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Bayesian optimization (BO)-assisted screening was applied to identify improved reaction conditions toward a hundred-gram scale-up synthesis of 2,3,7,8-tetrathiaspiro[4.4]nonane (1), a key synthetic intermediate of 2,2-bis(mercaptomethyl)propane-1,3-dithiol [tetramercaptan pentaerythritol]. Starting from the initial training set (ITS) consisting of six trials sampled by random screening for BO, suitable parameters were predicted (78% conversion yield of spiro-dithiolane 1) within seven experiments. Moreover, BO-assisted screening with the ITS selected by Latin hypercube sampling (LHS) further improved the yield of 1 to 89% within the eight trials. The established conditions were confirmed to be satisfactory for a hundred grams scale-up synthesis of 1.
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Leaf area index (LAI) is a key biophysical variable to characterize vegetation canopy. Accurate and quantitative LAI estimation is significant for monitoring vegetation growth status. ZhuHai-1 (ZH-1), which is a commercial remote sensing micro-nano satellite, provides a possibility for quantitative detection of vegetation with high spatial and spectral resolution. However, the band characteristics of ZH-1 are closely related to the accuracy of vegetation monitoring. In this study, a simulation dataset containing 32 bands of ZH-1 was generated by using the PROSAIL model, which was used to analyze the performance of 32 bands for LAI estimation by using the hybrid inversion method. Meanwhile, the effect of different band combinations on LAI estimation was discussed based on sensitivity analysis and the correlation between bands. Then, the optimal band combination from ZH-1 hyperspectral satellite data for LAI estimation was obtained. LAI estimation was performed based on the selected optimal band combination of ZH-1 satellite images in Xiantao city, Hubei province, and compared with the Sentinel-2 normalized difference vegetation index (NDVI) values and LAI product. The results demonstrated that the obtained LAI map based on the optimal band combination of ZH-1 was generally consistent with the overall distribution of Sentinel-2 NDVI and the LAI product, but had a moderate correlation with Sentinel-2 LAI (R = 0.60), which may not favorably indicate the validity of indirect validation. However, the method of this study on the analysis of hyperspectral data bands has application potential to provide a reference for selecting appropriate bands of hyperspectral satellite data to estimate LAI and improve the application of hyperspectral data such as ZH-1 in vegetation monitoring.
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Future food supply will become increasingly dependent on edible material extracted from insects. The growing popularity of artisanal food products enhanced by insect proteins creates particular needs for establishing effective methods for quality control. This study focuses on developing rapid and efficient on-site quantitative analysis of protein content in handcrafted insect bars by miniaturized near-infrared (NIR) spectrometers. Benchtop (Büchi NIRFlex N-500) and three miniaturized (MicroNIR 1700 ES, Tellspec Enterprise Sensor and SCiO Sensor) in hyphenation to partial least squares regression (PLSR) and Gaussian process regression (GPR) calibration methods and data fusion concept were evaluated via test-set validation in performance of protein content analysis. These NIR spectrometers markedly differ by technical principles, operational characteristics and cost-effectiveness. In the non-destructive analysis of intact bars, the root mean square error of cross prediction (RMSEP) values were 0.611% (benchtop) and 0.545-0.659% (miniaturized) with PLSR, and 0.506% (benchtop) and 0.482-0.580% (miniaturized) with GPR calibration, while the analyzed total protein content was 19.3-23.0%. For milled samples, with PLSR the RMSEP values improved to 0.210% for benchtop spectrometer but remained in the inferior range of 0.525-0.571% for the miniaturized ones. GPR calibration improved the predictive performance of the miniaturized spectrometers, with RMSEP values of 0.230% (MicroNIR 1700 ES), 0.326% (Tellspec) and 0.338% (SCiO). Furthermore, Tellspec and SCiO sensors are consumer-oriented devices, and their combined use for enhanced performance remains a viable economical choice. With GPR calibration and test-set validation performed for fused (Tellspec + SCiO) data, the RMSEP values were improved to 0.517% (in the analysis of intact samples) and 0.295% (for milled samples).
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Técnicas Biossensoriais , Proteínas de Insetos/análise , Proteínas de Insetos/química , Espectroscopia de Luz Próxima ao Infravermelho , Análise Custo-Benefício , Análise dos Mínimos Quadrados , Modelos Estatísticos , Distribuição Normal , Reprodutibilidade dos Testes , Espectroscopia de Luz Próxima ao Infravermelho/métodosRESUMO
Leaf area index (LAI) is an important biophysical parameter, which can be effectively applied in the estimation of vegetation growth status. At present, amounts of studies just focused on the LAI estimation of a single plant type, while plant types are usually mixed rather than single distribution. In this study, the suitability of GF-1 data for multi-species LAI estimation was evaluated by using Gaussian process regression (GPR), and a look-up table (LUT) combined with a PROSAIL radiative transfer model. Then, the performance of the LUT and GPR for multi-species LAI estimation was analyzed in term of 15 different band combinations and 10 published vegetation indices (VIs). Lastly, the effect of the different band combinations and published VIs on the accuracy of LAI estimation was discussed. The results indicated that GF-1 data exhibited a good potential for multi-species LAI retrieval. Then, GPR exhibited better performance than that of LUT for multi-species LAI estimation. What is more, modified soil adjusted vegetation index (MSAVI) was selected based on the GPR algorithm for multi-species LAI estimation with a lower root mean squared error (RMSE = 0.6448 m2/m2) compared to other band combinations and VIs. Then, this study can provide guidance for multi-species LAI estimation.
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Folhas de Planta , Imagens de Satélites , Algoritmos , China , Humanos , Modelos Teóricos , Distribuição Normal , Plantas , Análise de Regressão , Solo , Análise EspectralRESUMO
The availability of satellite optical information is often hampered by the natural presence of clouds, which can be problematic for many applications. Persistent clouds over agricultural fields can mask key stages of crop growth, leading to unreliable yield predictions. Synthetic Aperture Radar (SAR) provides all-weather imagery which can potentially overcome this limitation, but given its high and distinct sensitivity to different surface properties, the fusion of SAR and optical data still remains an open challenge. In this work, we propose the use of Multi-Output Gaussian Process (MOGP) regression, a machine learning technique that learns automatically the statistical relationships among multisensor time series, to detect vegetated areas over which the synergy between SAR-optical imageries is profitable. For this purpose, we use the Sentinel-1 Radar Vegetation Index (RVI) and Sentinel-2 Leaf Area Index (LAI) time series over a study area in north west of the Iberian peninsula. Through a physical interpretation of MOGP trained models, we show its ability to provide estimations of LAI even over cloudy periods using the information shared with RVI, which guarantees the solution keeps always tied to real measurements. Results demonstrate the advantage of MOGP especially for long data gaps, where optical-based methods notoriously fail. The leave-one-image-out assessment technique applied to the whole vegetation cover shows MOGP predictions improve standard GP estimations over short-time gaps (R2 of 74% vs 68%, RMSE of 0.4 vs 0.44 [m 2 m -2]) and especially over long-time gaps (R2 of 33% vs 12%, RMSE of 0.5 vs 1.09 [m 2 m -2]). A second assessment is focused on crop-specific regions, clustering pixels fulfilling specific model conditions where the synergy is profitable. Results reveal the MOGP performance is crop type and crop stage dependent. For long time gaps, best R2 are obtained over maize, ranging from 0.1 (tillering) to 0.36 (development) up to 0.81 (maturity); for moderate time gap, R2 = 0.93 (maturity) is obtained. Crops such as wheat, oats, rye and barley, can profit from the LAI-RVI synergy, with R2 varying between 0.4 and 0.6. For beet or potatoes, MOGP provides poorer results, but alternative descriptors to RVI should be tested for these specific crops in the future before discarding synergy real benefits. In conclusion, active-passive sensor fusion with MOGP represents a novel and promising approach to cope with crop monitoring over cloud-dominated areas.
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We examine the deployment of multiple mobile sensors to explore an unknown region to map regions containing concentration of a physical quantity such as heat, electron density, and so on. The exploration trades off between two desiderata: to continue taking data in a region known to contain the quantity of interest with the intent of refining the measurements vs. taking data in unobserved areas to attempt to discover new regions where the quantity may exist. Making reasonable and practical decisions to simultaneously fulfill both goals of exploration and data refinement seem to be hard and contradictory. For this purpose, we propose a general framework that makes value-laden decisions for the trajectory of mobile sensors. The framework employs a Gaussian process regression model to predict the distribution of the physical quantity of interest at unseen locations. Then, the decision-making on the trajectories of sensors is performed using an epistemic utility controller. An example is provided to illustrate the merit and applicability of the proposed framework.
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This study explores the potential of photocatalytic degradation using novel NML-BiFeO3 (noble metal-incorporated bismuth ferrite) compounds for eliminating malachite green (MG) dye from wastewater. The effectiveness of various Gaussian process regression (GPR) models in predicting MG degradation is investigated. Four GPR models (Matern, Exponential, Squared Exponential, and Rational Quadratic) were employed to analyze a dataset of 1200 observations encompassing various experimental conditions. The models have considered ten input variables, including catalyst properties, solution characteristics, and operational parameters. The Exponential kernel-based GPR model achieved the best performance, with a near-perfect R2 value of 1.0, indicating exceptional accuracy in predicting MG degradation. Sensitivity analysis revealed process time as the most critical factor influencing MG degradation, followed by pore volume, catalyst loading, light intensity, catalyst type, pH, anion type, surface area, and humic acid concentration. This highlights the complex interplay between these factors in the degradation process. The reliability of the models was confirmed by outlier detection using William's plot, demonstrating a minimal number of outliers (66-71 data points depending on the model). This indicates the robustness of the data utilized for model development. This study suggests that NML-BiFeO3 composites hold promise for wastewater treatment and that GPR models, particularly Matern-GPR, offer a powerful tool for predicting MG degradation. Identifying fundamental catalyst properties can expedite the application of NML-BiFeO3, leading to optimized wastewater treatment processes. Overall, this study provides valuable insights into using NML-BiFeO3 compounds and machine learning for efficient MG removal from wastewater.
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This study explores machine learning (ML) capabilities for predicting the shear strength of reinforced concrete deep beams (RCDBs). For this purpose, eight typical machine-learning models, i.e., symbolic regression (SR), XGBoost (XGB), CatBoost (CATB), random forest (RF), LightGBM, support vector regression (SVR), artificial neural networks (ANN), and Gaussian process regression (GPR) models, are selected and compared based on a database of 840 samples with 14 input features. The hyperparameter tuning of the introduced ML models is performed using the Bayesian optimization (BO) technique. The comparison results show that the CatBoost model is the most reliable and accurate ML model (R2 = 0.997 and 0.947 in the training and testing sets, respectively). In addition, simple and practical design expressions for RCDBs have been proposed based on the SR model with a physical meaning and acceptable accuracy (an average prediction-to-test ratio of 0.935 and a standard deviation of 0.198). Meanwhile, the shear strength predicted by ML models was then compared with classical mechanics-driven shear models, including two prominent practice codes (i.e., ACI318, EC2) and two previous mechanical models, which indicated that the ML approach is highly reliable and accurate over conventional methods. In addition, a reliability-based design was conducted on two ML models, and their reliability results were compared with those of two code standards. The findings revealed that the ML models demonstrate higher reliability compared to code standards.
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Organic solar cells (OSCs) now approach power conversion efficiencies of 20%. However, in order to enter mass markets, problems in upscaling and operational lifetime have to be solved, both concerning the connection between processing conditions and active layer morphology. Morphological studies supporting the development of structure-process-property relations are time-consuming, complex, and expensive to undergo and for which statistics, needed to assess significance, are difficult to be collected. This work demonstrates that causal relationships between processing conditions, morphology, and stability can be obtained in a high-throughput method by combining low-cost automated experiments with data-driven analysis methods. An automatic spectral modeling feeds parametrized absorption data into a feature selection technique that is combined with Gaussian process regression to quantify deterministic relationships linking morphological features and processing conditions with device functionality. The effect of the active layer thickness and the morphological order is further modeled by drift-diffusion simulations and returns valuable insight into the underlying mechanisms for improving device stability by tuning the microstructure morphology with versatile approaches. Predicting microstructural features as a function of processing parameters is decisive know-how for the large-scale production of OSCs.
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This paper proposed a hybrid intelligent process model, based on a hybrid model combining the two-temperature model (TTM) and molecular dynamics simulation (MDS) (TTM-MDS). Combined atomistic-continuum modeling of short-pulse laser melting and disintegration of metal films [Physical Review B, 68, (064114):1-22.], and Gaussian process regression (GPR), for micro-electrical discharge machining (micro-EDM) were also used. A model of single-spark micro-EDM process has been constructed based on TTM-MDS model to predict the removed depth (RD) and material removal rate (MRR). Then, a GPR model was proposed to establish the relationship between input process parameters (energy area density and pulse-on duration) and the process responses (RD and MRR) for micro-EDM machining. The GPR model was trained, tested, and tuned using the data generated from the numerical simulations. Through the GPR model, it was found that micro-EDM process responses can be accurately predicted for the chosen process conditions. Therefore, the hybrid intelligent model proposed in this paper can be used for a micro-EDM process to predict the performance.
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Space-based cropland phenology monitoring substantially assists agricultural managing practices and plays an important role in crop yield predictions. Multitemporal satellite observations allow analyzing vegetation seasonal dynamics over large areas by using vegetation indices or by deriving biophysical variables. The Nile Delta represents about half of all agricultural lands of Egypt. In this region, intensifying farming systems are predominant and multi-cropping rotations schemes are increasing, requiring a high temporal and spatial resolution monitoring for capturing successive crop growth cycles. This study presents a workflow for cropland phenology characterization and mapping based on time series of green Leaf Area Index (LAI) generated from NASA's Harmonized Landsat 8 (L8) and Sentinel-2 (S2) surface reflectance dataset from 2016 to 2019. LAI time series were processed for each satellite dataset, which were used separately and combined to identify seasonal dynamics for a selection of crop types (wheat, clover, maize and rice). For the combination of L8 with S2 LAI products, we proposed two time series smoothing and fitting methods: (1) the Savitzky-Golay (SG) filter and (2) the Gaussian Processes Regression (GPR) fitting function. Single-sensor and L8-S2 combined LAI time series were used for the calculation of key crop Land Surface Phenology (LSP) metrics (start of season, end of season, length of season), whereby the detection of cropland growing seasons was based on two established threshold methods, i.e., a seasonal or a relative amplitude value. Overall, the developed phenology extraction scheme enabled identifying up to two successive crop cycles within a year, with a superior performance observed for the seasonal than for the relative threshold method, in terms of consistency and cropland season detection capability. Differences between the time series collections were analyzed by comparing the phenology metrics per crop type and year. Results suggest that L8-S2 combined LAI data streams with GPR led to a more precise detection of the start and end of growing seasons for most crop types, reaching an overall detection of 74% over the total planted crops versus 69% with S2 and 63% with L8 alone. Finally, the phenology mapping allowed us to evaluate the spatial and temporal evolution of the croplands over the agroecosystem in the Nile Delta.
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BACKGROUND: Congenital heart disease (CHD) is one of the most important and common group of congenital malformations in humans. Concurrent development and close functional links between the fetal heart and placenta emphasise the importance of understanding placental function and its influence in pregnancy outcomes. The aim of this study was to evaluate placental oxygenation by relaxometry (T2*) to assess differences in placental phenotype and function in CHD. METHODS: In this prospective cross-sectional observational study, 69 women with a fetus affected with CHD and 37 controls, whole placental T2* was acquired using a 1.5-Tesla MRI scanner. Gaussian Process Regression was used to assess differences in placental phenotype in CHD cohorts compared to our controls. RESULTS: Placental T2* maps demonstrated significant differences in CHD compared to controls at equivalent gestational age. Mean T2* values over the entire placental volume were lowest compared to predicted normal in right sided obstructive lesions (RSOL) (Z-Score 2.30). This cohort also showed highest lacunarity indices (Z-score -1.7), as a marker of lobule size. Distribution patterns of T2* values over the entire placental volume were positively skewed in RSOL (Z-score -4.69) and suspected, not confirmed coarctation of the aorta (CoA-) (Z-score -3.83). Deviations were also reflected in positive kurtosis in RSOL (Z-score -3.47) and CoA- (Z-score -2.86). CONCLUSION: Placental structure and function appear to deviate from normal development in pregnancies with fetal CHD. Specific patterns of altered placental function assessed by T2* deliver crucial complementary information to antenatal assessments in the presence of fetal CHD.
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Doenças Fetais/diagnóstico por imagem , Cardiopatias Congênitas/diagnóstico por imagem , Imageamento por Ressonância Magnética/métodos , Placenta/diagnóstico por imagem , Adulto , Estudos de Casos e Controles , Feminino , Humanos , Gravidez , Estudos ProspectivosRESUMO
Monitoring cropland phenology from optical satellite data remains a challenging task due to the influence of clouds and atmospheric artifacts. Therefore, measures need to be taken to overcome these challenges and gain better knowledge of crop dynamics. The arrival of cloud computing platforms such as Google Earth Engine (GEE) has enabled us to propose a Sentinel-2 (S2) phenology end-to-end processing chain. To achieve this, the following pipeline was implemented: (1) the building of hybrid Gaussian Process Regression (GPR) retrieval models of crop traits optimized with active learning, (2) implementation of these models on GEE (3) generation of spatiotemporally continuous maps and time series of these crop traits with the use of gap-filling through GPR fitting, and finally, (4) calculation of land surface phenology (LSP) metrics such as the start of season (SOS) or end of season (EOS). Overall, from good to high performance was achieved, in particular for the estimation of canopy-level traits such as leaf area index (LAI) and canopy chlorophyll content, with normalized root mean square errors (NRMSE) of 9% and 10%, respectively. By means of the GPR gap-filling time series of S2, entire tiles were reconstructed, and resulting maps were demonstrated over an agricultural area in Castile and Leon, Spain, where crop calendar data were available to assess the validity of LSP metrics derived from crop traits. In addition, phenology derived from the normalized difference vegetation index (NDVI) was used as reference. NDVI not only proved to be a robust indicator for the calculation of LSP metrics, but also served to demonstrate the good phenology quality of the quantitative trait products. Thanks to the GEE framework, the proposed workflow can be realized anywhere in the world and for any time window, thus representing a shift in the satellite data processing paradigm. We anticipate that the produced LSP metrics can provide meaningful insights into crop seasonal patterns in a changing environment that demands adaptive agricultural production.
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For the last decade, Gaussian process regression (GPR) proved to be a competitive machine learning regression algorithm for Earth observation applications, with attractive unique properties such as band relevance ranking and uncertainty estimates. More recently, GPR also proved to be a proficient time series processor to fill up gaps in optical imagery, typically due to cloud cover. This makes GPR perfectly suited for large-scale spatiotemporal processing of satellite imageries into cloud-free products of biophysical variables. With the advent of the Google Earth Engine (GEE) cloud platform, new opportunities emerged to process local-to-planetary scale satellite data using advanced machine learning techniques and convert them into gap-filled vegetation properties products. However, GPR is not yet part of the GEE ecosystem. To circumvent this limitation, this work proposes a general adaptation of GPR formulation to parallel processing framework and its integration into GEE. To demonstrate the functioning and utility of the developed workflow, a GPR model predicting green leaf area index (LAI G ) from Sentinel-2 imagery was imported. Although by running this GPR model into GEE any corner of the world can be mapped into LAI G at a resolution of 20 m, here we show some demonstration cases over western Europe with zoom-ins over Spain. Thanks to the computational power of GEE, the mapping takes place on-the-fly. Additionally, a GPR-based gap filling strategy based on pre-optimized kernel hyperparameters is also put forward for the generation of multi-orbit cloud-free LAI G maps with an unprecedented level of detail, and the extraction of regularly-sampled LAI G time series at a pixel level. The ability to plugin a locally-trained GPR model into the GEE framework and its instant processing opens up a new paradigm of remote sensing image processing.
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The global demand for natural products grows rapidly, intensifying the request for the development of high-throughput, fast, non-invasive tools for quality control applicable on-site. Moisture content is one of the most important quality parameters of natural products. It determines their market suitability, stability and shelf life and should preferably be constantly monitored. Miniaturized near-infrared (NIR) spectroscopy is a powerful method for on-site analysis, potentially fulfilling this requirement. Here, a feasibility study for applicability and analytical performance of three miniaturized NIR spectrometers and two benchtop instruments was evaluated in that scenario. The case study involved 192 dried plant extracts composed of five different plants harvested in different countries at various times within two years. The reference analysis by Karl Fischer titration determined the water content in this sample set between 1.36% and 6.47%. For the spectroscopic analysis half of the samples were laced with a drying agent to comply with the industry standard. The performance of various calibration models for NIR analysis was evaluated on the basis of root-mean square error of prediction (RMSEP) determined for an independent test set. Partial least squares regression (PLSR), Gaussian process regression (GPR) and artificial neural network (ANN) models were constructed for the spectral sets from each instrument. GPR and ANN models performed superior for all samples measured by handheld spectrometers and for native ones analyzed by benchtop instruments. Moreover, the accuracy penalty when analyzing native samples was lower for GPR and ANN prediction as well. With GPR or ANN calibration, miniaturized spectrometers offered the prediction performance at the level of the benchtop instruments. Therefore, in this analytical application miniaturized spectrometers can be used on-site with no penalty to the performance vs. laboratory-based NIR analysis.
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Redes Neurais de Computação , Espectroscopia de Luz Próxima ao Infravermelho , Calibragem , Análise dos Mínimos Quadrados , Distribuição NormalRESUMO
Timely monitoring nitrogen status of rice crops with remote sensing can help us optimize nitrogen fertilizer management and reduce environmental pollution. Recently, the use of near-surface imaging spectroscopy is emerging as a promising technology that can collect hyperspectral images with spatial resolutions ranging from millimeters to decimeters. The spatial resolution is crucial for the efficiency in the image sampling across rice plants and the separation of leaf signals from the background. However, the optimal spatial resolution of such images for monitoring the leaf nitrogen concentration (LNC) in rice crops remains unclear. To assess the impact of spatial resolution on the estimation of rice LNC, we collected ground-based hyperspectral images throughout the entire growing season over 2 consecutive years and generated ten sets of images with spatial resolutions ranging from 1.3 to 450 mm. These images were used to determine the sensitivity of LNC prediction to spatial resolution with three groups of vegetation indices (VIs) and two multivariate methods Gaussian Process regression (GPR) and Partial least squares regression (PLSR). The reflectance spectra of sunlit-, shaded-, and all-leaf leaf pixels separated from background pixels at each spatial resolution were used to predict LNC with VIs, GPR and PLSR, respectively. The results demonstrated all-leaf pixels generally exhibited more stable performance than sunlit- and shaded-leaf pixels regardless of estimation approaches. The predictions of LNC required stage-specific LNC~VI models for each vegetative stage but could be performed with a single model for all the reproductive stages. Specifically, most VIs achieved stable performances from all the resolutions finer than 14 mm for the early tillering stage but from all the resolutions finer than 56 mm for the other stages. In contrast, the global models for the prediction of LNC across the entire growing season were successfully established with the approaches of GPR or PLSR. In particular, GPR generally exhibited the best prediction of LNC with the optimal spatial resolution being found at 28 mm. These findings represent significant advances in the application of ground-based imaging spectroscopy as a promising approach to crop monitoring and understanding the effects of spatial resolution on the estimation of rice LNC.
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The prevalence, age of onset, and symptomatology of many neuropsychiatric conditions differ between males and females. To understand the causes and consequences of sex differences it is important to establish where they occur in the human brain. We report the first meta-analysis of typical sex differences on global brain volume, a descriptive account of the breakdown of studies of each compartmental volume by six age categories, and whole-brain voxel-wise meta-analyses on brain volume and density. Gaussian-process regression coordinate-based meta-analysis was used to examine sex differences in voxel-based regional volume and density. On average, males have larger total brain volumes than females. Examination of the breakdown of studies providing total volumes by age categories indicated a bias towards the 18-59 year-old category. Regional sex differences in volume and tissue density include the amygdala, hippocampus and insula, areas known to be implicated in sex-biased neuropsychiatric conditions. Together, these results suggest candidate regions for investigating the asymmetric effect that sex has on the developing brain, and for understanding sex-biased neurological and psychiatric conditions.