Modeling global oceanic nitrogen deposition from food systems and its mitigation potential by reducing overuse of fertilizers.

Growing population and consumption pose unprecedented demands on food production. However, ammonia emissions mainly from food systems increase oceanic nitrogen deposition contributing to eutrophication. Here, we developed a long-term oceanic nitrogen deposition dataset (1970 to 2018) with updated ammonia emissions from food systems, evaluated the impact of ammonia emissions on oceanic nitrogen deposition patterns, and discussed the potential impact of nitrogen fertilizer overuse. Based on the chemical transport modeling approach, oceanic ammonia-related nitrogen deposition increased by 89% globally between 1970 and 2018, and now, it exceeds oxidized nitrogen deposition by over 20% in coastal regions including China Sea, India Coastal, and Northeastern Atlantic Shelves. Approximately 38% of agricultural nitrogen fertilizer was excessive, which corresponds to 15% of global oceanic ammonia-related nitrogen deposition. Policymakers and water quality managers need to pay increasingly more attention to ammonia associated with food production if the goal of reducing coastal nitrogen pollution is to be achieved for Sustainable Development Goals.

Exploring global changes in agricultural ammonia emissions and their contribution to nitrogen deposition since 1980.

SignificanceAgricultural systems are already major forces of ammonia pollution and environmental degradation. How agricultural ammonia emissions affect the spatio-temporal patterns of nitrogen deposition and where to target future mitigation efforts, remains poorly understood. We develop a substantially complete and coherent agricultural ammonia emissions dataset in nearly recent four decades, and evaluate the relative role of reduced nitrogen in total nitrogen deposition in a spatially explicit way. Global reduced nitrogen deposition has grown rapidly, and will occupy a greater dominant position in total nitrogen deposition without future ammonia regulations. Recognition of agricultural ammonia emissions on nitrogen deposition is critical to formulate effective policies to address ammonia related environmental challenges and protect ecosystems from excessive nitrogen inputs.

Setting goals for agricultural nitrogen emission reduction to ensure safe air and groundwater quality: A case study of Quzhou, the North China Plain.

Setting nitrogen (N) emission targets for agricultural systems is crucial to prevent to air and groundwater pollution, yet such targets are rarely defined at the county level. In this study, we employed a forecasting-and-back casting approach to establish human health-based nitrogen targets for air and groundwater quality in Quzhou county, located in the North China Plain. By adopting the World Health Organization (WHO) phase I standard for PM2.5 concentration (35 µg m-3) and a standard of 11.3 mg NO3--N L-1 for nitrate in drinking water, we found that ammonia (NH3) emissions from the entire county must be reduced by at least 3.2 kilotons year-1 in 2050 to meet the WHO's PM2.5 phase I standard. Additionally, controlling other pollutants such as sulfur dioxide (SO2) and nitrogen oxides (NOx) is necessary, with required reductions ranging from 16% to 64% during 2017-2050. Furthermore, to meet the groundwater quality standard, nitrate nitrogen (NO3--N) leaching to groundwater should not exceed 0.8 kilotons year-1 by 2050. Achieving this target would require a 50% reduction in NH3 emissions and a 21% reduction in NO3--N leaching from agriculture in Quzhou in 2050 compared to their respective levels in 2017 (5.0 and 2.1 kilotons, respectively). Our developed method and the resulting N emission targets can support the development of environmentally-friendly agriculture by facilitating the design of control strategies to minimize agricultural N losses.

Atmospheric nitrogen deposition: A review of quantification methods and its spatial pattern derived from the global monitoring networks.

Atmospheric nitrogen (N) deposition is a vital component of the global N cycle. Excessive N deposition on the Earth's surface has adverse impacts on ecosystems and humans. Quantification of atmospheric N deposition is indispensable for assessing and addressing N deposition-induced environmental issues. In the present review, we firstly summarized the current methods applied to quantify N deposition (wet, dry, and total N deposition), their advantages and major limitations. Secondly, we illustrated the long-term N deposition monitoring networks worldwide and the results attained via such long-term monitoring. Results show that China faces heavier N deposition than the United States, European countries, and other countries in East Asia. Next, we proposed a framework for estimating the atmospheric wet and dry N deposition using a combined method of surface monitoring, modeling, and satellite remote sensing. Finally, we put forth the critical research challenges and future directions of the atmospheric N deposition. CAPSULE: A review of quantification methods and the global data on nitrogen deposition and a systematic framework was proposed for quantifying nitrogen deposition.

Identifying Ammonia Hotspots in China Using a National Observation Network.

The limited availability of ammonia (NH3) measurements is currently a barrier to understanding the vital role of NH3 in secondary aerosol formation during haze pollution events and prevents a full assessment of the atmospheric deposition of reactive nitrogen. The observational gaps motivated us to design this study to investigate the spatial distributions and seasonal variations in atmospheric NH3 on a national scale in China. On the basis of a 1-year observational campaign at 53 sites with uniform protocols, we confirm that abundant concentrations of NH3 [1 to 23.9 µg m-3] were identified in typical agricultural regions, especially over the North China Plain (NCP). The spatial pattern of the NH3 surface concentration was generally similar to those of the satellite column concentrations as well as a bottom-up agriculture NH3 emission inventory. However, the observed NH3 concentrations at urban and desert sites were comparable with those from agricultural sites and 2-3 times those of mountainous/forest/grassland/waterbody sites. We also found that NH3 deposition fluxes at urban sites account for only half of the emissions in the NCP, suggesting the transport of urban NH3 emissions to downwind areas. This finding provides policy makers with insights into the potential mitigation of nonagricultural NH3 sources in developed regions.

Sources and Processes Affecting Fine Particulate Matter Pollution over North China: An Adjoint Analysis of the Beijing APEC Period.

The stringent emission controls during the APEC 2014 (the Asia-Pacific Economic Cooperation Summit; November 5-11, 2014) offer a unique opportunity to quantify factors affecting fine particulate matter (PM2.5) pollution over North China. Here we apply a four-dimensional variational data assimilation system using the adjoint model of GEOS-Chem to address this issue. Hourly surface measurements of PM2.5 and SO2 for October 15-November 14, 2014 are assimilated into the model to optimize daily aerosol primary and precursor emissions over North China. Measured PM2.5 concentrations in Beijing average 50.3 µg m(-3) during APEC, 43% lower than the mean concentration (88.2 µg m(-3)) for the whole period including APEC. Model results attribute about half of the reduction to meteorology due to active cold surge occurrences during APEC. Assimilation of surface measurements largely reduces the model biases and estimates 6%-30% lower aerosol emissions in the Beijing-Tianjin-Hebei region during APEC than in late October. We further demonstrate that high PM2.5 events in Beijing during this period can be occasionally contributed by natural mineral dust, but more events show large sensitivities to inorganic aerosol sources, particularly emissions of ammonia (NH3) and nitrogen oxides (NOx) reflecting strong formation of aerosol nitrate in the fall season.

Combined short-term and long-term emission controls improve air quality sustainably in China.

The effectiveness of national policies for air pollution control has been demonstrated, but the relative effectiveness of short-term emission reduction measures in comparison with national policies has not. Here we show that short-term abatement measures during important international events substantially reduced PM2.5 concentrations, but air quality rebounded to pre-event levels after the measures ceased. Long-term adherence to strict emission reduction policies led to successful decreases of 54% in PM2.5 concentrations in Beijing, and 23% in atmospheric nitrogen deposition in China from 2012 to 2020. Incentivized by "blue skies" type campaigns, economic development and reactive nitrogen pollution are quickly decoupled, showing that a combination of inspiring but aggressive short-term measures and effective but durable long-term policies delivers sustainable air quality improvement. However, increased ammonia concentrations, transboundary pollutant flows, and the complexity to achieving reduction targets under climate change scenarios, underscore the need for the synergistic control of multiple pollutants and inter-regional action.

Ammonia mitigation campaign with smallholder farmers improves air quality while ensuring high cereal production.

Reducing cropland ammonia (NH3) emissions while improving air quality and food supply is a challenge, particularly in China where there are millions of smallholder farmers. We tested the effectiveness of a tailored nitrogen (N) management strategy applied to wheat-maize cropping systems in 'demonstration squares' across Quzhou County in the North China Plain. The N-management techniques included optimal N rates, deep fertilizer placement and application of urease inhibitors, implemented through cooperation between government, researchers, businesses and smallholders. Compared with conventional local smallholder practice, our NH3 mitigation campaign reduced NH3 volatilization from wheat and maize by 49% and 39%, and increased N-use efficiency by 28% and 40% and farmers' profitability by 25% and 19%, respectively, with no detriment to crop yields. County-wide atmospheric NH3 and fine particulate matter (with aerodynamic diameter <2.5 µm) concentrations decreased by 40% and 8%, respectively. County-wide net benefits were estimated at US$7.0 million. Our demonstration-square approach shows that cropland NH3 mitigation and improved air quality and farm profitability can be achieved simultaneously by coordinated actions at the county level.

Numerical study of the amplification effects of cold-front passage on air pollution over the North China Plain.

Cold-front systems provide scavenging mechanisms for air pollution in the North China Plain (NCP), but the transport of pollutants with cold fronts aggravates air quality downstream. The impact of cold fronts on PM2.5 concentrations over the NCP during 8-14 December 2019 was studied using the WRF-Chem model. Results indicate that cold fronts directly influence PM2.5 concentration through regional transport of pollutants and adjustment of meteorological systems, and they indirectly affect air quality by influencing aerosol-radiation interaction. Pollutants affecting downstream areas may be transported to altitudes of ~3 km along the frontal surface, with near-surface PM2.5 concentrations increasing temporarily at up to 15 µg·m-3·h-1 behind the surface frontal line owing to the inversion layer triggered by the oblique frontal surface. The transport process plays an essential role in affecting air pollution levels, more than vertical mixing and chemical reaction processes. Changes in the meteorological system (eastward shift of the high-pressure center) occurring with the passage of cold fronts facilitate the accumulation and transport of pollutants in the NCP, reducing air quality in the western and northern NCP. Cold fronts may also indirectly exacerbate near-surface pollutant diffusion conditions by affecting solar radiation incidence, with a reduction of the 2-m temperature by as much as 1 °C, increasing near-surface (<1 and 0.5 km agl on the pre- and post-frontal sides, respectively) PM2.5 concentrations by up to 40 µg·m-3, while reducing upper-layer concentrations by up to 30 µg·m-3. This study emphasizes the amplification effect of cold fronts on air pollution, with inter-regional cooperation being essential in improving air quality in the NCP region.

Food wanting is mediated by transient activation of dopaminergic signaling in the honey bee brain.

The biological bases of wanting have been characterized in mammals, but whether an equivalent wanting system exists in insects remains unknown. In this study, we focused on honey bees, which perform intensive foraging activities to satisfy colony needs, and sought to determine whether foragers leave the hive driven by specific expectations about reward and whether they recollect these expectations during their waggle dances. We monitored foraging and dance behavior and simultaneously quantified and interfered with biogenic amine signaling in the bee brain. We show that a dopamine-dependent wanting system is activated transiently in the bee brain by increased appetite and individual recollection of profitable food sources, both en route to the goal and during waggle dances. Our results show that insects share with mammals common neural mechanisms for encoding wanting of stimuli with positive hedonic value.

Anthropogenic emission is the main contributor to the rise of atmospheric methane during 1993-2017.

Atmospheric methane (CH4) concentrations have shown a puzzling resumption in growth since 2007 following a period of stabilization from 2000 to 2006. Multiple hypotheses have been proposed to explain the temporal variations in CH4 growth, and attribute the rise of atmospheric CH4 either to increases in emissions from fossil fuel activities, agriculture and natural wetlands, or to a decrease in the atmospheric chemical sink. Here, we use a comprehensive ensemble of CH4 source estimates and isotopic δ13C-CH4 source signature data to show that the resumption of CH4 growth is most likely due to increased anthropogenic emissions. Our emission scenarios that have the fewest biases with respect to isotopic composition suggest that the agriculture, landfill and waste sectors were responsible for 53 ± 13% of the renewed growth over the period 2007-2017 compared to 2000-2006; industrial fossil fuel sources explained an additional 34 ± 24%, and wetland sources contributed the least at 13 ± 9%. The hypothesis that a large increase in emissions from natural wetlands drove the decrease in atmospheric δ13C-CH4 values cannot be reconciled with current process-based wetland CH4 models. This finding suggests the need for increased wetland measurements to better understand the contemporary and future role of wetlands in the rise of atmospheric methane and climate feedback. Our findings highlight the predominant role of anthropogenic activities in driving the growth of atmospheric CH4 concentrations.

Efficient synthesis of esermethole and its analogues.

In this work, a general and flexible synthetic route towards the synthesis of pyrroloindoline alkaloids was developed. This new strategy features with a palladium mediated sequential arylation-allylation of o-bromoanilides and leads to the construction of oxindoles bearing a full carbon quaternary center. The cheap triphenylphosphine was proved to be a highly effective ligand for this one pot transformation. On the basis of this new method, esermethole and its analogues were synthesized.

The underappreciated role of agricultural soil nitrogen oxide emissions in ozone pollution regulation in North China.

Intensive agricultural activities in the North China Plain (NCP) lead to substantial emissions of nitrogen oxides (NOx) from soil, while the role of this source on local severe ozone pollution is unknown. Here we use a mechanistic parameterization of soil NOx emissions combined with two atmospheric chemistry models to investigate the issue. We find that the presence of soil NOx emissions in the NCP significantly reduces the sensitivity of ozone to anthropogenic emissions. The maximum ozone air quality improvements in July 2017, as can be achieved by controlling all domestic anthropogenic emissions of air pollutants, decrease by 30% due to the presence of soil NOx. This effect causes an emission control penalty such that large additional emission reductions are required to achieve ozone regulation targets. As NOx emissions from fuel combustion are being controlled, the soil emission penalty would become increasingly prominent and shall be considered in emission control strategies.

Pharmacokinetic Comparisons of Different Combinations of Yigan Jiangzhi Formula in Rats: Simultaneous Determination of Fourteen Components by UPLC-MS/MS.

A rapid, specific, and sensitive analysis for simultaneous determination of fourteen components (daidzein, fermononetin, apigenin, luteolin, puerarin, ononin, calycosin-7-O-ß-D-glucoside, tanshinol, rosmarinic acid, alkanoic acid, salvianolic acid B, berberine, jatrorrhizin, and palmatine) of Yigan Jiangzhi formula (YGJZF, a clinical experienced formula for damp-heat syndrome) in rat plasma was developed and validated using ultraperformance liquid chromatography coupled with mass spectrometry. Lower limit of quantitation ranged from 0.2-10.0 ng/mL, and the calibration curves showed good linearity over 500 times of measuring range. The validated method was successfully applied to the pharmacokinetics investigation of the fourteen compounds in rat plasma after oral administration of two different doses of YGJZF. Compared with the low-dose group of YGJZF, the high-dose group showed significant increase (P < 0.01 or P < 0.05) in maximum plasma concentration, maximum concentration time, and area under the plasma concentration-time curve and decrease (P < 0.01 or P < 0.05) in clearance of most of the fourteen analytes, which suggested that the bioavailability of these components could be enhanced by increasing dosage. The above results may provide useful information for cognizing the relationship between in vitro and in vivo data of the fourteen bioactive ingredients of YGJZF and further guiding rational clinical drug prescription.

Characteristics of Atmospheric Reactive Nitrogen Deposition in Nyingchi City.

Atmospheric reactive nitrogen (N) deposition has been proven to be an important nutrient input from external environments to forest ecosystems. However, the magnitude of atmospheric N deposition in the Tibetan region of China is not well known. In this study, multi-year (between 2005 and 2016) measurements of dry and wet N deposition were carried out in Nyingchi (NC) city, southeastern Tibet. Bulk deposition was collected by the rain gauge method; dry deposition was calculated by the inferential method, namely, multiplying ambient N concentrations by dry deposition velocity (Vd) of the N species. During the entire period, annual bulk and dry N deposition fluxes averaged 2.19 and 1.85 kg N ha-1 yr-1, respectively. Total N deposition fluxes (the sum of reduced and oxidized N species in dry and bulk deposition) showed an obvious increasing trend, especially for oxidized N species. Both bulk and dry N deposition showed a consistent seasonal pattern, with the highest fluxes in summer and the lowest in winter. Our findings suggest that N deposition to the urban environment in southeast Tibet has recently shifted from ammonium-dominated to nitrate-dominated conditions.

Surface and tropospheric ozone trends in the Southern Hemisphere since 1990: possible linkages to poleward expansion of the Hadley circulation.

Increases in free tropospheric ozone over the past two decades are mainly in the Northern Hemisphere that have been widely documented, while ozone trends in the Southern Hemisphere (SH) remain largely unexplained. Here we first show that in-situ and satellite observations document increases of tropospheric ozone in the SH over 1990-2015. We then use a global chemical transport model to diagnose drivers of these trends. We find that increases of anthropogenic emissions (including methane) are not the most significant contributors. Instead, we explain the trend as due to changes in meteorology, and particularly in transport patterns. We propose a possible linkage of the ozone increases to meridional transport pattern shifts driven by poleward expansion of the SH Hadley circulation (SHHC). The SHHC poleward expansion allows more downward transport of ozone from the stratosphere to the troposphere at higher latitudes, and also enhances tropospheric ozone production through stronger lifting of tropical ozone precursors to the upper troposphere. These together may lead to increasing tropospheric ozone in the extratropical SH, particularly in the middle/upper troposphere and in austral autumn. Poleward expansion of the Hadley circulation is partly driven by greenhouse warming, and the associated increase in tropospheric ozone potentially provides a positive climate feedback amplifying the warming that merits further quantification.

Long-term survival in a patient with pulmonary spindle cell carcinoma treated with traditional Chinese medicine.

Spindle cell carcinoma (SCC) is a rare pulmonary malignancy, accounting for only 0.2%-0.3% of all lung cancers. Therefore, the prognosis and treatment of pulmonary SCC is unclear. There are only 13 reported cases in literature, only three of which had a survival of more than 11 months. Here we reported a long-term survival of a patient with pulmonary SCC who underwent treatment with traditional Chinese medicine. At the most recent follow-up in July 2018, her survival after diagnosis is 48 months and she continues to do well. To our knowledge, this is the longest survival of late stage SCC with the largest tumour burden.

Atmospheric nitrogen deposition in the Yangtze River basin: Spatial pattern and source attribution.

The Yangtze River basin is one of the world's hotspots for nitrogen (N) deposition and likely plays an important role in China's riverine N output. Here we constructed a basin-scale total dissolved inorganic N (DIN) deposition (bulk plus dry) pattern based on published data at 100 observational sites between 2000 and 2014, and assessed the relative contributions of different reactive N (Nr) emission sectors to total DIN deposition using the GEOS-Chem model. Our results show a significant spatial variation in total DIN deposition across the Yangtze River basin (33.2 kg N ha-1 yr-1 on average), with the highest fluxes occurring mainly in the central basin (e.g., Sichuan, Hubei and Hunan provinces, and Chongqing municipality). This indicates that controlling N deposition should build on mitigation strategies according to local conditions, namely, implementation of stricter control of Nr emissions in N deposition hotspots but moderate control in the areas with low N deposition levels. Total DIN deposition in approximately 82% of the basin area exceeded the critical load of N deposition for semi-natural ecosystems along the basin. On the basin scale, the dominant source of DIN deposition is fertilizer use (40%) relative to livestock (11%), industry (13%), power plant (9%), transportation (9%), and others (18%, which is the sum of contributions from human waste, residential activities, soil, lighting and biomass burning), suggesting that reducing NH3 emissions from improper fertilizer (including chemical and organic fertilizer) application should be a priority in curbing N deposition. This, together with distinct spatial variations in emission sector contributions to total DIN deposition also suggest that, in addition to fertilizer, major emission sectors in different regions of the basin should be considered when developing synergistic control measures.

Effects of elevated ozone concentration and nitrogen addition on ammonia stomatal compensation point in a poplar clone.

The stomatal compensation point of ammonia (χs) is a key factor controlling plant-atmosphere NH3 exchange, which is dependent on the nitrogen (N) supply and varies among plant species. However, knowledge gaps remain concerning the effects of elevated atmospheric N deposition and ozone (O3) on χs for forest species, resulting in large uncertainties in the parameterizations of NH3 incorporated into atmospheric chemistry and transport models (CTMs). Here, we present leaf-scale measurements of χs for hybrid poplar clone '546' (Populusdeltoides cv. 55/56 x P. deltoides cv. Imperial) growing in two N treatments (N0, no N added; N50, 50 kg N ha-1 yr-1 urea fertilizer added) and two O3 treatments (CF, charcoal-filtered air; E-O3, non-filtered air plus 40 ppb) for 105 days. Our results showed that χs was significantly reduced by E-O3 (41%) and elevated N (19%). The interaction of N and O3 was significant, and N can mitigate the negative effects of O3 on χs. Elevated O3 significantly reduced the light-saturated photosynthetic rate (Asat) and chlorophyll (Chl) content and significantly increased intercellular CO2 concentrations (Ci), but had no significant effect on stomatal conductance (gs). By contrast, elevated N did not significantly affect all measured photosynthetic parameters. Overall, χs was significantly and positively correlated with Asat, gs and Chl, whereas a significant and negative relationship was observed between χs and Ci. Our results suggest that O3-induced changes in Asat, Ci and Chl may affect χs. Our findings provide a scientific basis for optimizing parameterizations of χs in CTMs in response to environmental change factors (i.e., elevated N deposition and/or O3) in the future.

A new and efficient strategy for the synthesis of podophyllotoxin and its analogues.

[structure: see text]. An efficient and stereoselective strategy for the total synthesis of podophyllotoxin was developed. This route leads to podophyllotoxin 1 in only 12 steps with 29% overall yield. A notable feature of this synthetic strategy is the use of the cascade addition-alkylation to ensure the key C1-C2 stereochemistry that is pivotal for the synthesis of podophyllotoxin.