Evaluation of offline sampling for atmospheric C3-C11 non-methane hydrocarbons.

The concentration variation of C3-C11 non-methane hydrocarbons (NMHCs) collected in several types of commercial flexible bags and adsorption tubes was systematically investigated using a gas chromatography-flame ionization detector (GC-FID) system. The percentage loss of each NMHC in the polyvinyl fluoride (PVF) bags was less than 5% during a 7-hr storage period; significant NMHCs loss was detected in aluminum foil composite film and fluorinated ethylene propylene bags. The thermal desorption efficiency of NMHCs for adsorption tubes filled Carbopack B and Carboxen1000 sorbents was greater than 95% at 300℃, and the loss of NMHCs in the adsorption tubes during 20-days storage at 4℃ was less than 8%. The thermal desorption efficiency for C11 NMHCs in the adsorption tube filled with Carbograph 1 and Carbosieve SⅢ absorbents was less than 40% at 300℃, and pyrolysis of the absorbents at 330℃ interfered significantly with the measurements of some alkenes. The loss of alkenes was significant when NMHCs were sampled by cryo-enrichment at -90℃ in the presence of O3 for the online NMHC measurements, and negligible for enrichment using adsorption tubes at 25℃. Although O3 scrubbers have been widely used to eliminate the influence of O3 on NMHC measurements, the loss of NMHCs with carbon numbers greater than 8 was more than 10%. Therefore, PVF bags and adsorption tubes filled Carbopack B and Carboxen1000 sorbents were recommended for the sampling of atmospheric NMHCs.

Responses of surface O3 and PM2.5 trends to changes of anthropogenic emissions in summer over Beijing during 2014-2019: A study based on multiple linear regression and WRF-Chem.

Owing to the implementation of air pollution control actions, anthropogenic emissions in Beijing have changed in recent years. Understanding the impact of changes in anthropogenic emissions on O3 and PM2.5 trends is helpful for developing air quality management strategies. Herein, we investigated the variations of air pollutants in summer over Beijing using long-term data sets from 2014 to 2019, and explored the responses of O3 and PM2.5 trends to changes in anthropogenic emissions based on multiple linear regression (MLR) analysis and WRF-Chem model. The results indicated a significant decrease in PM2.5, but a near constant level of O3 during 2014-2019. The decrease rate of PM2.5, which was lower than that of SO2, might be due to the effect of NO2 on atmospheric PM2.5. Both the slightly increasing correlations between PM2.5 and NO2 and the WRF-Chem model simulations implied that atmospheric PM2.5 in Beijing is trending to be more sensitive to NOx than SO2. The emissions of NOx and VOCs from industry and transportation were found to make great contribution to O3 production in Beijing. Due to the titration of NOx in VOC-limited regime, the relatively low emission ratios of NOx and VOCs from industry and transportation in Beijing provided convincing evidence for the persistently high O3 concentrations during 2014-2019. However, the noticeable increase of the O3 trends in other areas (e.g., Hebei, Tianjin) could be explained by the significant decline in the emission ratios of NOx and VOCs from anthropogenic emissions especially industry during 2014-2019. Controlling the emission of NOx can substantially reduce PM2.5 pollution, but may aggravate O3 pollution, and thus effective VOC emission control strategies need to be considered for simultaneously controlling O3 and PM2.5 pollution in Beijing and other regions of China.

Abiotic degradation of field wheat straw as a notable source of atmospheric carbonyls in the North China Plain.

Carbonyl compounds (carbonyls) play a crucial role in atmospheric chemistry, but their atmospheric sources are not fully identified. Here we show unexpectedly high carbonyl emissions from extensive field returning wheat straw over the North China Plain (NCP). The emission rates of carbonyls exhibit distinct diurnal variations with the noontime peak value of total carbonyls greater than 135 µg∙kg-1 (dry straw weight) ∙h-1. The carbonyl emission is mainly attributed to biomass abiotic degradation processes that are affected by air temperature and sunlight intensity. Given that the photolysis of carbonyls is the major primary source of ROx radicals in the troposphere, carbonyl emissions would lead to increasing atmospheric oxidants. The mean daytime O3 concentration over the NCP increases by 12.3% when coupling carbonyl emissions from wheat straw with the current emission inventory through the model simulation. It might be one of the important reasons for the occurrence of the most serious O3 pollution in June when winter wheat is intensively harvested in the region. Further studies are warranted to explore the influence of field returning wheat straw on regional air quality.

Ozone and SOA formation potential based on photochemical loss of VOCs during the Beijing summer.

Volatile organic compounds (VOCs) are easily degraded by oxidants during atmospheric transport. Therefore, the contribution of VOCs to ozone (O3) and secondary organic aerosol (SOA) formation at a receptor site is different from that in a source area. In this study, hourly concentrations of VOCs and other pollutants, such as O3, NOx, HONO, CO, and PM2.5, were measured in the suburbs (Daxing district) of Beijing in August 2019. The photochemical initial concentrations (PICs), in which the photochemical losses of VOCs were accounted for, were calculated to evaluate the contribution of the VOCs to O3 and SOA formation. The mean (±standard deviation) measured VOC concentrations and the PICs were 11.2 ± 5.7 and 14.6 ± 8.4 ppbv, respectively, which correspond to O3 formation potentials (OFP) of 57.8 ± 26.3 and 103.9 ± 109.4 ppbv and SOA formation potentials (SOAP) of 8.4 ± 4.1 and 10.3 ± 7.4 µg m-3, respectively. Alkenes contributed 80.5% of the consumed VOCs, followed by aromatics (13.3%) and alkanes (6.2%). The contributions of the alkenes and aromatics to the OFPPICs were 56.8% and 30.3%, respectively; while their corresponding contributions to the SOAPPICs were 1.9% and 97.3%, respectively. The OFPPICs was linearly correlated with the observed O3 concentrations (OFPPICs = 41.5 + 1.40 × cO3, R2 = 0.87). The O3 formation was associated with a VOC-limited regime at the receptor site based on the measured VOCs and changed to a transition regime and a NOx sensitive regime based on the PIC. Our results suggest that more attention should be paid to biogenic VOCs when studying O3 formation in summer in Beijing, while the control of anthropogenic aromatic compounds should be given priority in terms of SOA formation.

[Effect of Long-term Dairy Manure Amendment on N2O and NO Emissions from Summer Maize-Winter Wheat Cropping Systems].

Annual nitrous oxide (N2O) and nitric oxide (NO) emissions were measured within a 27 year fertilization experiment in Guanzhong Plain. Gas samples were collected using static chambers from June 2017 to June 2018. The primary objectives of this study were to quantify the variations in N2O and NO emissions and evaluate the effect of manure amendment on gas losses. Three treatments were set up in the field using a completely random block design. The control treatment (CK) remained unfertilized throughout the year. The synthetic fertilizers (NPK) and NPK plus dairy manure (NPKM) treatments received an annual nitrogen (N) input at a rate of 353 kg·hm-2. In the summer maize season, the NPK and NPKM treatments received urea as a N source at 188 kg·hm-2. In the winter wheat season, the NPK treatments received urea at 165 kg·hm-2. The NPKM treatment received the same amount of N as the NPK treatment but with 30% from urea and 70% from dairy manure. The results showed that N2O and NO emissions from the CK treatment were consistently low during the experimental period. Large emission peaks were captured in the NPK and NPKM treatments, mostly responding to fertilizer application and irrigation. The largest N2O and NO peaks were up to 103.0 g·(hm2·d)-1 and 71.0 g·(hm2·d)-1, respectively, and both occurred in the NPKM treatment during the summer maize season. The NO/N2O ratio was negatively related to soil water-filled pore space (P<0.01) at soil temperatures above 20℃ for the NPK and NPKM treatments, indicating the regulatory effect of soil temperature and water content on gas fluxes. Annual N2O emissions from the CK, NPK, and NPKM treatments were 0.21 kg·hm-2, 2.32 kg·hm-2, and 2.15 kg·hm-2, respectively, with a non-significant difference between the NPK and NPKM treatments (P=0.74). Annual NO emissions from the CK, NPK, and NPKM treatments were 0.23 kg·hm-2, 0.80 kg·hm-2, and 1.46 kg·hm-2, respectively, with a significant difference between the NPK and NPKM treatments (P<0.05). We concluded that long-term dairy manure amendment did not influence N2O emissions but increased NO emissions.