ALBERT

Description: For the past two decades, the measurement of nitrous oxide (N2O) isotopocules – isotopically substituted molecules 14N15N16O, 15N14N16O and 14N14N18O of the main isotopic species 14N14N16O – has been a promising technique for understanding N2O production and consumption pathways. The coupling of non-cryogenic and tuneable light sources with different detection schemes, such as direct absorption quantum cascade laser absorption spectroscopy (QCLAS), cavity ring-down spectroscopy (CRDS) and off-axis integrated cavity output spectroscopy (OA-ICOS), has enabled the production of commercially available and field-deployable N2O isotopic analyzers. In contrast to traditional isotope-ratio mass spectrometry (IRMS), these instruments are inherently selective for position-specific 15N substitution and provide real-time data, with minimal or no sample pretreatment, which is highly attractive for process studies. Here, we compared the performance of N2O isotope laser spectrometers with the three most common detection schemes: OA-ICOS (N2OIA-30e-EP, ABB – Los Gatos Research Inc.), CRDS (G5131-i, Picarro Inc.) and QCLAS (dual QCLAS and preconcentration, trace gas extractor (TREX)-mini QCLAS, Aerodyne Research Inc.). For each instrument, the precision, drift and repeatability of N2O mole fraction [N2O] and isotope data were tested. The analyzers were then characterized for their dependence on [N2O], gas matrix composition (O2, Ar) and spectral interferences caused by H2O, CO2, CH4 and CO to develop analyzer-specific correction functions. Subsequently, a simulated two-end-member mixing experiment was used to compare the accuracy and repeatability of corrected and calibrated isotope measurements that could be acquired using the different laser spectrometers. Our results show that N2O isotope laser spectrometer performance is governed by an interplay between instrumental precision, drift, matrix effects and spectral interferences. To retrieve compatible and accurate results, it is necessary to include appropriate reference materials following the identical treatment (IT) principle during every measurement. Remaining differences between sample and reference gas compositions have to be corrected by applying analyzer-specific correction algorithms. These matrix and trace gas correction equations vary considerably according to N2O mole fraction, complicating the procedure further. Thus, researchers should strive to minimize differences in composition between sample and reference gases. In closing, we provide a calibration workflow to guide researchers in the operation of N2O isotope laser spectrometers in order to acquire accurate N2O isotope analyses. We anticipate that this workflow will assist in applications where matrix and trace gas compositions vary considerably (e.g., laboratory incubations, N2O liberated from wastewater or groundwater), as well as extend to future analyzer models and instruments focusing on isotopic species of other molecules.

Description: The urban heat island intensity (UHII) is the temperature difference between urban areas and their rural surroundings. It is commonly attributed to changes in the underlying surface structure caused by urbanization. Air pollution caused by aerosol particles can affect the UHII through changing (1) the surface energy balance by the aerosol radiative effect (ARE) and (2) planetary-boundary-layer (PBL) stability and airflow intensity by modifying thermodynamic structure, which is referred to as the aerosol dynamic effect (ADE). By analyzing satellite data and ground-based observations collected from 2001 to 2010 at 35 cities in China and using the WRF-Chem model, we find that the impact of aerosols on UHII differs considerably: reducing the UHII in summer but increasing the UHII in winter. This seasonal contrast is proposed to be caused by the different strengths of the ARE and ADE between summer and winter. In summer, the ARE on UHII is dominant over the ADE, cooling down surface temperature more strongly in urban areas than in rural areas because of much higher aerosol loading, and offsets the urban heating, therefore weakening UHII. In winter, however, the ADE is more dominant, because aerosols stabilize the PBL more in the polluted condition, weakening the near-surface heat transport over urban areas in both vertical and horizontal directions. This means that the heat accumulated in urban areas is dispersed less effectively, and thus the UHII is enhanced. These findings shed new light on the impact of the interaction between urbanization-induced surface changes and air pollution on urban climate.

Description: Since the industrial revolution, human activities have dramatically changed the nitrogen (N) cycle in natural systems. Anthropogenic emissions of reactive nitrogen (Nr) can return to the earth's surface through atmospheric Nr deposition. Increased Nr deposition may improve ecosystem productivity. However, excessive Nr deposition can cause a series of negative effects on ecosystem health, biodiversity, soil, and water. Thus, accurate estimations of Nr deposition are necessary for evaluating its environmental impacts. The United States, Canada and Europe have successively launched a number of satellites with sensors that allow retrieval of atmospheric NO2 and NH3 column density and therefore estimation of surface Nr concentration and deposition at an unprecedented spatiotemporal scale. Atmosphere NH3 column can be retrieved from atmospheric infra-red emission, while atmospheric NO2 column can be retrieved from reflected solar radiation. In recent years, scientists attempted to estimate surface Nr concentration and deposition using satellite retrieval of atmospheric NO2 and NH3 columns. In this study, we give a thorough review of recent advances of estimating surface Nr concentration and deposition using the satellite retrievals of NO2 and NH3, present a framework of using satellite data to estimate surface Nr concentration and deposition based on recent works, and summarize the existing challenges for estimating surface Nr concentration and deposition using the satellite-based methods. We believe that exploiting satellite data to estimate Nr deposition has a broad and promising prospect.

Description: Satellite-derived aerosol products provide long-term and large-scale observations for analysing aerosol distributions and variations, climate-scale aerosol simulations, and aerosol–climate interactions. Therefore, a better understanding of the consistencies and differences among multiple aerosol products is important. The objective of this study is to compare 11 global monthly aerosol optical depth (AOD) products, which are the European Space Agency Climate Change Initiative (ESA-CCI) Advanced Along-Track Scanning Radiometer (AATSR), Advanced Very High Resolution Radiometer (AVHRR), Multi-angle Imaging SpectroRadiometer (MISR), Moderate Resolution Imaging Spectroradiometer (MODIS), Sea-viewing Wide Field-of-view Sensor (SeaWiFS), Visible Infrared Imaging Radiometer (VIIRS), and POLarization and Directionality of the Earth's Reflectance (POLDER) products. AErosol RObotic NEtwork (AERONET) Version 3 Level 2.0 monthly measurements at 308 sites around the world are selected for comparison. Our results illustrate that the spatial distributions and temporal variations of most aerosol products are highly consistent globally but exhibit certain differences on regional and site scales. In general, the AATSR Dual View (ADV) and SeaWiFS products show the lowest spatial coverage with numerous missing values, while the MODIS products can cover most areas (average of 87 %) of the world. The best performance is observed in September–October–November (SON) and the worst is in June–July–August (JJA). All the products perform unsatisfactorily over northern Africa and Middle East, southern and eastern Asia, and their coastal areas due to the influence from surface brightness and human activities. In general, the MODIS products show the best agreement with the AERONET-based AOD values on different spatial scales among all the products. Furthermore, all aerosol products can capture the correct aerosol trends at most cases, especially in areas where aerosols change significantly. The MODIS products perform best in capturing the global temporal variations in aerosols. These results provide a reference for users to select appropriate aerosol products for their particular studies.

Description: Ammonia (NH3), as an alkaline gas in the atmosphere, can cause direct or indirect effects on the air quality, soil acidification, climate change and human health. Estimating surface NH3 concentrations is critically important for modeling the dry deposition of NH3 and for modeling the formation of ammonium nitrate, which have important impacts on the natural environment. However, sparse monitoring sites make it challenging and difficult to understand the global distribution of surface NH3 concentrations in both time and space. We estimated the global surface NH3 concentrations for the years of 2008–2016 using satellite NH3 retrievals combining vertical profiles from GEOS-Chem. The accuracy assessment indicates that the satellite-based approach has achieved a high predictive power for annual surface NH3 concentrations compared with the measurements of all sites in China, the US and Europe (R2=0.76 and RMSE = 1.50 µg N m−3). The satellite-derived surface NH3 concentrations had higher consistency with the ground-based measurements in China (R2=0.71 and RMSE = 2.6 µg N m−3) than the US (R2=0.45 and RMSE = 0.76 µg N m−3) and Europe (R2=0.45 and RMSE = 0.86 µg N m−3) at a yearly scale. Annual surface NH3 concentrations higher than 6 µg N m−3 are mainly concentrated in the North China Plain of China and northern India, followed by 2–6 µg N m−3 mainly in southern and northeastern China, India, western Europe, and the eastern United States (US). High surface NH3 concentrations were found in the croplands in China, the US and Europe, and surface NH3 concentrations in the croplands in China were approximately double those in the croplands in the US and Europe. The linear trend analysis shows that an increase rate of surface NH3 concentrations (〉 0.2 µg N m−3 yr−1) appeared in eastern China during 2008–2016, and a middle increase rate (0.1–0.2 µg N m−3 yr−1) occurred in northern Xinjiang over China. NH3 increase was also found in agricultural regions in the central and eastern US with an annual increase rate of lower than 0.10 µg N m−3 yr−1. The satellite-derived surface NH3 concentrations help us to determine the NH3 pollution status in the areas without monitoring sites and to estimate the dry deposition of NH3 in the future.

Description: Fine particulate matter with aerodynamic diameters ≤2.5 µm (PM2.5) has adverse effects on human health and the atmospheric environment. The estimation of surface PM2.5 concentrations has made intensive use of satellite-derived aerosol products. However, it has been a great challenge to obtain high-quality and high-resolution PM2.5 data from both ground and satellite observations, which is essential to monitor air pollution over small-scale areas such as metropolitan regions. Here, the space–time extremely randomized trees (STET) model was enhanced by integrating updated spatiotemporal information and additional auxiliary data to improve the spatial resolution and overall accuracy of PM2.5 estimates across China. To this end, the newly released Moderate Resolution Imaging Spectroradiometer Multi-Angle Implementation of Atmospheric Correction AOD product, along with meteorological, topographical and land-use data and pollution emissions, was input to the STET model, and daily 1 km PM2.5 maps for 2018 covering mainland China were produced. The STET model performed well, with a high out-of-sample (out-of-station) cross-validation coefficient of determination (R2) of 0.89 (0.88), a low root-mean-square error of 10.33 (10.93) µg m−3, a small mean absolute error of 6.69 (7.15) µg m−3 and a small mean relative error of 21.28 % (23.69 %). In particular, the model captured well the PM2.5 concentrations at both regional and individual site scales. The North China Plain, the Sichuan Basin and Xinjiang Province always featured high PM2.5 pollution levels, especially in winter. The STET model outperformed most models presented in previous related studies, with a strong predictive power (e.g., monthly R2=0.80), which can be used to estimate historical PM2.5 records. More importantly, this study provides a new approach for obtaining high-resolution and high-quality PM2.5 dataset across mainland China (i.e., ChinaHighPM2.5), important for air pollution studies focused on urban areas.

Description: The aerosol–planetary boundary layer (PBL) interaction was proposed as an important mechanism to stabilize the atmosphere and exacerbate surface air pollution. Despite the tremendous progress made in understanding this process, its magnitude and significance still have large uncertainties and vary largely with aerosol distribution and meteorological conditions. In this study, we focus on the role of aerosol vertical distribution in thermodynamic stability and PBL development by jointly using micropulse lidar, sun photometer, and radiosonde measurements taken in Beijing. Despite the complexity of aerosol vertical distributions, cloud-free aerosol structures can be largely classified into three types: well-mixed, decreasing with height, and inverse structures. The aerosol–PBL relationship and diurnal cycles of the PBL height and PM2.5 associated with these different aerosol vertical structures show distinct characteristics. The vertical distribution of aerosol radiative forcing differs drastically among the three types, with strong heating in the lower, middle, and upper PBL, respectively. Such a discrepancy in the heating rate affects the atmospheric buoyancy and stability differently in the three distinct aerosol structures. Absorbing aerosols have a weaker effect of stabilizing the lower atmosphere under the decreasing structure than under the inverse structure. As a result, the aerosol–PBL interaction can be strengthened by the inverse aerosol structure and can be potentially neutralized by the decreasing structure. Moreover, aerosols can both enhance and suppress PBL stability, leading to both positive and negative feedback loops. This study attempts to improve our understanding of the aerosol–PBL interaction, showing the importance of the observational constraint of aerosol vertical distribution for simulating this interaction and consequent feedbacks.

Description: Satellite-derived aerosol products provide long-term and large-scale observations for analysing aerosol distributions and variations, climate-scale aerosol simulations, and aerosol-climate interactions. Therefore, a better understanding of the consistencies and differences among multiple aerosol products is of great importance. The objective of this study is to evaluate nine operational global aerosol optical depth (AOD) products, including the European Space Agency Climate Change Initiative (ESA-CCI) Advanced Along-Track Scanning Radiometer (AATSR), Advanced Very High Resolution Radiometer (AVHRR), Multi-angle Imaging Spectro Radiometer (MISR), Moderate Resolution Imaging Spectroradiometer (MODIS), and Sea-Viewing Wide Field-of-View Sensor (SeaWiFS) over the land and oceans during the period from 1997 to 2017. Aerosol Robotic Network (AERONET) Version 3 Level 2.0 (cloud screened and quality assured) measurements at 243 sites around the world are selected for validation purposes. Our results illustrate that noticeable inconsistencies exist in spatial coverages, variations, and temporal trends among different aerosol products. Large annual mean AOD differences greater than 0.15 are mainly found in North Africa, Central Africa, the Middle East, and East Asia, as well as in the coastal areas of western North America and Asia. In general, the AATSR Swansea University (SU) product appears to have the best accuracy, the SeaWiFS product obviously underestimates aerosol loadings over the land and ocean, and the MODIS products seriously overestimate aerosol loadings over the land and ocean. For temporal trends, more than 77% and 72% of land and ocean sites, respectively, show the same trends direction as the ground observations. However, numerical differences are non-negligible in North Africa, the Middle East, and South Asia and in most open oceans. MODIS products are generally more accurate in describing the temporal trends over the land and ocean. The aerosol loadings trend changed from positive to negative over the past two decades (2000−2017) in some continental areas. These results suggest that multiple AOD products show significant numerical inconsistencies in describing spatial distributions and temporal trends, which should be carefully considered when users choose aerosol products for their studies.

Description: Nitrous oxide (N2O) is the primary atmospheric constituent involved in stratospheric ozone depletion and contributes strongly to changes in the climate system through a positive radiative forcing mechanism. The atmospheric abundance of N2O has increased from 270 ppb (parts per billion, 10−9 mole mole−1) during the pre-industrial era to approx. 330 ppb in 2018. Even though it is well known that microbial processes in agricultural and natural soils are the major N2O source, the contribution of specific soil processes is still uncertain. The relative abundance of N2O isotopocules (14N14N16N, 14N15N16O, 15N14N16O, and 14N14N18O) carries process-specific information and thus can be used to trace production and consumption pathways. While isotope ratio mass spectroscopy (IRMS) was traditionally used for high-precision measurement of the isotopic composition of N2O, quantum cascade laser absorption spectroscopy (QCLAS) has been put forward as a complementary technique with the potential for on-site analysis. In recent years, pre-concentration combined with QCLAS has been presented as a technique to resolve subtle changes in ambient N2O isotopic composition. From the end of May until the beginning of August 2016, we investigated N2O emissions from an intensively managed grassland at the study site Fendt in southern Germany. In total, 612 measurements of ambient N2O were taken by combining pre-concentration with QCLAS analyses, yielding δ15Nα, δ15Nβ, δ18O, and N2O concentration with a temporal resolution of approximately 1 h and precisions of 0.46 ‰, 0.36 ‰, 0.59 ‰, and 1.24 ppb, respectively. Soil δ15N-NO3- values and concentrations of NO3- and NH4+ were measured to further constrain possible N2O-emitting source processes. Furthermore, the concentration footprint area of measured N2O was determined with a Lagrangian particle dispersion model (FLEXPART-COSMO) using local wind and turbulence observations. These simulations indicated that night-time concentration observations were largely sensitive to local fluxes. While bacterial denitrification and nitrifier denitrification were identified as the primary N2O-emitting processes, N2O reduction to N2 largely dictated the isotopic composition of measured N2O. Fungal denitrification and nitrification-derived N2O accounted for 34 %–42 % of total N2O emissions and had a clear effect on the measured isotopic source signatures. This study presents the suitability of on-site N2O isotopocule analysis for disentangling source and sink processes in situ and found that at the Fendt site bacterial denitrification or nitrifier denitrification is the major source for N2O, while N2O reduction acted as a major sink for soil-produced N2O.

Description: Nitrous oxide (N2O) is the primary atmospheric constituent involved in stratospheric ozone depletion and contributes strongly to changes in the climate system through a positive radiative forcing mechanism. The atmospheric abundance of N2O has increased from 270 ppb during the pre-industrial era to approx. 330 ppb in 2018. Even though it is well known that microbial processes in agricultural and natural soils are the major N2O source, the contribution of specific soil processes is still uncertain. The relative abundance of N2O isotopocules (14N14N16N, 14N15N16O, 15N14N16O and 14N14N18O) carries process-specific in-formation and thus can be used to trace production and consumption pathways. While isotope ratio mass spectroscopy (IRMS) was traditionally used for high-precision measurement of the isotopic composition of N2O, quantum cascade laser absorption spectroscopy (QCLAS) has been put forward as a complementary technique with the potential for on-site analysis. In recent years, preconcentration combined with QCLAS has been presented as a technique to resolve subtle changes in ambient N2O isotopic composition. From the end of May until the beginning of August 2016, we investigated N2O emissions from an intensively managed grassland at the study site Fendt in Southern Germany. In total, 612 measurements of ambient N2O were taken by combining preconcentration with QCLAS analyses, yielding δ15Nα, δ15Nβ, δ18O and N2O concentration with a temporal resolution of approximately one hour and precisions of 0.46 ‰, 0.36 ‰, 0.59 ‰ and 1.24 ppb, respectively. Soil δ15N-NO3− values and concentrations of NO3− and NH4+ were measured to further constrain possible N2O-emitting source processes. Furthermore, the concentration footprint area of measured N2O was determined with a Lagrangian particle dispersion model (FLEXPART-COSMO) using local wind and turbulence observations. These simulations indicated that night-time concentration observations were largely sensitive to local fluxes. While bacterial denitrification and nitrifier denitrification were identified as the primary N2O-emitting processes, N2O reduction to N2 largely dictated the isotopic composition of measured N2O. Fungal denitrification and nitrification-derived N2O accounted for 34–42 % of total N2O emissions and had a clear effect on the measured isotopic source signatures. This study presents the suitability of on-site N2O isotopocule analysis for disentangling source and sink processes in-situ and found that at the Fendt site bacterial denitrification/nitrifier denitrification is the major source for N2O, while N2O reduction acted as a major sink.