift. Overall, the algorithms trained with buoy observations have the best performances when the forecasts are evaluated using drifting buoys as reference. However, there is a large spatial variability in these results, and the models trained with buoy observations have particularly poor performances for predicting the speed of sea ice drift near the Greenland and Russian coastlines compared to the models trained with SAR observations.

Introduction Exposure to early life stress (ELS) strongly predicts prevalent, impairing, and costly psychiatric illness throughout life including mental disorders. The reason, some individuals are more vulnerable to ELS whereas others remain resilient, is poorly understood. There is a need for better understanding of early biological changes triggered by ELS with responsibility to negative outcomes in health. Objectives We stratify animals after ELS according to corticosterone levels. [1] Re-challenging the animals to a second stressor, chronic social defeat (CSD) [2], in adulthood was performed to understand individual trajectories depending on corticosterone exposure during early adverse conditions. Methods We performed ELS as previously reported [1]. Behavior of mothers was observed during ELS. Correlation between level of corticosterone and behavior observed in dams. ELS animals were exposed to a second stress in adulthood. A battery of tests for different behavioral domains was performed. Behavioral analyses was combined with assessment of litter HPA system reactivity and observed behavior in dams. Results Stress dams where significantly higher in number of sorties over whole observation period, time dams spent outside the nest differed. We could correlate the number of sorties on p3 with corticosterone plasma level at p9. Control dams spent significantly more time outside in 9pm recordings than stress animals. We could show reduced interaction with social juvenile targets in sociability test for CSD mice. Light dark transition was significantly higher for control mice compared to CSD but lower for control vs ELS animals. Conclusions Behavior in dams during ELS correlates with chronic stress coping mechanisms in offspring’s adulthood. Disclosure No significant relationships.

Abstract Sacroiliac joint dysfunction (SIJD) is an underappreciated source of back pain. Mineralization patterns of the sacroiliac (SIJ) subchondral bone plate (SCB) may reflect long-term adaptations to the loading of the joint. Mineralization densitograms of 27 SIJD patients and 39 controls, were obtained using CT osteoabsorptiometry. Hounsfield unit (HU) values of the SCB mineralization of superior, anterior and inferior regions on the iliac and sacral auricular surfaces were derived and statistically compared between SIJD-affected and control cohorts. Healthy controls showed higher HU values in the iliac; 868 ± 211 (superior), 825 ± 121 (anterior), 509 ± 114 (inferior), than in the sacral side; 541 ± 136 (superior), 618 ± 159 (anterior), 447 ± 91 (inferior), of all regions (p

The Brewer ozone spectrophotometer (the Brewer) was designed at Environment and Climate Change Canada (ECCC) in the 1970s to make accurate automated total ozone column measurements. Since the 1980s, the Brewer instrument has become a World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) standard ozone monitoring instrument. Now, more than 230 Brewers have been produced. To assure the quality of the Brewer measurements, a calibration chain is maintained, i.e., first, the reference instruments are independently absolutely calibrated, and then the calibration is transferred from the reference instrument to the travelling standard, and subsequently from the travelling standard to field instruments. ECCC has maintained the world Brewer reference instruments since the 1980s to provide transferable calibration to field instruments at monitoring sites. Three single-monochromator (Mark II) type instruments (serial numbers 008, 014, and 015) formed this world Brewer reference triad (BrT) and started their service in Toronto, Canada, in 1984. In the 1990s, the Mark III type Brewer (known as the double Brewer) was developed, which has two monochromators to reduce the internal instrumental stray light. The double-Brewer world reference triad (BrT-D) was formed in 2013 (serial numbers 145, 187 and 191), co-located with the BrT. The first assessment of the BrT's performance was made in 2005, covering the period between 1984 and 2004 (Fioletov et al., 2005). The current work provides an updated assessment of the BrT's performance (from 1999 to 2019) and the first comprehensive assessment of the BrT-D. The random uncertainties of individual reference instruments are within the WMO/GAW requirement of 1 % (WMO, 2001): 0.49 % and 0.42 % for BrT and BrT-D, respectively, as estimated in this study. The long-term stability of the reference instruments is also evaluated in terms of uncertainties of the key instrument characteristics: the extraterrestrial calibration constant (ETC) and effective ozone absorption coefficients (both having an effect of less than 2 % on total column ozone). Measurements from a ground-based instrument (Pandora spectrometer), satellites (11 datasets, including the most recent high-resolution satellite, TROPOspheric Monitoring Instrument), and reanalysis model (the second Modern-Era Retrospective analysis for Research and Applications, MERRA-2) are used to further assess the performance of world Brewer reference instruments and to provide a context for the requirements of stratospheric ozone observations during the last two decades.

Aerosols over Earth's remote and spatially extensive ocean surfaces have important influences on planetary climate. However, these aerosols and their effects remain poorly understood, in part due to the remoteness and limited observations over these regions. In this study, we seek to understand factors that shape marine aerosol size distributions and composition in the northwest Atlantic Ocean region. We use the GEOS-Chem model with the TwO-Moment Aerosol Sectional (TOMAS) microphysics algorithm model to interpret measurements collected from ship and aircraft during the four seasonal campaigns of the North Atlantic Aerosols and Marine Ecosystems Study (NAAMES) conducted between 2015 and 2018. Observations from the NAAMES campaigns show enhancements in the campaign-median number of aerosols with diameters larger than 3 nm in the lower troposphere (below 6 km), most pronounced during the phytoplankton bloom maxima (May/June) below 2 km in the free troposphere. Our simulations, combined with NAAMES ship and aircraft measurements, suggest several key factors that contribute to aerosol number and size in the northwest Atlantic lower troposphere, with significant regional-mean (40–60∘ N and 20–50∘ W) cloud-albedo aerosol indirect effect (AIE) and direct radiative effect (DRE) processes during the phytoplankton bloom. These key factors and their associated simulated radiative effects in the region include the following: (1) particle formation near and above the marine boundary layer (MBL) top (AIE: −3.37 W m−2, DRE: −0.62 W m−2); (2) particle growth due to marine secondary organic aerosol (MSOA) as the nascent particles subside into the MBL, enabling them to become cloud-condensation-nuclei-sized particles (AIE: −2.27 W m−2, DRE: −0.10 W m−2); (3) particle formation and growth due to the products of dimethyl sulfide, above and within the MBL (−1.29 W m−2, DRE: −0.06 W m−2); (4) ship emissions (AIE: −0.62 W m−2, DRE: −0.05 W m−2); and (5) primary sea spray emissions (AIE: +0.04 W m−2, DRE: −0.79 W m−2). Our results suggest that a synergy of particle formation in the lower troposphere (particularly near and above the MBL top) and growth by MSOA contributes strongly to cloud-condensation-nuclei-sized particles with significant regional radiative effects in the northwest Atlantic. To gain confidence in radiative effect magnitudes, future work is needed to understand (1) the sources and temperature dependence of condensable marine vapors forming MSOA, (2) primary sea spray emissions, and (3) the species that can form new particles in the lower troposphere and grow these particles as they descend into the marine boundary layer.

Proton-transfer-reaction mass spectrometry (PTR-MS) is widely used in atmospheric sciences for measuring volatile organic compounds in real time. In the most widely used type of PTR-MS instruments, air is directly introduced into a chemical ionization reactor via an inlet capillary system. The reactor has a volumetric exchange time of ∼0.1 s, enabling PTR-MS analyzers to measure at a frequency of 10 Hz. The time response does, however, deteriorate if low-volatility analytes interact with surfaces in the inlet or in the instrument. Herein, we present the extended volatility range (EVR) PTR-MS instrument which mitigates this issue. In the EVR configuration, inlet capillaries are made of passivated stainless steel, and all wetted metal parts in the chemical ionization reactor are surface-passivated with a functionalized hydrogenated amorphous silicon coating. Heating the entire setup (up to 120 ∘C) further improves the time-response performance. We carried out time-response performance tests on a set of 29 analytes having saturation mass concentrations C0 in the range between 10−3 and 105 µg m−3. The 1/e-signal decay times after instant removal of the analyte from the sampling flow were between 0.2 and 90 s for gaseous analytes. We also tested the EVR PTR-MS instrument in combination with the chemical analysis of aerosols online (CHARON) particle inlet, and 1/e-signal decay times were in the range between 5 and 35 s for particulate analytes. We show on a set of example compounds that the time-response performance of the EVR PTR-MS instrument is comparable to that of the fastest flow tube chemical ionization mass spectrometers that are currently in use. The fast time response can be used for rapid (∼1 min equilibration time) switching between gas and particle measurements. The CHARON EVR PTR-MS instrument can thus be used for real-time monitoring of both gaseous and particulate organics in the atmosphere. Finally, we show that the CHARON EVR PTR-MS instrument also rapidly detects highly oxygenated species (with up to eight oxygen atoms) in particles formed by limonene ozonolysis.

This paper reports on consolidated ground-based validation results of the atmospheric NO2 data produced operationally since April 2018 by the TROPOspheric Monitoring Instrument (TROPOMI) on board of the ESA/EU Copernicus Sentinel-5 Precursor (S5P) satellite. Tropospheric, stratospheric, and total NO2 column data from S5P are compared to correlative measurements collected from, respectively, 19 Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS), 26 Network for the Detection of Atmospheric Composition Change (NDACC) Zenith-Scattered-Light DOAS (ZSL-DOAS), and 25 Pandonia Global Network (PGN)/Pandora instruments distributed globally. The validation methodology gives special care to minimizing mismatch errors due to imperfect spatio-temporal co-location of the satellite and correlative data, e.g. by using tailored observation operators to account for differences in smoothing and in sampling of atmospheric structures and variability and photochemical modelling to reduce diurnal cycle effects. Compared to the ground-based measurements, S5P data show, on average, (i) a negative bias for the tropospheric column data, of typically −23 % to −37 % in clean to slightly polluted conditions but reaching values as high as −51 % over highly polluted areas; (ii) a slight negative median difference for the stratospheric column data, of about −0.2 Pmolec cm−2, i.e. approx. −2 % in summer to −15 % in winter; and (iii) a bias ranging from zero to −50 % for the total column data, found to depend on the amplitude of the total NO2 column, with small to slightly positive bias values for columns below 6 Pmolec cm−2 and negative values above. The dispersion between S5P and correlative measurements contains mostly random components, which remain within mission requirements for the stratospheric column data (0.5 Pmolec cm−2) but exceed those for the tropospheric column data (0.7 Pmolec cm−2). While a part of the biases and dispersion may be due to representativeness differences such as different area averaging and measurement times, it is known that errors in the S5P tropospheric columns exist due to shortcomings in the (horizontally coarse) a priori profile representation in the TM5-MP chemical transport model used in the S5P retrieval and, to a lesser extent, to the treatment of cloud effects and aerosols. Although considerable differences (up to 2 Pmolec cm−2 and more) are observed at single ground-pixel level, the near-real-time (NRTI) and offline (OFFL) versions of the S5P NO2 operational data processor provide similar NO2 column values and validation results when globally averaged, with the NRTI values being on average 0.79 % larger than the OFFL values.

Analysis of formaldehyde measurements by the Pandora spectrometer systems between 2016 and 2019 suggested that there was a temperature-dependent process inside the Pandora head sensor that emitted formaldehyde. Some parts in the head sensor were manufactured from the thermal plastic polyoxymethylene homopolymer (E.I. Du Pont de Nemour & Co., USA; POM-H Delrin®) and were responsible for formaldehyde production. Laboratory analysis of the four Pandora head sensors showed that internal formaldehyde production had exponential temperature dependence with a damping coefficient of 0.0911±0.0024 ∘C−1 and the exponential function amplitude ranging from 0.0041 to 0.049 DU. No apparent dependency on the head sensor age and heating and cooling rates was detected. The total amount of formaldehyde internally generated by the POM-H Delrin components and contributing to the direct-sun measurements were estimated based on the head sensor temperature and solar zenith angle of the measurements. Measurements in winter, during colder (< 10 ∘C) days in general, and at high solar zenith angles (> 75∘) were minimally impacted. Measurements during hot days (> 28 ∘C) and small solar zenith angles had up to 1 DU (2.69×1016 molec. cm−2) contribution from POM-H Delrin parts. Multi-axis differential slant column densities were minimally impacted ( DU) due to the reference spectrum being collected within a short time period with a small difference in head sensor temperature. Three new POM-H Delrin free Pandora head sensors (manufactured in summer 2019) were evaluated for temperature-dependent attenuation across the entire spectral range (300 to 530 nm). No formaldehyde absorption or any other absorption above the instrumental noise was observed across the entire spectral range.

Abstract Endogenous immune mediated reactions of inflammation and angiogenesis are components of the spinal cord injury in patients with degenerative cervical myelopathy (DCM). The aim of this study was to identify alteration of certain mediators participating in angiogenetic and inflammatory reactions in patients with DCM. A consecutive series of 42 patients with DCM and indication for surgical decompression were enrolled for the study. 28 DCM patients were included, as CSF samples were taken preoperatively. We enrolled 42 patients requiring surgery for a thoracic abdominal aortic aneurysm (TAAA) as neurologically healthy controls. In 38 TAAA patients, CSF samples were taken prior to surgery and thus included. We evaluated the neurological status of patients and controls prior to surgery including NDI and mJOA. Protein-concentrations of factors with a crucial role in inflammation and angiogenesis were measured in CSF via ELISA testing (pg/ml): Angiopoietin 2, VEGF-A and C, RANTES, IL 1 beta and IL 8. Additionally, evaluated the status of the blood-spinal cord barrier (BSCB) by Reibers´diagnostic in all participants. Groups evidently differed in their neurological status (mJOA: DCM 10.1 ± 3.3, TAAA 17.3 ± 1.2, p

A fast crosslinking reaction is crucial for the economical production of automotive components in liquid composite molding (LCM) processes. Although a large number of works have focused on modeling of shrinkage induced surface waviness and part distortions and the underlying phenomena an accurate determination of material properties under consideration of processing parameters still represents a major challenge for fast-curing epoxy resins. Fast-curing epoxy polymers allow manufacturing of thermoset composite parts in minutes while entailing a highly exothermic heat generation. Cure is carried out under elevated temperatures and pressures and is accompanied by a change in density due to chemical shrinkage and followed by thermal contraction. In the present study, comprehensive results on the characterization of thermo-mechanical properties, pressure dependent reaction kinetics and shrinkage are presented for a fast curing epoxy resin. The obtained results give important advice for improved process modeling and facilitate prioritisation for future characterisation of fast-curing epoxy resins.

During development, oriented cell division is important to proper body axis extension. Here, the authors show that sphingolipids are required to direct spindle rotation and oriented mitosis via Anthrax receptor palmitoylation in zebrafish gastrulation.

More than 300 non-dispersive infrared (NDIR) CO2 low-cost sensors labelled as LP8 were integrated into sensor units and evaluated for the purpose of long-term operation in the Carbosense CO2 sensor network in Switzerland. Prior to deployment, all sensors were calibrated in a pressure and climate chamber and in ambient conditions co-located with a reference instrument. To investigate their long-term performance and to test different data processing strategies, 18 sensors were deployed at five locations equipped with a reference instrument after calibration. Their accuracy during 19 to 25 months deployment was between 8 and 12 ppm. This level of accuracy requires careful sensor calibration prior to deployment, continuous monitoring of the sensors, efficient data filtering, and a procedure to correct drifts and jumps in the sensor signal during operation. High relative humidity (> ∼85 %) impairs the LP8 measurements, and corresponding data filtering results in a significant loss during humid conditions. The LP8 sensors are not suitable for the detection of small regional gradients and long-term trends. However, with careful data processing, the sensors are able to resolve CO2 changes and differences with a magnitude larger than about 30 ppm. Thereby, the sensor can resolve the site-specific CO2 signal at most locations in Switzerland. A low-power network (LPN) using LoRaWAN allowed for reliable data transmission with low energy consumption and proved to be a key element of the Carbosense low-cost sensor network.

In September 2016, 36 spectrometers from 24 institutes measured a number of key atmospheric pollutants for a period of 17 d during the Second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) that took place at Cabauw, the Netherlands (51.97∘ N, 4.93∘ E). We report on the outcome of the formal semi-blind intercomparison exercise, which was held under the umbrella of the Network for the Detection of Atmospheric Composition Change (NDACC) and the European Space Agency (ESA). The three major goals of CINDI-2 were (1) to characterise and better understand the differences between a large number of multi-axis differential optical absorption spectroscopy (MAX-DOAS) and zenith-sky DOAS instruments and analysis methods, (2) to define a robust methodology for performance assessment of all participating instruments, and (3) to contribute to a harmonisation of the measurement settings and retrieval methods. This, in turn, creates the capability to produce consistent high-quality ground-based data sets, which are an essential requirement to generate reliable long-term measurement time series suitable for trend analysis and satellite data validation. The data products investigated during the semi-blind intercomparison are slant columns of nitrogen dioxide (NO2), the oxygen collision complex (O4) and ozone (O3) measured in the UV and visible wavelength region, formaldehyde (HCHO) in the UV spectral region, and NO2 in an additional (smaller) wavelength range in the visible region. The campaign design and implementation processes are discussed in detail including the measurement protocol, calibration procedures and slant column retrieval settings. Strong emphasis was put on the careful alignment and synchronisation of the measurement systems, resulting in a unique set of measurements made under highly comparable air mass conditions. The CINDI-2 data sets were investigated using a regression analysis of the slant columns measured by each instrument and for each of the target data products. The slope and intercept of the regression analysis respectively quantify the mean systematic bias and offset of the individual data sets against the selected reference (which is obtained from the median of either all data sets or a subset), and the rms error provides an estimate of the measurement noise or dispersion. These three criteria are examined and for each of the parameters and each of the data products, performance thresholds are set and applied to all the measurements. The approach presented here has been developed based on heritage from previous intercomparison exercises. It introduces a quantitative assessment of the consistency between all the participating instruments for the MAX-DOAS and zenith-sky DOAS techniques.

Southeast Asian peatland-draining rivers have attracted much attention due to their high dissolved organic carbon (DOC) yield and high CO2 emissions under anthropogenic influences. In August 2016, we carried out a field investigation of the Rajang River and its estuary, a tropical system located in Sarawak, Malaysia. The Rajang has peatland in its estuary, while the river basin is covered by tropical rainforest. DOC-δ13C in the Rajang ranged from −28.7 ‰ to −20.1 ‰, with a U-shaped trend from river to estuary. For particulate organic carbon (POC), δ13C ranged between −29.4 ‰ and −31.1 ‰ in the river, and there was a clear increasing trend towards more enriched δ13C values with higher salinity. In the estuary, there was a linear conservative dilution pattern for dissolved organic matter composition (as quantified by D- and L-amino acid enantiomers) plotted against DOC-δ13C, whereas when plotted against salinity, dissolved D- and L-amino acid enantiomer values were higher than the theoretical dilution value. Together, these data indicate that the addition of DOC to the estuary (by peatland) not only increased the DOC concentration but also altered its composition, by adding more biodegraded, 13C-depleted organic matter into the bulk dissolved organic matter. Alteration of organic matter composition (addition of a more degraded subpart) was also apparent for the particulate phase, but patterns were less clear. The Rajang was characterized by DOC to DON (dissolved organic nitrogen) ratios of 50 in the river section, with loss of DON in the estuary increasing the ratio to 140, suggesting an unbalanced export of organic carbon and nitrogen. Where affected by anthropogenic activities, further assessment of organic carbon to nitrogen ratios is needed.

Dissolved iron (dFe) is essential for multiple biogeochemical reactions in oceans, such as photosynthesis, respiration and nitrogen fixation. Currently, large uncertainties remain regarding the input of riverine dFe into coastal oceans, especially in tropical rivers in southeastern Asia. In the present study, the concentrations of dFe and distribution patterns of dFe were determined along the salinity gradient in the Rajang River and three blackwater rivers that drain from peatlands, including the Maludam River, the Sebuyau River and the Simunjan River. In the Rajang River, the dFe concentration in freshwater samples (salinity  PSU – practical salinity units) in the wet season (March 2017) was higher than that in the dry season (August 2016), which might be related to the resuspension of sediment particles and soil erosion from cropland. In the Rajang estuary, an intense removal of dFe in low-salinity waters (salinity  PSU) was observed, which was likely due to salt-induced flocculation and absorption of dFe onto suspended particulate matter (SPM). However, increases in the dFe concentration in the wet season were also found, which may be related to dFe desorption from SPM and the influences of agricultural activities. In the blackwater rivers, the dFe concentration reached 44.2 µmol L−1, indicating a strong contribution to the dFe budget from peatland leaching. The dFe flux derived from the Rajang estuary to the South China Sea was estimated to be 6.4±2.3×105 kg yr−1. For blackwater rivers, the dFe flux was approximately 1.1±0.5×105 kg yr−1 in the Maludam River. Anthropogenic activities may play an important role in the dFe yield, such as in the Serendeng tributary of the Rajang River and Simunjan River, where intensive oil palm plantations were observed.

The TROPOspheric Monitoring Instrument (TROPOMI) aboard the Sentinel-5 Precursor satellite (launched on 13 October 2017) is a nadir-viewing spectrometer measuring reflected sunlight in the ultraviolet, visible, near-infrared, and shortwave infrared spectral ranges. The measured spectra are used to retrieve total columns of trace gases, including nitrogen dioxide (NO2). For ground validation of these satellite measurements, Pandora spectrometers, which retrieve high-quality NO2 total columns via direct-sun measurements, are widely used. In this study, Pandora NO2 measurements made at three sites located in or north of the Greater Toronto Area (GTA) are used to evaluate the TROPOMI NO2 data products, including a standard Royal Netherlands Meteorological Institute (KNMI) tropospheric and stratospheric NO2 data product and a TROPOMI research data product developed by Environment and Climate Change Canada (ECCC) using a high-resolution regional air quality forecast model (in the air mass factor calculation). It is found that these current TROPOMI tropospheric NO2 data products (standard and ECCC) met the TROPOMI design bias requirement (NO2 emissions, which can be used to evaluate regional air quality changes. The TROPOMI ECCC NO2 research data product shows improved agreement with Pandora measurements compared to the TROPOMI standard tropospheric NO2 data product (e.g., lower multiplicative bias at the suburban and urban sites by about 10 %), demonstrating benefits from the high-resolution regional air quality forecast model.

Selenium (Se) is an essential micronutrient for aquatic organisms. Despite its importance, our current knowledge of the biogeochemical cycling of dissolved Se in tropical estuaries is limited, especially in Southeast Asia. To gain insights into Se cycling in tropical peat-draining rivers and estuaries, samples were collected from the Rajang, Maludam, Sebuyau, Simunjan, Sematan, Samunsam and Lunda rivers and estuaries in western Sarawak, Malaysia, in March and September 2017 and analysed for various forms of Se (dissolved inorganic and organic). Mean total dissolved Se (TDSe), dissolved inorganic Se (DISe) and dissolved organic Se concentrations (DOSe) were 2.2 nmol L−1 (range: 0.7 to 5.7 nmol L−1), 0.18 nmol L−1 (range: less than the detection limit to 0.47 nmol L−1) and 2.0 nmol L−1 (range: 0.42 to 5.7 nmol L−1), respectively. In acidic, low-oxygen, organic-rich blackwater (peatland-draining) rivers, the concentrations of DISe were extremely low (near or below the detection limit, i.e. 0.0063 nmol L−1), whereas those of DOSe were high. In rivers and estuaries that drained peatland, DOSe ∕ TDSe ratios ranged from 0.67 to 0.99, showing that DOSe dominated. The positive relationship between DISe and salinity and the negative relationship between DOSe and salinity indicate marine and terrestrial origins of DISe and DOSe, respectively. The positive correlations of DOSe with the humification index and humic-like chromophoric dissolved organic matter components in freshwater river reaches suggest that peat soils are probably the main source of DOSe. The DOSe fractions may be associated with high molecular weight peatland-derived aromatic and black carbon compounds and may photodegrade to more bioavailable forms once transported to coastal waters. The TDSe flux delivered by the peat-draining rivers exceeded those reported for other small rivers and is quantitatively more significant than previously thought.

It is known that pigs can acquire flavour preferences by brief social interactions with conspecifics that previously consumed a flavoured solid feed. However, there is no information about whether a flavoured solution could support flavour preferences through social transmission. Ninety-six pigs (49 days old) were housed in 12 pens (8 pigs/pen). Four animals per pen were randomly selected to act as observers and four as demonstrators. Demonstrator animals were temporarily moved to an empty pen where a protein solution was offered (porcine digestive peptides (PDPs), 4% weight/volume) with the addition of 0.075% aniseed (six pens) or garlic (six pens) powdered artificial flavours for 30 min. Afterwards, demonstrators were returned to interact with observer animals for 30 min. A choice test (30 min) between aniseed and garlic PDP was performed for each observer group after the interaction. Observers showed a higher intake of solutions previously consumed by their demonstrator conspecifics (648 v. 468 ml; SEM 61.36, P < 0.05). As with flavoured solid feeds, protein solutions containing artificial flavours can create preferences in pigs for those flavours through social transmission from conspecifics.

Chamber oxidation experiments conducted at the Fire Sciences Laboratory in 2016 are evaluated to identify important chemical processes contributing to the hydroxy radical (OH) chemistry of biomass burning non-methane organic gases (NMOGs). Based on the decay of primary carbon measured by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS), it is confirmed that furans and oxygenated aromatics are among the NMOGs emitted from western United States fuel types with the highest reactivities towards OH. The oxidation processes and formation of secondary NMOG masses measured by PTR-ToF-MS and iodide-clustering time-of-flight chemical ionization mass spectrometry (I-CIMS) is interpreted using a box model employing a modified version of the Master Chemical Mechanism (v. 3.3.1) that includes the OH oxidation of furan, 2-methylfuran, 2,5-dimethylfuran, furfural, 5-methylfurfural, and guaiacol. The model supports the assignment of major PTR-ToF-MS and I-CIMS signals to a series of anhydrides and hydroxy furanones formed primarily through furan chemistry. This mechanism is applied to a Lagrangian box model used previously to model a real biomass burning plume. The customized mechanism reproduces the decay of furans and oxygenated aromatics and the formation of secondary NMOGs, such as maleic anhydride. Based on model simulations conducted with and without furans, it is estimated that furans contributed up to 10 % of ozone and over 90 % of maleic anhydride formed within the first 4 h of oxidation. It is shown that maleic anhydride is present in a biomass burning plume transported over several days, which demonstrates the utility of anhydrides as markers for aged biomass burning plumes.

Pathophysiological models are urgently needed for personalized treatments of mental disorders. However, most potential neural markers for psychopathology are limited by low interpretability, prohibiting reverse inference from brain measures to clinical symptoms and traits. Neural signatures—i.e. multivariate brain-patterns trained to be both sensitive and specific to a construct of interest—might alleviate this problem, but are rarely applied to mental disorders. We tested whether previously developed neural signatures for negative affect and discrete emotions distinguish between healthy individuals and those with mental disorders characterized by emotion dysregulation, i.e. Borderline Personality Disorder (BPD) and complex Post-traumatic Stress Disorder (cPTSD). In three different fMRI studies, a total sample of 192 women (49 BPD, 62 cPTSD, 81 healthy controls) were shown pictures of scenes with negative or neutral content. Based on pathophysiological models, we hypothesized higher negative and lower positive reactivity of neural emotion signatures in participants with emotion dysregulation. The expression of neural signatures differed strongly between neutral and negative pictures (average Cohen's d = 1.17). Nevertheless, a mega-analysis on individual participant data showed no differences in the reactivity of neural signatures between participants with and without emotion dysregulation. Confidence intervals ruled out even small effect sizes in the hypothesized direction and were further supported by Bayes factors. Overall, these results support the validity of neural signatures for emotional states during fMRI tasks, but raise important questions concerning their link to individual differences in emotion dysregulation.

Herein we report on the first successful airborne deployment of the CHemical Analysis of AeRosol ONline (CHARON) particle inlet which allowed us to measure the chemical composition of atmospheric submicrometer particles in real time using a state-of-the-art proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) analyzer. The data were collected aboard the NASA DC-8 Airborne Science Laboratory on 26 June 2018 over California in the frame of NASA's Student Airborne Research Program (SARP). We show exemplary data collected when the airplane (i) shortly encountered a fresh ( h old) smoke plume that had emanated from the Lions Fire in the Sierra Nevada, (ii) intercepted a particle plume emitted from an amine gas treating unit of a petroleum refinery close to Bakersfield, (iii) carried out a spatial survey in the boundary layer over the San Joaquin Valley and (iv) performed a vertical profile measurement over the greater Bakersfield area. The most important finding from this pilot study is that the CHARON PTR-ToF-MS system measures fast enough to be deployed on a jet research aircraft. The data collected during 3 to 15 s long plume encounters demonstrate the feasibility of airborne point or small area emission measurements. Further improvements are, however, warranted to eliminate or reduce the observed signal tailing (1/e decay time between 6 and 20 s). The fast time response of the analyzer allowed us to generate highly spatially resolved maps (1–2 km in the horizontal, 100 m in the vertical) of atmospheric particle chemical constituents. The chemical information that was extracted from the recorded particle mass spectra includes (i) mass concentrations of ammonium, nitrate and total organics; (ii) mass concentrations of different classes of organic compounds (CH vs. CHO vs. CHN vs. CHNO compounds; monoaromatic vs. polyaromatic compounds); (iii) aerosol bulk average O:C‾ and H:C‾ ratios; (iv) mass concentrations of selected marker molecules (e.g., levoglucosan in particles emitted from a wildfire, an alkanolamine in particles emitted from a petroleum refinery) and (v) wildfire emission ratios (Δtotal organics/ΔCO = 0.054; Δlevoglucosan/ΔCO = 7.9×10-3; Δvanillic acid/ΔCO = 4.4×10-4 and Δretene/ΔCO = 1.9×10-4; all calculated as peak area ratios, in grams per gram). The capability of the CHARON PTR-ToF-MS instrument to chemically characterize submicrometer atmospheric particles in a quantitative manner, at the near-molecular level, and in real time brings a new and unprecedented measurement capability to the airborne atmospheric science community.

Tropical peatlands are one of the largest pools of terrestrial organic carbon (OCterr); however, our understanding of the dynamics of OCterr in peat-draining rivers remains limited, especially in Southeast Asia. This study used bulk parameters and lignin phenol concentrations to investigate the characteristics of OCterr in a tropical peat-draining river system (the main channel of the Rajang and three smaller rivers: the Maludam, Simunjan, and Sebuyau) in the western part of Sarawak, Malaysian Borneo. The depleted δ13C levels and lignin composition of the organic matter indicates that the most important plant source of the organic matter in these rivers is woody angiosperm C3 plants, especially in the three small rivers sampled. The diagenetic indicator ratio, i.e., the ratio of acid to aldehyde of vanillyl phenols ((Ad∕Al)V), increased with decreasing mean grain size of sediment from the small rivers. The selective sorption of acid relative to aldehyde phenols might explain the variations in the (Ad∕Al)V ratio. Elevated (Ad∕Al)V values observed from the Maludam's sediments may also be attributed to source plant variations. The (Ad∕Al)V ratio appears to be related to the C∕N ratio (the ratio of total organic carbon to total nitrogen) in the Rajang and small rivers. In small rivers, a quick decline of C∕N ratios is a response to the slower modification of (Ad∕Al)V ratios due to better preservation of lignin phenols. An accumulation of lignin phenols with higher total nitrogen percentages (TN%) in the studied systems was observed. Most of the OCterr discharged from the Rajang and small river systems was material derived from woody angiosperm plants with limited diagenetic alteration before deposition and thus could potentially provide significant carbon to the atmosphere after degradation.

Nitrous oxide (N2O) and methane (CH4) are atmospheric trace gases which play important roles in the climate and atmospheric chemistry of the Earth. However, little is known about their emissions from rivers and estuaries, which seem to contribute significantly to the atmospheric budget of both gases. To this end concentrations of N2O and CH4 were measured in the Rajang, Maludam, Sebuyau and Simunjan rivers draining peatland in northwestern (NW) Borneo during two campaigns in March and September 2017. The Rajang River was additionally sampled in August 2016 and the Samunsam and Sematan rivers were additionally sampled in March 2017. The Maludam, Sebuyau, and Simunjan rivers are typical “blackwater” rivers with very low pH (3.7–7.8), very high dissolved organic carbon (DOC) concentrations (235–4387 mmol L−1) and very low O2 concentrations (31–246 µmol L−1; i.e. 13 %–116 % O2 saturation). The spatial and temporal variability of N2O and CH4 concentrations (saturations) in the six rivers or estuaries was large and ranged from 2.0 nmol L−1 (28 %) to 41.4 nmol L−1 (570 %) and from 2.5 nmol L−1 (106 %) to 1372 nmol L−1 (57 459 %), respectively. We found no overall trends of N2O with O2 or NO3-, NO2- or NH4+, and there were no trends of CH4 with O2 or dissolved nutrients or DOC. N2O concentrations showed a positive linear correlation with rainfall. We conclude, therefore, that rainfall is the main factor determining the riverine N2O concentrations since N2O production or consumption in the blackwater rivers themselves seems to be low because of the low pH. CH4 concentrations were highest at salinity = 0 and most probably result from methanogenesis as part of the decomposition of organic matter under anoxic conditions. CH4 in the concentrations in the blackwater rivers showed an inverse relationship with rainfall. We suggest that CH4 oxidation in combination with an enhanced river flow after the rainfall events might be responsible for the decrease in the CH4 concentrations. The rivers and estuaries studied here were an overall net source of N2O and CH4 to the atmosphere. The total annual N2O and CH4 emissions were 1.09 Gg N2O yr−1 (0.7 Gg N yr−1) and 23.8 Gg CH4 yr−1, respectively. This represents about 0.3 %–0.7 % of the global annual riverine and estuarine N2O emissions and about 0.1 %–1 % of the global riverine and estuarine CH4 emissions. Therefore, we conclude that rivers and estuaries in NW Borneo – despite the fact their water area covers only 0.05 % of the global river/estuarine area – contribute significantly to global riverine and estuarine emissions of N2O and CH4.