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Seasonal prediction of winter haze days in the north central North China Plain

Recently, the winter (December–February) haze pollution over the north central North China Plain (NCP) has become severe. By treating the year-to-year increment as the predictand, two new statistical schemes were established using the multiple linear regression (MLR) and the generalized additive model (GAM). By analyzing the associated increment of atmospheric circulation, seven leading predictors were selected to predict the upcoming winter haze days over the NCP (WHDNCP). After cross validation, the root mean square error and explained variance of the MLR (GAM) prediction model was 3.39 (3.38) and 53 % (54 %), respectively. For the final predicted WHDNCP, both of these models could capture the interannual and interdecadal trends and the extremums successfully. Independent prediction tests for 2014 and 2015 also confirmed the good predictive skill of the new schemes. The predicted bias of the MLR (GAM) prediction model in 2014 and 2015 was 0.09 (−0.07) and −3.33 (−1.01), respectively. Compared to the MLR model, the GAM model had a higher predictive skill in reproducing the rapid and continuous increase of WHDNCP after 2010.
Derivation of the reduced reaction mechanisms of ozone depletion events in the Arctic spring by using concentration sensitivity analysis and principal component analysis

The ozone depletion events (ODEs) in the springtime Arctic have been investigated since the 1980s. It is found that the depletion of ozone is highly associated with an auto-catalytic reaction cycle, which involves mostly the bromine-containing compounds. Moreover, bromide stored in various substrates in the Arctic such as the underlying surface covered by ice and snow can be also activated by the absorbed HOBr. Subsequently, this leads to an explosive increase of the bromine amount in the troposphere, which is called the “bromine explosion mechanism”. In the present study, a reaction scheme representing the chemistry of ozone depletion and halogen release is processed with two different mechanism reduction approaches, namely, the concentration sensitivity analysis and the principal component analysis. In the concentration sensitivity analysis, the interdependence of the mixing ratios of ozone and principal bromine species on the rate of each reaction in the ODE mechanism is identified. Furthermore, the most influential reactions in different time periods of ODEs are also revealed. By removing 11 reactions with the maximum absolute values of sensitivities lower than 10 %, a reduced reaction mechanism of ODEs is derived. The onsets of each time period of ODEs in simulations using the original reaction mechanism and the reduced reaction mechanism are identical while the maximum deviation of the mixing ratio of principal bromine species between different mechanisms is found to be less than 1 %. By performing the principal component analysis on an array of the sensitivity matrices, the dependence of a particular species concentration on a combination of the reaction rates in the mechanism is revealed. Redundant reactions are indicated by principal components corresponding to small eigenvalues and insignificant elements in principal components with large eigenvalues. Through this investigation, aside from the 11 reactions identified as unimportant in the concentration sensitivity analysis, additionally nine reactions were indicated to contribute only little to the total response of the system. Thus, they can be eliminated from the original reaction scheme. The results computed by applying the reduced reaction mechanism derived after the principal component analysis agree well with those by using the original reaction scheme. The maximum deviation of the mixing ratio of principal bromine species is found to be less than 10 %, which is guaranteed by the selection criterion adopted in the simplification process. Moreover, it is shown in the principal component analysis that O(1D) in the mechanism of ODEs is in quasi-steady state, which enables a following simplification of the reduced reaction mechanism obtained in the present study.
Impacts of heterogeneous uptake of dinitrogen pentoxide and chlorine activation on ozone and reactive nitrogen partitioning: improvement and application of the WRF-Chem model in southern China

The uptake of dinitrogen pentoxide (N2O5) on aerosol surfaces and the subsequent production of nitryl chloride (ClNO2) can have a significant impact on the oxidising capability and thus on secondary pollutants such as ozone. The range of such an impact, however, has not been well quantified in different geographical regions. In this study, we applied the Weather Research and Forecasting coupled with Chemistry (WRF-Chem) model to investigate the impact of the N2O5 uptake processes in the Hong Kong–Pearl River Delta (HK–PRD) region, where the highest ever reported N2O5 and ClNO2 concentrations were observed in our recent field study. We first incorporated into the WRF-Chem an aerosol thermodynamics model (ISORROPIA II), recent parameterisations for N2O5 heterogeneous uptake and ClNO2 production and gas-phase chlorine chemistry. The revised model was then used to simulate the spatiotemporal distribution of N2O5 and ClNO2 over the HK–PRD region and the impact of N2O5 uptake and Cl activation on ozone and reactive nitrogen in the planetary boundary layer (PBL). The updated model can generally capture the temporal variation of N2O5 and ClNO2 observed at a mountaintop site in Hong Kong, but it overestimates N2O5 uptake and ClNO2 production. The model results suggest that under average conditions, elevated levels of ClNO2 (> 0.25 ppb within the PBL) are present in the south-western PRD, with the highest values (> 1.00 ppb) predicted near the ground surface (0–200 m above ground level; a.g.l.). In contrast, during the night when very high levels of ClNO2 and N2O5 were measured in well-processed plumes from the PRD, ClNO2 is mostly concentrated within the residual layer ( ∼  300 m a.g.l.). The addition of N2O5 heterogeneous uptake and Cl activation reduces the NO and NO2 levels by as much as 1.93 ppb ( ∼  7.4 %) and 4.73 ppb ( ∼  16.2 %), respectively, and it increases the total nitrate and ozone concentrations by up to 13.45 µg m−3 ( ∼  57.4 %) and 7.23 ppb ( ∼  16.3 %), respectively, in the PBL. Sensitivity tests show that the simulated chloride and ClNO2 concentrations are highly sensitive to chlorine emission. Our study suggests the need to measure the vertical profiles of N2O5 ∕ ClNO2 under various meteorological conditions, to consider the chemistry of N2O5 ∕ ClNO2 in the chemical transport model and to develop an updated chlorine emission inventory over China.
A top-down approach of surface carbonyl sulfide exchange by a Mediterranean oak forest ecosystem in southern France

The role that soil, foliage, and atmospheric dynamics have on surface carbonyl sulfide (OCS) exchange in a Mediterranean forest ecosystem in southern France (the Oak Observatory at the Observatoire de Haute Provence, O3HP) was investigated in June of 2012 and 2013 with essentially a top-down approach. Atmospheric data suggest that the site is appropriate for estimating gross primary production (GPP) directly from eddy covariance measurements of OCS fluxes, but it is less adequate for scaling net ecosystem exchange (NEE) to GPP from observations of vertical gradients of OCS relative to CO2 during the daytime. Firstly, OCS and carbon dioxide (CO2) diurnal variations and vertical gradients show no net exchange of OCS at night when the carbon fluxes are dominated by ecosystem respiration. This contrasts with other oak woodland ecosystems of a Mediterranean climate, where nocturnal uptake of OCS by soil and/or vegetation has been observed. Since temperature, water, and organic carbon content of soil at the O3HP should favor the uptake of OCS, the lack of nocturnal net uptake would indicate that its gross consumption in soil is compensated for by emission processes that remain to be characterized. Secondly, the uptake of OCS during the photosynthetic period was characterized in two different ways. We measured ozone (O3) deposition velocities and estimated the partitioning of O3 deposition between stomatal and non-stomatal pathways before the start of a joint survey of OCS and O3 surface concentrations. We observed an increasing trend in the relative importance of the stomatal pathway during the morning hours and synchronous steep drops of mixing ratios of OCS (amplitude in the range of 60–100 ppt) and O3 (amplitude in the range of 15–30 ppb) after sunrise and before the break up of the nocturnal boundary layer. The uptake of OCS by plants was also characterized from vertical profiles. However, the time window for calculation of the ecosystem relative uptake (ERU) of OCS, which is a useful tool for partitioning measured NEE, was limited in June 2012 to a few hours after midday. This was due to the disruption of the vertical distribution of OCS by entrainment of OCS rich tropospheric air in the morning and because the vertical gradient of CO2 reverses when it is still light. Moreover, polluted air masses (up to 700 ppt of OCS) produced dramatic variation in atmospheric OCS ∕ CO2 ratios during the daytime in June 2013, further reducing the time window for ERU calculation.
Revisiting the steering principal of tropical cyclone motion in a numerical experiment

The steering principle of tropical cyclone motion has been applied to tropical cyclone forecasting and research for nearly 100 years. Two fundamental questions remain unanswered. One is why the steering flow plays a dominant role in tropical cyclone motion, and the other is when tropical cyclone motion deviates considerably from the steering. A high-resolution numerical experiment was conducted with the tropical cyclone in a typical large-scale monsoon trough over the western North Pacific. The simulated tropical cyclone experiences two eyewall replacement processes. Based on the potential vorticity tendency (PVT) diagnostics, this study demonstrates that the conventional steering, which is calculated over a certain radius from the tropical cyclone center in the horizontal and a deep pressure layer in the vertical, plays a dominant role in tropical cyclone motion since the contributions from other processes are largely cancelled out due to the coherent structure of tropical cyclone circulation. Resulting from the asymmetric dynamics of the tropical cyclone inner core, the trochoidal motion around the mean tropical cyclone track cannot be accounted for by the conventional steering. The instantaneous tropical cyclone motion can considerably deviate from the conventional steering that approximately accounts for the combined effect of the contribution of the advection of the symmetric potential vorticity component by the asymmetric flow and the contribution from the advection of the wave-number-one potential vorticity component by the symmetric flow.
Significant concentrations of nitryl chloride sustained in the morning: investigations of the causes and impacts on ozone production in a polluted region of northern China

Nitryl chloride (ClNO2) is a dominant source of chlorine radical in polluted environment, and can significantly affect the atmospheric oxidative chemistry. However, the abundance of ClNO2 and its exact role are not fully understood under different environmental conditions. During the summer of 2014, we deployed a chemical ionization mass spectrometer to measure ClNO2 and dinitrogen pentoxide (N2O5) at a rural site in the polluted North China Plain. Elevated mixing ratios of ClNO2 (> 350 pptv) were observed at most of the nights with low levels of N2O5 (< 200 pptv). The highest ClNO2 mixing ratio of 2070 pptv (1 min average) was observed in a plume from a megacity (Tianjin), and was characterized with a faster N2O5 heterogeneous loss rate and ClNO2 production rate compared to average conditions. The abundant ClNO2 concentration kept increasing even after sunrise, and reached a peak 4 h later. Such highly sustained ClNO2 peaks after sunrise are discrepant from the previously observed typical diurnal pattern. Meteorological and chemical analysis shows that the sustained ClNO2 morning peaks are caused by significant ClNO2 production in the residual layer at night followed by downward mixing after breakup of the nocturnal inversion layer in the morning. We estimated that ∼  1.7–4.0 ppbv of ClNO2 would exist in the residual layer in order to maintain the observed morning ClNO2 peaks at the surface site. Observation-based box model analysis show that photolysis of ClNO2 produced chlorine radical with a rate up to 1.12 ppbv h−1, accounting for 10–30 % of primary ROx production in the morning hours. The perturbation in total radical production leads to an increase of integrated daytime net ozone production by 3 % (4.3 ppbv) on average, and with a larger increase of 13 % (11 ppbv) in megacity outflow that was characterized with higher ClNO2 and a relatively lower oxygenated hydrocarbon (OVOC) to non-methane hydrocarbon (NMHC) ratio.
Wintertime organic and inorganic aerosols in Lanzhou, China: sources, processes, and comparison with the results during summer

Lanzhou, which is located in a steep alpine valley in western China, is one of the most polluted cities in China during the wintertime. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a seven-wavelength aethalometer, and a scanning mobility particle sizer (SMPS) were deployed during 10 January to 4 February 2014 to study the mass concentrations, chemical processes, and sources of submicrometer particulate matter (PM1). The average PM1 concentration during this study was 57.3 µg m−3 (ranging from 2.1 to 229.7 µg m−3 for hourly averages), with organic aerosol (OA) accounting for 51.2 %, followed by nitrate (16.5 %), sulfate (12.5 %), ammonium (10.3 %), black carbon (BC, 6.4 %), and chloride (3.0 %). The mass concentration of PM1 during winter was more than twice the average value observed at the same site in summer 2012 (24.5 µg m−3), but the mass fraction of OA was similar in the two seasons. Nitrate contributed a significantly higher fraction to the PM1 mass in winter than summer (16.5 % vs. 10 %), largely due to more favored partitioning to the particle phase at low air temperature. The mass fractions of both OA and nitrate increased by ∼  5 % (47 to 52 for OA and 13 to 18 % for nitrate) with the increase of the total PM1 mass loading, while the average sulfate fraction decreased by 6 % (17 to 11 %), indicating the importance of OA and nitrate for the heavy air pollution events in Lanzhou. The size distributions of OA, nitrate, sulfate, ammonium, and chloride all peaked at ∼  500 nm, with OA being slightly broader, suggesting that aerosol particles were internally mixed during winter, likely due to frequently calm and stagnant air conditions during wintertime in Lanzhou (average wind speed: 0.82 m s−1). The average mass spectrum of OA showed a medium oxidation degree (average O ∕ C ratio of 0.28), which was lower than that during summer 2012 (O ∕ C  =  0.33). This is consistent with weaker photochemical processing during winter. Positive matrix factorization (PMF) with the multi-linear engine (ME-2) solver identified six OA sources, i.e., a hydrocarbon-like OA (HOA), a biomass burning OA (BBOA), a cooking-emitted OA (COA), a coal combustion OA (CCOA), and two oxygenated OA (OOA) factors. One of the OOAs was less oxidized (LO-OOA), and the other one more oxidized (MO-OOA). LO-OOA was the most abundant OA component (22.3 % of OA mass), followed by CCOA (22.0 %), COA (20.2 %), MO-OOA (14.9 %), BBOA (10.8 %), and HOA (9.8 %). The mass fraction of primary OA ( =  HOA + BBOA + COA + CCOA) increased during high PM pollution periods, indicating that local primary emissions were a main reason for the formation of air pollution events in Lanzhou during winter. Radiocarbon (14C) measurement was conducted on four PM2.5 filter samples from this study, which allowed for a quantitative source apportionment of organic carbon (OC). The non-fossil sources on average accounted for 55 ± 3 % of OC, which could be mainly from biomass burning and cooking activities, suggesting the importance of non-fossil sources for the PM pollution in Lanzhou. Together with the PMF results, we also found that a large fraction (66 ± 10 %) of the secondary OC was from non-fossil OC.
Gridded uncertainty in fossil fuel carbon dioxide emission maps, a CDIAC example

Due to a current lack of physical measurements at appropriate spatial and temporal scales, all current global maps and distributions of fossil fuel carbon dioxide (FFCO2) emissions use one or more proxies to distribute those emissions. These proxies and distribution schemes introduce additional uncertainty into these maps. This paper examines the uncertainty associated with the magnitude of gridded FFCO2 emissions. This uncertainty is gridded at the same spatial and temporal scales as the mass magnitude maps. This gridded uncertainty includes uncertainty contributions from the spatial, temporal, proxy, and magnitude components used to create the magnitude map of FFCO2 emissions. Throughout this process, when assumptions had to be made or expert judgment employed, the general tendency in most cases was toward overestimating or increasing the magnitude of uncertainty. The results of the uncertainty analysis reveal a range of 4–190 %, with an average of 120 % (2σ) for populated and FFCO2-emitting grid spaces over annual timescales. This paper also describes a methodological change specific to the creation of the Carbon Dioxide Information Analysis Center (CDIAC) FFCO2 emission maps: the change from a temporally fixed population proxy to a temporally varying population proxy.
The impact of historical land use change from 1850 to 2000 on secondary particulate matter and ozone

Anthropogenic land use change (LUC) since preindustrial (1850) has altered the vegetation distribution and density around the world. We use a global model (GEOS-Chem) to assess the attendant changes in surface air quality and the direct radiative forcing (DRF). We focus our analysis on secondary particulate matter and tropospheric ozone formation. The general trend of expansion of managed ecosystems (croplands and pasturelands) at the expense of natural ecosystems has led to an 11 % decline in global mean biogenic volatile organic compound emissions. Concomitant growth in agricultural activity has more than doubled ammonia emissions and increased emissions of nitrogen oxides from soils by more than 50 %. Conversion to croplands has also led to a widespread increase in ozone dry deposition velocity. Together these changes in biosphere–atmosphere exchange have led to a 14 % global mean increase in biogenic secondary organic aerosol (BSOA) surface concentrations, a doubling of surface aerosol nitrate concentrations, and local changes in surface ozone of up to 8.5 ppb. We assess a global mean LUC-DRF of +0.017, −0.071, and −0.01 W m−2 for BSOA, nitrate, and tropospheric ozone, respectively. We conclude that the DRF and the perturbations in surface air quality associated with LUC (and the associated changes in agricultural emissions) are substantial and should be considered alongside changes in anthropogenic emissions and climate feedbacks in chemistry–climate studies.
Changes in regional meteorology induced by anthropogenic heat and their impacts on air quality in South China

Anthropogenic heat (AH) emissions from human activities can change the urban circulation and thereby affect the air pollution in and around cities. Based on statistic data, the spatial distribution of AH flux in South China is estimated. With the aid of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem), in which the AH parameterization is developed to incorporate the gridded AH emissions with temporal variation, simulations for January and July in 2014 are performed over South China. By analyzing the differences between the simulations with and without adding AH, the impact of AH on regional meteorology and air quality is quantified. The results show that the regional annual mean AH fluxes over South China are only 0.87 W m−2, but the values for the urban areas of the Pearl River Delta (PRD) region can be close to 60 W m−2. These AH emissions can significantly change the urban heat island and urban-breeze circulations in big cities. In the PRD city cluster, 2 m air temperature rises by 1.1° in January and over 0.5° in July, the planetary boundary layer height (PBLH) increases by 120 m in January and 90 m in July, 10 m wind speed is intensified to over 0.35 m s−1 in January and 0.3 m s−1 in July, and accumulative precipitation is enhanced by 20–40 % in July. These changes in meteorological conditions can significantly impact the spatial and vertical distributions of air pollutants. Due to the increases in PBLH, surface wind speed and upward vertical movement, the concentrations of primary air pollutants decrease near the surface and increase in the upper levels. But the vertical changes in O3 concentrations show the different patterns in different seasons. The surface O3 concentrations in big cities increase with maximum values of over 2.5 ppb in January, while O3 is reduced at the lower layers and increases at the upper layers above some megacities in July. This phenomenon can be attributed to the fact that chemical effects can play a significant role in O3 changes over South China in winter, while the vertical movement can be the dominant effect in some big cities in summer. Adding the gridded AH emissions can better describe the heterogeneous impacts of AH on regional meteorology and air quality, suggesting that more studies on AH should be carried out in climate and air quality assessments.