Shengzhen Zhou

Microscopic Observation of Metal-Containing Particles from Chinese Continental Outflow Observed from a Non-Industrial Site

Atmospheric metal-containing particles adversely affect human health because of their physiological toxicity. Mixing state, size, phase, aspect ratio, and sphericity of individual metal-containing particles collected in Hong Kong air in winter are examined through transmission electron microscopy (TEM). Eighteen percent of the sulfate particles have one or more tiny metal inclusions. Size distributions of metal and fly ash particles (or inclusions) with diameters from 15 nm to 2.7 μm show the same peak at 210 nm. The major metal particles were classified as Fe-rich (e.g., hematite), Zn-rich (e.g., zinc sulfate and zinc oxide), Pb-rich (e.g., anglesite), Mn-rich, and As-rich, which were likely emitted from industries and coal-fired power plants at high temperatures in mainland China. Compared to fly ash and S-rich particles, metal particles display a lower sphericity of 0.51 and a higher aspect ratio of 1.47, which means their shapes are poorly defined. The elemental mapping of individual particles reveal that sulfate areas without metal inclusions also contain minor Fe, Mn, or Zn. Therefore, the internal mixing of metals and acidic constituents likely solubilize metals and modify metal inclusion shapes. Solubilization of metals in airborne particles can extend their toxicity into nontoxicity parts in the particles. The structure of the metal-containing particles may provide important information for assessing health effects of fine sulfate and nitrate particles with metal inclusions in urban areas.

High time-resolved elemental components in fine and coarse particles in the Pearl River Delta region of Southern China: Dynamic variations and effects of meteorology.

Hourly-resolved PM2.5 and PM10-2.5 samples were collected in the industrial city Foshan in the Pearl River Delta region, China. The samples were subsequently analyzed for elemental components and black carbon (BC). A key purpose of the study was to understand the composition of particulate matter (PM) at high-time resolution in a polluted urban atmosphere to identify key components contributing to extreme PM concentration events and examine the diurnal chemical concentration patterns for air quality management purposes. It was found that BC and S concentrations dominated in the fine mode, while elements with mostly crustal and oceanic origins such as Si, Ca, Al and Cl were found in the coarse size fraction. Most of the elements showed strong diurnal variations. S did not show clear diurnal variations, suggesting regional rather than local origin. Based on empirical orthogonal functions (EOF) method, 3 forcing factors were identified contributing to the extreme events of PM2.5 and selected elements, i.e., urban direct emissions, wet deposition and a combination of coarse mode sources. Conditional probability functions (CPF) were performed using wind profiles and elemental concentrations. The CPF results showed that BC and elemental Cl, K, Fe, Cu and Zn in the fine mode were mostly from the northwest, indicating that industrial emissions and combustion were the main sources. For elements in the coarse mode, Si, Al, K, Ca, Fe and Ti showed similar patterns, suggesting same sources such as local soil dust/construction activities. Coarse elemental Cl was mostly from the south and southeast, implying the influence of marine aerosol sources. For other trace elements, we found vanadium (V) in fine PM was mainly from the sources located to the southeast of the measuring site. Combined with CPF results of S and V in fine PM, we concluded shipping emissions were likely an important elemental emission source.

Photochemical indicators of ozone sensitivity: application in the Pearl River Delta, China

Surface O3 production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O3-NOx-VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O3 sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NOy, H2O2/ HNO3, O3/NOy, O3/NOz, O3/HNO3, and H2O2/NOz, were evaluated based on the distribution of NOx- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NOx-sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H2O2/HNO3 being the best indicator. The threshold sensitivity levels for HCHO/NOy, H2O2/HNO3, O3/NOy, O3/NOz, O3/HNO3, and H2O2/NOz were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H2O2/HNO3, O3/NOy, O3/NOz, O3/HNO3, and H2O2/NOz were able to identify more than 95% of VOC- and NOx-sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H2O2/HNO3 and H2O2/NOz were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.

Regional to Global Biogenic Isoprene Emission Responses to Changes in Vegetation From 2000 to 2015

Isoprene, a dominant biogenic volatile organic compound that is mainly emitted by trees, has a significant impact on the atmospheric chemistry. Regional to global changes in biogenic isoprene emission associated with vegetation variations between 2000 and 2015 were estimated using the MEGAN model with satellite land cover data for inputs in this study. The satellite data estimates of land cover changes were compared to results from previous investigators that have either conducted regional studies or have used lower resolution land cover data. The analysis indicates that tree coverage increases of >5% occurred in 13% of locations including in central China and Europe. In contrast, a decrease of >5% was observed in about 5% of locations, especially in tropical regions. The trends in global tree coverage from 2000 to 2015 resulted in a global isoprene emission decrease of only 1.5%, but there were significant regional variations. Obvious decreases in tree coverage in some tropical areas (e.g., Amazon Basin, Western Africa, Southeast Asia) resulted in a similar to 10% reduction of regional isoprene emission due to agricultural expansion. Distinct increments of isoprene emission (5-10%) were mainly found in Northeast China and India and were associated with afforestation efforts. Deforestation and afforestation associated with managed plantations does not only affect the total forest coverage but also impacts average isoprene emission capacity, which can result in accelerated isoprene emission variations. Consequently, isoprene variation assessments are needed that not only account for changes in vegetation fractions but also consider the changes in plant species compositions of forests and other landscapes.

Characterization of diurnal variations of PM2.5 acidity using an open thermodynamic system: A case study of Guangzhou, China

Aerosol acidity has significant implications for atmospheric processing, and high time-resolution measurements can provide critical insights into those processes. This paper reports diurnal variations of aerosol acidity characterized using an open thermodynamic system in Guangzhou, China. Hourly measurements of PM2.5-associated ionic species and related parameters were carried out during June-September 2013 followed by application of the Extended Aerosol Inorganic Model in open mode to estimate aerosol pH. The model-estimated aerosol pH was 2.4 ± 0.3, and the pH diurnal profile exhibited peaks in the early morning (6 a.m.) and troughs in the afternoon (2 p.m.) that appeared to be constrained by liquid water content (LWC) and free H+. A linear regression model was developed to predict aerosol pH, which performed strongly with 4 variables during daytime (NH4+, Na+, SO42- and RH; R2 = 0.95) and 3 during nighttime (NH4+, SO42- and RH; R2 = 0.91). The effect of aerosol acidity on the partitioning of HNO3, HCl and NH3 was studied based on theoretical considerations and measurement data. The fractions in particulate phase for acidic compounds correlated strongly with pH (R2 = 0.64-0.69) while that for NH3, interestingly, was weak (R2 = 0.17). Analytical expressions were developed to explain these observations and it was concluded that the partitioning of HCl and HNO3 was more sensitive to pH compared to that of NH3. These results are significant in terms of potential atmospheric depletion rates of HCl and HNO3 in the region and stress the need for future studies in this direction.

Evaluate dry deposition velocity of the nitrogen oxides using Noah-MP physics ensemble simulations for the Dinghushan Forest, Southern China

There has been a rapid growth of reactive nitrogen (Nr) deposition over the world in the past decades. The Pearl River Delta region is one of the areas with high loading of nitrogen deposition. But there are still large uncertainties in the study of dry deposition because of its complex processes of physical chemistry and vegetation physiology. At present, the forest canopy parameterization scheme used in WRF-Chem model is a single-layer “big leaf” model, and the simulation of radiation transmission and energy balance in forest canopy is not detailed and accurate. Noah-MP land surface model (Noah-MP) is based on the Noah land surface model (Noah LSM) and has multiple parametric options to simulate the energy, momentum, and material interactions of the vegetation-soil-atmosphere system. Therefore, to investigate the improvement of the simulation results of WRF-Chem on the nitrogen deposition in forest area after coupled with Noah-MP model and to reduce the influence of meteorological simulation biases on the dry deposition velocity simulation, a dry deposition single-point model coupled by Noah- MP and the WRF-Chem dry deposition module (WDDM) was used to simulate the deposition velocity (Vd). The model was driven by the micro-meteorological observation of the Dinghushan Forest Ecosystem Location Station. And a series of numerical experiments were carried out to identify the key processes influencing the calculation of dry deposition velocity, and the effects of various surface physical and plant physiological processes on dry deposition were discussed. The model captured the observed Vd well, but still underestimated the Vd. The self-defect of Wesely scheme applied by WDDM, and the inaccuracy of built-in parameters in WDDM and input data for Noah-MP (e.g. LAI) were the key factors that cause the underestimation of Vd. Therefore, future work is needed to improve model mechanisms and parameterization.