The Impact of Agroecosystems on Nitrous Acid (HONO) Emissions during Spring and Autumn in the North China Plain.

Solar radiation triggers atmospheric nitrous acid (HONO) photolysis, producing OH radicals, thereby accelerating photochemical reactions, leading to severe secondary pollution formation. Missing daytime sources were detected in the extensive HONO budget studies carried out in the past. In the rural North China Plain, some studies attributed those to soil emissions and more recent studies to dew evaporation. To investigate the contributions of these two processes to HONO temporal variations and unknown production rates in rural areas, HONO and related field observations obtained at the Gucheng Agricultural and Ecological Meteorological Station during spring and autumn were thoroughly analyzed. Morning peaks in HONO frequently occurred simultaneously with those of ammonia (NH3) and water vapor both during spring and autumn, which were mostly caused by dew and guttation water evaporation. In spring, the unknown HONO production rate revealed pronounced afternoon peaks exceeding those in the morning. In autumn, however, the afternoon peak was barely detectable compared to the morning peak. The unknown afternoon HONO production rates were attributed to soil emissions due to their good relationship to soil temperatures, while NH3 soil emissions were not as distinctive as dew emissions. Overall, the relative daytime contribution of dew emissions was higher during autumn, while soil emissions dominated during spring. Nevertheless, dew emission remained the most dominant contributor to morning time HONO emissions in both seasons, thus being responsible for the initiation of daytime OH radical formation and activation of photochemical reactions, while soil emissions further maintained HONO and associated OH radial formation rates at a high level, especially during spring. Future studies need to thoroughly investigate the influencing factors of dew and soil emissions and establish their relationship to HONO emission rates, form reasonable parameterizations for regional and global models, and improve current underestimations in modeled atmospheric oxidation capacity.

Severe photochemical pollution formation associated with strong HONO emissions from dew and guttation evaporation.

The unknown daytime source of HONO has been extensively investigated due to unexplained atmospheric oxidation capacity and current modelling bias, especially during cold seasons. In this study, abrupt morning increases in atmospheric HONO at a rural site in the North China Plain (NCP) were observed almost on daily basis, which were closely linked to simultaneous rises in atmospheric water vapor content and NH3 concentrations. Dew and guttation water formation was frequently observed on wheat leaves, from which water samples were taken and chemically analyzed for the first time. Results confirmed that such natural processes likely governed the daily nighttime deposition and daytime release of HONO and NH3, which have not been considered in the numerous HONO budget studies investigating its large missing daytime source in the NCP. The dissolved HONO and NH3 in leaf surface water droplets reached 1.4 and 23 mg L-1 during the morning on average, resulting in averaged atmospheric HONO and NH3 increases of 0.89 ± 0.61 and 43.7 ± 29.3 ppb during morning hours, with relative increases of 186 ± 212 % and 233 ± 252 %, respectively. The high atmospheric oxidation capacity contained within HONO was stored in near surface liquid water (such as dew, guttation and soil surface water) during nighttime, which prevented its atmospheric dispersion after sunset and protected it from photodissociation during early morning hours. HONO was released in a blast during later hours with stronger solar radiation, which triggered and then accelerated daytime photochemistry through the rapid photolysis of HONO and subsequent OH production, especially under high RH conditions, forming severe secondary gaseous and particulate pollution. Results of this study demonstrate that global ecosystems might play significant roles in atmospheric photochemistry through nighttime dew formation and guttation processes.

First long-term surface ozone variations at an agricultural site in the North China Plain: Evolution under changing meteorology and emissions.

Significant upward trends in surface ozone (O3) have been widely reported in China during recent years, especially during warm seasons in the North China Plain (NCP), exerting adverse environmental effects on human health and agriculture. Quantifying long-term O3 variations and their attributions helps to understand the causes of regional O3 pollution and to formulate according control strategy. In this study, we present long-term trends of O3 in the warm seasons (April-September) during 2006-2019 at an agricultural site in the NCP and investigate the relative contributions of meteorological and anthropogenic factors. Overall, the maximum daily 8-h average (MDA8) O3 exhibited a weak decreasing trend with large interannual variability. < 6 % of the observed trend could be explained by changes in meteorological conditions, while the remaining 94 % was attributed to anthropogenic impacts. However, the interannual variability of warm season MDA8 O3 was driven by both meteorology (36 ± 28 %) and anthropogenic factors (64 ± 27 %). Daily maximum temperature was the most essential factor affecting O3 variations, followed by ultraviolet radiation b (UVB) and boundary layer height (BLH), with rising temperature trends inducing O3 inclines throughout April to August, while UVB mainly influenced O3 during summer months. Under changes in emissions and air quality, warm season O3 production regime gradually shifted from dominantly VOCs-limited during 2006-2015 to NOx-limited afterwards. Relatively steady HCHO and remarkably rising NOx levels resulted in the fast decreasing MDA8 O3 (-2.87 ppb yr-1) during 2006-2012. Rapidly decreasing NOx, flat or slightly increasing HCHO promoted O3 increases during 2012-2015 (9.76 ppb yr-1). While afterwards, slow increases in HCHO and downwards fluctuating NOx led to decreases in MDA8 O3 (-4.97 ppb yr-1). Additionally, continuous warming trends might promote natural emissions of O3 precursors and magnify their impacts on agricultural O3 by inducing high variability, which would require even more anthropogenic reduction to compensate for.

On the fossil and non-fossil fuel sources of carbonaceous aerosol with radiocarbon and AMS-PMF methods during winter hazy days in a rural area of North China plain.

Regional transport is a key source of carbonaceous aerosol in many Chinese megacities including Beijing. The sources of carbonaceous aerosol in urban areas have been studied extensively but are poorly known in upwind rural areas. This work aims to quantify the contributions of fossil and non-fossil fuel emissions to carbonaceous aerosols at a rural site in North China Plain in winter 2016. We integrated online high resolution-time of flight-aerosol mass spectrometer (HR-TOF-AMS) observations and radiocarbon (14C) measurements of fine particles with Positive Matrix Factorization (PMF) analysis as well as Extended Gelencsér (EG) method. We found that fine particle concentration is much higher at the rural site than in Beijing during the campaign (Dec 7, 2016 to Jan 8, 2017). PMF analysis of the AMS data showed that coal-combustion related organic aerosol (CCOA + Oxidized CCOA) and more oxidized oxygenated organic aerosol (MO-OOA) contributed 48% and 30% of organic matter to non-refractory PM1 (NR-PM1) mass. About 2/3 of the OC and EC were from fossil-fuel combustion. The EG method, combining AMS-PMF and 14C data, showed that primary and secondary OC from fossil fuel contribute 35% and 22% to total carbon (TC), coal combustion emission dominates the fossil fuel sources, and biomass burning accounted for 21% of carbonaceous aerosol. In summary, our results confirm that fossil fuel combustion was the dominant source of carbonaceous aerosol during heavy pollution events in the rural areas. Significant emissions of solid fuel carbonaceous aerosols at rural areas can affect air quality in downwind cities such as Beijing and Tianjin, highlighting the benefits of energy transition from solid fuels to cleaner energy in rural areas.

Drivers of the rapid rise and daily-based accumulation in PM1.

Submicron particle matter (PM1) that rapidly reaches exceedingly high levels in several or more hours in the North China Plain (NCP) has been threating~400 million individuals' health for decades. The precise cause of the rapid rise in PM1 remains uncertain. Based on sophisticated measurements in PM1 characterizations and corresponding boundary-layer (BL) meteorology in the NCP, it demonstrates that this rising is mainly driven by BL meteorological variability. Large increases in near-ground inversions and decreases in vertical heat/momentum fluxes during the day-night transition result in a significant reduction in mixing space. The PM1 that is vertically distributed before accumulates at the near-ground and then experiences a rapid rise. Besides meteorological variability, a part of the rise in organics is ascribed to an increase of coal combustion at midnight. The daily-based accumulation of PM1 is attributed to day-to-day vertical meteorological variability, particularly diminishing mixing layer height exacerbated by aerosol-radiation feedback. Resolved by a multiple linear regression model, BL meteorological variability can explain 71% variances of PM1. In contrast, secondary chemical reactions facilitate the daily-based accumulation of PM1 rather than the rapid rise. Our results show that BL meteorological variability plays a dominant role in PM1 rising and day-to-day accumulation, which is crucial for understanding the mechanism of heavy pollution formation.

Explosive morning growth phenomena of NH3 on the North China Plain: Causes and potential impacts on aerosol formation.

Atmospheric ammonia (NH3) as the most important alkaline gas in the atmosphere has attracted much attention in recent years due to its critical role in haze formation, especially on the North China Plain (NCP). Comprehensive studies are needed for investigating diurnal variations of NH3 and underlying mechanisms in different seasons and their potential impacts on atmospheric chemistry. In this study, continuous long-term observation (Mar. 2016 to May 2017) of NH3 at a rural site in the NCP was used to characterize the diurnal variation of NH3 in different seasons and to unveil its causes and potential impacts on atmospheric chemistry. NH3 concentrations displayed rapid increases during the morning, reaching very prominent peaks mostly between 8:00 to 11:00 LT. Such frequent (55%) morning peaks were mainly caused by the evaporation of dew and guttation water droplets. Average dew and guttation water volume concentrations of 750 mL m-2 was estimated for spring, which resulted in approximate NH3 emissions of 800 ng m-2 s- 1. Such high emission fluxes from dew and guttation water evaporation have never been reported before, suggesting dew and guttation droplets to be significant night-time reservoirs and strong morning sources for NH3. In light of recent studies putting forward that NH3 can promote the heterogeneous formation of HONO and nitrate under high humidity conditions, we investigated the differences in HONO and aerosol chemical composition diurnal variations between days with and without NH3 morning spikes during November. HONO, nitrate and sulfate concentrations were significantly higher for days with NH3 morning spikes, with HONO displaying a morning peak near that of NH3. These results demonstrate that the prevailing NH3 morning spikes on the NCP have significant influences on aerosol formation and atmospheric chemistry. NH3 emission mitigation strategies and regulations are urgently needed.

Retrieving the Diurnal FPAR of a Maize Canopy from the Jointing Stage to the Tasseling Stage with Vegetation Indices under Different Water Stresses and Light Conditions.

The fraction of absorbed photosynthetically active radiation (FPAR) is a key variable in the model of vegetation productivity. Vegetation indices (VIs) that were derived from instantaneous remote-sensing data have been successfully used to estimate the FPAR of a day or a longer period. However, it has not yet been verified whether continuous VIs can be used to accurately estimate the diurnal dynamics of a vegetation canopy FPAR, which may fluctuate dramatically within a day. In this study, we measured the high temporal resolution spectral data (480 to 850 nm) and FPAR data of a maize canopy from the jointing stage to the tasseling stage under different irrigation and illumination conditions using two automatic observation systems. To estimate the FPAR, we developed regression models based on a quadratic function using 13 kinds of VIs. The results show the following: (1) Under nondrought conditions, although the illumination condition (sunny or cloudy) influenced the trend of the canopy diurnal FPAR, it had only a slight effect on the model accuracies of the FPAR-VIs. The maximum coefficients of determination (R²) of the FPAR-VIs models generated for the sunny nondrought data, the cloudy nondrought data, and all of the nondrought data were 0.895, 0.88, and 0.828, respectively. The VIs-including normalized difference vegetation index (NDVI), green NDVI (GNDVI), red-edge simple ratio (SR705), modified simple ratio 2 (mSR2), red-edge normalized difference vegetation index (NDVI705), and enhanced vegetation index (EVI)-that were related to the canopy structure had higher estimation accuracies (R² > 0.8) than the other VIs that were related to the soil adjustment, chlorophyll, and physiology. The estimation accuracies of the GNDVI and some red-edge VIs (including NDVI705, SR705, and mSR2) were higher than the estimation accuracy of the NDVI. (2) Under drought stress, the FPAR decreased significantly because of leaf wilting and the effective leaf area index decrease around noon. When we included drought data in the model, accuracies were reduced dramatically and the R² value of the best model was only 0.59. When we built the regression models based only on drought data, the EVI, which can weaken the influence of soil, had the best estimate accuracy (R² = 0.68).

Combined effects of elevated temperature and CO2 enhance threat from low temperature hazard to winter wheat growth in North China.

We examined the growth and yield of winter wheat (Triticum aestivum) in response to the predicted elevated CO2 concentration and temperature to determine the mechanism of the combined impacts in North China Plain. An elevated treatment (CO2: 600 µmol mol-1, temperature: +2.5~3.0 °C, ECTI) and a control treatment (ambient CO2 and temperature, CK) were conducted in open-top chambers from October 2013 to June 2016. Post-winter growth stages of winter wheat largely advanced and shifted to a cooler period of nature season under combined impact of elevated CO2 and temperature during the entire growing season. The mean temperature and accumulated photosynthetic active radiations (PAR) over the post-winter growing period in ECTI decreased by 0.8-1.5 °C and 10-13%, respectively compared with that in CK, negatively impacted winter wheat growth. As a result, winter wheat in ECTI suffered from low temperature hazards during critical period of floret development and anthesis and grain number per ear was reduced by 10-31% in the three years. Although 1000-kernel weight in ECTI increased by 8-9% mainly due to elevated CO2, increasing CO2 concentration from 400 to 600 µmol mol-1 throughout the growth stage was not able to offset the adverse effect of warming on winter wheat growth and yield.

Infrared warming reduced winter wheat yields and some physiological parameters, which were mitigated by irrigation and worsened by delayed sowing.

Winter wheat has a central role in ensuring the food security and welfare of 1.3 billion people in China. Extensive previous studies have concluded that winter wheat yields would decrease with higher temperatures, owing to warming-induced soil drying or shortening of phenophase. Temperature in China is predicted to increase by 1-5°C by 2100, which may greatly impact plant production and cause other negative effects. We performed a manipulative field experiment, creating diverse growth regimes for wheat by infrared radiation (IR) warming day and night, including IR warming only (DW), IR warming + delayed sowing dates (DS), IR warming + increased irrigation (IW), and a control (CK). The results show that IR warming increased daily average wheat canopy and soil temperatures by 2.0°C and 2.3°C, respectively. DW was associated with an advanced maturity of 10 days and yield reduction of 8.2%. IR-warming effects on the photosynthetic apparatus of wheat varied with season as well as significant differences were found in the booting stage. DS represented a worsened situation, lowering yield per plant by 16.4%, with a significant decline in aboveground biomass and functional leaf area. Wheat under DS showed double-peak patterns of diurnal gas exchange during booting stages and, consequently, lower photosynthetic capacity with high transpiration for cooling. Significantly lower actual water use efficiency and intrinsic water use efficiency from jointing to anthesis stages were also found under DS. However, IW had no significant difference from CK, irrespective of yield and photosynthesis. Therefore, we concluded that delayed sowing date may not be a good choice for winter wheat, whereas a thoroughly-watered wheat agroecosystem should be promoted in the context of global warming.