Measurement of aerosol number size distributions in the Yangtze River delta in China: Formation and growth of particles under polluted conditions

Particle size distribution is important for understanding the sources and effects of atmospheric aerosols. In this paper we present particle number size distributions (10 nm–10 μm) measured at a suburban site in the fast developing Yangtze River Delta (YRD) region (near Shanghai) in summer 2005. The average number concentrations of ultrafine (10–100 nm) particles were 2–3 times higher than those reported in the urban areas of North America and Europe. The number fraction of the ultrafine particles to total particle count was also 20–30% higher. The sharp increases in ultrafine particle number concentrations were frequently observed in late morning, and the particle bursts on 5 of the 12 nucleation event days can be attributed to the homogeneous nucleation leading to new particle formation. The new particle formation events were characterized with a larger number of nucleation-mode particles, larger particle surface area, and larger condensational sink than usually reported in the literature. These suggest an intense production of sulfuric acid from photo-oxidation of sulfur dioxide in the YRD. Overall, the growth rate of newly formed particles was moderate (6.4 ± 1.6 nm h^?1), which was comparable to that reported in the literature.     

成都市道路细颗粒物污染特征

2013年9月20—28日,通过采集成都市城区道路大气环境中的PM2.5样品,分析测定了其中可溶性无机离子、碳组分和金属元素含量。结果表明,PM2.5中Fe、Mn、Ti、Si、Al等主要来源于机动车行驶产生的道路扬尘,Pb、Cu、Ni和Zn等主要来源于机动车尾气及零部件磨损;PM2.5中水溶性无机离子占道路大气环境细颗粒物的33.7%,A/C比值为0.95,表明细颗粒物偏弱碱性;机动车尾气排放的OC1、OC2、OC4和EC1等4种碳组分占道路大气环境细颗粒物碳组分的65.8%,且OC/EC比值为2.9,有二次有机碳(SOC)产生。     

凤眼莲在城市重污染河道修复中的应用

外港河是秦淮河重要支流,长期以来遭受严重污染。2006年4月份起对外港河进行了综合生态治理。在前期清淤和截污的基础上,7月份开始引种凤眼莲。在上游排污口附近和外港河河口段分别设置的4个生态区以及河面上布设的水面载体内全面放养以凤眼莲为主的浮水植物。经过5个多月的初步治理,外港河水体透明度从40 cm以下提高到120 cm左右,COD下降了70.4％,TSS、TN和NH₃-N分别下降了39.6％、49.7％和21.8％。结果证明,凤眼莲在净化严重污染的河道方面起到了良好的效果,引种凤眼莲治理城市重污染河道是切实可行的;此外,用PVC管设计制作的水面载体来放养浮水植物可以点缀水面环境,美化城市河道景观。     

Use of atmospheric elemental size distributions in estimating aerosol sources in the Helsinki area

In June 1996–June 1997 Berner impactors were used in the Helsinki area to measure size distributions of atmospheric aerosols simultaneously at an urban and at a rural site. Ten sample pairs were collected in the size range of 0.03–15.7 μm of equivalent aerodynamic diameter (EAD). Average size distributions at the two sites were calculated for 29 elements, particulate mass, and sulphate. At both sites especially sulphate, As, B, Bi, Cd, Ni, Tl, and V were enriched in fine particles (EAD<2.3 μm). In order to estimate local fine-particle sources of the various chemical components, the similarities and dissimilarities in the accumulation-mode parameters were studied separately for both sites. It was observed that often in different samples, different components had similar accumulation modes. At both sites, particulate mass, As, and Pb had similar accumulation modes to sulphate which suggests that long-range transport (LRT) is important for these components. V, Ni, Mo, and Co formed another group of similar accumulation modes at both sites suggesting that these elements largely originated from local and regional oil combustion. In addition, other groups of similar accumulation modes were observed but these groups were different between the sites. The meteorological parameters indicated that seven sample pairs formed a subset of the data in which the local emissions of the Helsinki area were transported to the urban site but not to the rural site. For this subset the rural fine-particle concentrations were considered to represent an upper limit estimate for the LRT. These upper limit LRT estimations were further improved by utilising the quantitative relative size distributions (QRSD) method at the rural site. The QRSD method supposes that in the fine-particle size range the LRT fractions of all chemical components have a similar shape in their size distributions. Fine-particle sulphate is typically long-range transported, and was therefore selected as the model component that represents the shape of LRT material. Sulphate size distribution was then scaled to give an estimation of the LRT contribution of each component at the rural site. These rural “sulphate scaled” LRT estimates were subtracted from the corresponding urban concentrations to give the local contributions (ng/m³) downwind of the Helsinki area. In particles with EAD below 2.3 μm, the highest absolute and relative downwind local contributions were observed for several common sea-salt and road-dust components. Also the combustion-related elements Ni and V showed fairly high downwind local contributions. Because of the limited number of samples, the local and LRT contributions were not estimated for different wind directions.     

曝气和pH对城市污染河道底泥氮形态的影响

以城市重污染河道表层沉积物为研究对象,采用模拟实验方法,探讨了不同曝气方式(水曝气和泥曝气)、上覆水初始pH(自然状态pH=7和pH=11)对城市污染河道底泥氮形态的影响。结果表明:采用水曝气+pH11方式对城市重污染河道上覆水、间隙水中总氮去除率分别为70.03%和44.66%;泥曝气+pH7方式对上覆水、间隙水、底泥中氨氮去除率分别为94.31%、84.07%和68.29%;底泥pH与上覆水总氮浓度呈正相关(p<0.05);泥曝气+pH11方式使底泥含水率、烧失率明显升高,继而影响各形态氮在泥水系统中的赋存,其中底泥吸附态氨氮含量与底泥含水率呈显著负相关(p<0.01),间隙水可溶态氨氮浓度与底泥烧失率显著正相关(p<0.01)。     

Coarse atmospheric aerosol: size distributions of trace elements

A sampler, employing nine single stage impactors placed in parallel within a portable wind tunnel, has been used to determine the metal content of coarse atmospheric aerosol. The wind tunnel maintains a constant flow environment for the collectors housed inside it, so that representative sampling conditions are achieved compared to the varied ambient wind conditions. At a flow rate of 8 m s⁻¹ the 50% cut-off diameters of the impactors ranged from 7.8 to 38.8 μm. Measurements were conducted at a rural and urban site near Colchester in south east England. The samplers were analysed by PIXE for P, K, Ca, Fe, Ti, Mn, Cu, V, Co, Cr, Br, Zn, Ni, Sc and Pb. It is found that the sampler can be employed to quantitatively characterise the elemental mass size distribution for aerosol larger than 10 μm. The results indicate that a small fraction of the above earth and trace elements’ metal mass is present in particles greater than 10 μm. This fraction for earth metals (Ca, K, Ti) is comparatively greater in the rural site than the urban site, while for trace metals (Mn, V, Cu, Cr) this fraction constitutes a more significant part of the coarse mass at the urban site. Trace element concentrations were of a similar order of magnitude to earlier literature reports. Although the number of measurements was limited it can be concluded that the size distributions obtained were characteristic of an unpolluted area.     

Size distributions and formation of dicarboxylic acids in atmospheric particles

The PM2.5 concentrations and the size distributions of dicarboxylic acids in Hong Kong were studied. Eleven sets of daily PM2.5 samples were obtained at a downtown sampling site during the period of 5–16 December 2000 using an R&P speciation PM2.5 sampler. About 6–12% of the total oxalic acid was found in the gas phase in some samples. A good correlation between succinate and sulfate (R²=0.88) and a moderate correlation between oxalate and sulfate (R²=0.74) were found. Sampling artifacts of oxalate, malonate and succinate were found to be negligible. A total of 18 sets of 48–96 h size distribution data on dicarboxylic acids, sulfate, nitrate and sodium at an urban site and a rural site from June 2000 to May 2001 were obtained using a Micro-Orifice Uniform Deposit Impactor. Data from both sites show similar size distribution characteristics of the dicarboxylic acids. The condensation mode of oxalate was usually observed at 0.177–0.32 μm. The location of the peak of the droplet mode of oxalate was associated with that of sulfate. When the peak of sulfate in the droplet mode appeared at 0.32–0.54 μm, the peak of oxalate sometimes appeared at 0.32–0.54 μm and sometimes shifted to 0.54–1.0 μm. When the peak of sulfate in the droplet mode appeared at 0.54–1.0 μm, the peak of oxalate sometimes appeared at 0.54–1.0 μm and sometimes shifted to 1.0–1.8 μm. Oxalate, succinate and sulfate found in the droplet mode were attributed to in-cloud formation. The slight shift of the oxalate peak from 0.32–0.54 to 0.54–1.0 μm or from 0.54–1.0 to 1.0–1.8 μm was ascribed to minor oxalate evaporation after in-cloud formation. The maximum peak of malonate sometimes appeared in the droplet mode and sometimes appeared at 3.1–6.2 μm. The formation of malonate is associated to the reactions between sea salt and malonic acid.     

Particle size distributions of polycyclic aromatic hydrocarbons in rural and urban atmosphere of Tianjin, China

The size distributions of 16 polycyclic aromatic hydrocarbons (PAHs) and particle mass less than 10 microm in aerodynamic diameter (Dp) were measured using a nine-stage low-volume cascade impactor at rural and urban sites in Tianjin, China in the winter of 2003-2004. The particles exhibited the trimodal distribution with the major peaks occurring at 0.43-2.1 and 9.0-10.0 microm for both urban and rural sites. The concentrations of the total PAH (sum of 16 PAH compound) at rural site were generally less than those of urban site. Mean fraction of 76.5% and 63.9% of the total PAH were associated with particles of 0.43-2.1 microm at rural and urban sites, respectively. Precipitation, temperature, wind speed and direction were the important meteorological factors influencing the concentration of PAHs in rural and urban sites. The distributions of PAHs concentration with respect to particle size were similar for rural and urban samples. The PAHs concentrations at the height of 40 m were higher than both of 20 and 60 m at urban site, but the mass median diameter (MMD) of total PAH increased with the increasing height. The mid-high molecular weight (278 >or= MW >or= 202) PAHs were mainly associated with fine particles (Dp or=MW >or=178) PAHs were distributed in both of fine and coarse particle. The fraction of PAHs associated with coarse particles (Dp>2.1 microm) decreased with increasing molecular weight. The relatively consistent distribution of PAHs seemed to indicate the similar combustion source of PAHs at both of rural and urban sites. The fine differences of concentration and distribution of PAHs at different levels at urban site suggested that the different source and transportation path of particulate PAHs.     

On the nature of nitrate particles in a coastal urban area

Application of micro spot and electron microscopy techniques to individual particles in a coastal urban site revealed the following:

• 1.(a) sulfate particles, some of them mixed, dominated the sub-μm (0.3–0.8 μm) size range;
• 2.(b) nitrates were found mostly in the μm size range, in the form of NaNO₃.

The latter was verified by X-ray analysis of individual nitrates. Apparently the NaNO₃ particles were formed through heterogeneous reaction of gaseous HNO₃ with sea salt particles.     

淮南矿区道路环境大气颗粒物重金属污染特征及来源解析

为了解煤矿开采区道路环境中大气颗粒物重金属元素的污染特征及来源,于2016年12月(采暖期)和2017年5月(非采暖期)分别采集了淮南潘集矿区交通主干线周围大气颗粒物样品,采用电感耦合等离子体质谱(ICP-MS)测定了As、Cd、Hg、Mn、Pb、Cu、Zn、Ni、V等9种重金属元素以及参比元素Al的含量,并利用富集因子法和因子分析法解析了其来源。结果表明:(1)Zn、Mn、Pb含量较高,占所测重金属元素的82%(质量分数)以上;采暖期总悬浮颗粒物(TSP)、PM10和PM2.5中重金属含量总体上均高于非采暖期。(2)富集程度较高的元素有Pb、Cd、Hg,随着颗粒物粒径减小,各重金属元素的富集因子呈现增大趋势。(3)通过因子分析法得出,潘集矿区道路环境中重金属主要来源为交通排放、煤炭燃烧和扬尘等。     

Particle size and time of the day influences on the morphology distributions of atmospheric fine particles at the Baltimore supersite

The morphology of size-classified ambient particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5) was studied in samples collected at the USEPA supersite located in Baltimore, MD. Size classification was accomplished through the use of a low pressure impactor to produce samples with cut-off diameters of 0.10, 0.15, 0.55, and 2.0 μm. Sampling was conducted in two campaigns during the fall of 2002, with separate sampling occurring during early morning, mid-day, late afternoon, and evening periods. Particles with cut-off diameters of 2 μm were generally round in shape, with a border fractal dimension close to 1 based on the analysis of transmission electron microscope (TEM) images of collected samples. Particles with a cut-off diameter of 0.15 μm had on average higher fractal dimensions than the other size classes considered, regardless of time of day associated with the sample. As expected, the time of the day influenced the shape of particle populations sampled. Particles collected during early morning were found to have higher fractal dimension than those collected at other sampling times. At night, particles presented mostly round shapes. This difference was particularly pronounced in particles with cut-off diameters of 0.15 μm.     

Particle size distributions and elemental composition of atmospheric particulate matter in southern Italy

Three 2-wk seasonal field campaigns were performed in 2003 and 2004 at a sampling site on the southern Tyrrhenian coast of Italy with the aim to investigate the dynamics and characteristics of particle-bound pollutants in the Mediterranean area. Fine (PM(2.5)) and coarse particulate matter (PM(10-2.5)) size fractions were collected by a manual dichotomous sampler on 37-mm Teflon filters over a 24-hr sampling period. On average, 70% of the total PM(10) (PM(2.5) + PM(10-2.5)) mass was associated with the coarse fraction and 30% with the fine fraction during the three campaigns. The ambient concentrations of Pb, Ni, Cr, Zn, Mn, V, Cd, Fe, Cu, Ca, and Mg associated with both size fractions were determined by atomic absorption spectrometry. Ambient concentrations showed differences in their absolute value, ranging from few ng x m(-3) to microg x m(-3), as well as in their variability within the PM(2.5) and PM(10-2.5) size fractions. PM(10) levels were well below the European Union (EU) limit value during the study period with the exception of three events during the first campaign (fall) and five events during the third campaign (spring). Two main sources were identified as the major contributors including mineral dust, transported from North Africa, and sea spray from the Tyrrhenian Sea. Comparing the results with backward trajectories, calculated using the Hybrid Single-Particle Lagrangian Integrated Trajectory Model (HYSPLIT) and Total Ozone Mapping Spectrometer-National Aeronautics and Space Administration (TOMS-NASA) maps, it was observed that in central and eastern Europe, the Tyrrhenian Sea and North Africa were the major emission source regions that affected the temporal variations and daily averages of PM(2.5) and PM(10-2.5) concentrations.     

Two extreme types of mixing of dust with urban aerosols observed in Kosa particles: ‘After’ mixing and ‘on-the-way’ mixing

Besides well-known episodic Kosa during spring, high concentrations of Ca²⁺ in aerosols were observed early in summer as well as in the semi-continuous data of the aerosols at the summit of Mt. Fuji. We further analysed the data to study the chemical characteristics of the high calcium event during early summer. The back trajectory analyses of the event indicated that Ca was transported from arid and semi-arid regions (e.g. the Taklamakan desert) through the westerly-dominated troposphere higher than the height of the summit of Fuji. The amount of SO₄^2? was always equivalent to that of NH₄⁺ unlike the case of the normal Kosa period where SO₄^2? is in excess with respect to NH₄⁺. This shows the ‘after’ mixing of unreacted CaCO₃ of Kosa origin with (NH₄)₂SO₄, which was only realized by the downward injection of Kosa particles from higher altitudes to the air masses of different origin. In the case of normal Kosa, the air bearing Kosa particles passed through the polluted area to absorb unneutralized acids (‘on-the-way’ mixing), whereas in the case of the Kosa-like phenomena in summer, the acids from the polluted area have been neutralized by NH₄⁺ and become inactive before mixing with CaCO₃ (“after” mixing). We have simplified the chemistry of aerosols using their three major components, Ca²⁺, SO₄^2? and NH₄⁺, and introduced a new triangle diagram with the three assumed end-members of CaCO₃, CaSO₄ and (NH₄)₂SO₄ to quantify the contribution of the ‘after’ mixing to the aerosols (AMI; ‘after’ mixing index). Based on the back trajectories of some high AMI cases, CaCO₃ in Kosa particles was transported through the middle troposphere (5000–7000 m) and descended to meet another air mass where SO₄^2? had been already neutralized by NH₃.     

受污染城市河道沉积物磷吸附特征及其影响因素

采集了典型受污染城市河道——陕西省新河不同季节的沉积物,研究其磷吸附特征及影响因素,并考察其缓冲外源污染的能力,评估其磷释放风险。结果显示,沉积物平均粒径在秋季小于夏季和春季,pH为7.64~8.88;沉积物总磷 (TP) 为870~2 173 mg·kg⁻¹;计算了沉积物磷富集系数,明确了新河部分点位为重度污染类型。吸附动力学研究结果表明：0~2 h沉积物对磷的吸附量在正负之间波动;2~4 h吸附量迅速增加,吸附速率也达到了峰值;之后吸附量增加趋势变缓,并在48 h达到平衡。绘制吸附等温线,可知沉积物的磷吸附-解吸平衡质量浓度 (EPC₀) 为0.39~2.21 mg·L⁻¹,高于同时段上覆水中磷的质量浓度,具有释放风险;磷最大缓冲容量MBC和Freundlich常数K_F呈现秋季>>夏季>春季的规律;经D-R模型拟合,绝大多数样品的吸附能为8.45~11.18 kJ·mol⁻¹,说明吸附机制为离子交换。相关性分析结果表明,沉积物的磷吸附速率常数与钙的相对含量呈显著相关 (P<0.05) 。EPC₀与沉积物的总磷和易释放态磷含量呈显著相关 (P<0.01) ,与沉积物平均粒径和有机质显著相关 (P<0.05) ,与pH显著相关 (P<0.05) 。本研究结果可为受污染城市河道治理提供参考。     

Sources and mass fluxes of the main contaminants in a heavily polluted and modified river of the North China Plain

Many rivers in China and other newly industrialized countries have suffered from severe degradation of water quality in the context of rapid economic growth. An accounting method was developed to investigate the source and mass fluxes of the main contaminants in the Ziya River, a severely polluted and heavily modified river in a semiarid area of the North China Plain, where chemical oxygen demand (COD) and ammonia nitrogen (NH₄-N) were the most important indicators of pollution. The results showed that the urban sewage with high concentration of COD and NH₄-N dominated the streams, contributing to 80.7 % of the streamflow, 92.2 % of COD, and 94.5 % of NH₄-N. The concentrations of COD and NH₄-N in streams varied from 24.0–195.0 to 5.8–43.8 mg/L, respectively. Mass fluxes of COD and NH₄-N of all pathways were quantified. Much of the polluted water was diverted to irrigation, and some eventually flowed into the Bohai Sea. Installation of adequate wastewater treatment facilities and making strict discharge standards can help improve the water quality. Our findings imply that a simple accounting method provides an extremely well-documented example for load estimation and can be useful for intervention strategies in heavily polluted and modified rivers in newly industrialized countries.     

Evaluating the size distribution characteristics and sources of atmospheric trace elements at two mountain sites: comparison of the clean and polluted regions in China

Size-resolved trace metal concentrations at two background sites were assessed during a 1-year observation campaign, with the measurements performed in parallel at two mountain sites, where Mt. Dinghu (DHS) located in the rural region of Pearl River Delta (PRD) and Mt. Gongga (GGS) located in the Tibetan Plateau region. In total, 15 selected trace elements (Mg, Al, K, V, Mn, Fe, Cu, Zn, As, Mo, Ag, Cd, Ba, Tl, and Pb) in aerosol samples were determined using inductively coupled plasma mass spectrometry (ICPMS). The major metals in these two mountain sites were Fe, K, Mg, and Ca with concentrations ranging between 241 and 1452 ng/m³, 428 and 1351 ng/m³, 334 and 875 ng/m³, and 376 and 870 ng/m³, respectively, while the trace metals with the lowest concentrations were Mo, Ag, Cd, and Tl with concentrations lower than 4 ng/m³ in DHS and 2 ng/m³ in GGS. The pronounced seasonal variability in the trace elements was observed in DHS, with lower concentrations in spring and summer and relatively high in winter and autumn, whereas seasonal variance of trace elements is hardly observed in Mt. Gongga. The size distribution pattern of crustal elements of Al, Mg, K, Ba, and Fe was quite similar in DHS and GGS, which were mainly found in coarse particles peaked at 4.7–5.8 μm. In addition, V, Mo, Ag, and Tl were also concentrated in coarse particles, although the high enrichment factor (EF?>?100) of which suggested anthropogenic origin, whereas trace metals of Cd, Mn, Zn, As, Cu, and Pb concentrated in fine mode particles. Specifically, these trace metals peak at approximately 1.5 μm in DHS, while those in GGS peaked at diameter smaller than 0.3 μm, indicating the responsible for long-range transport from the far urban and industrialized areas. Multivariate receptor model combined with the enrichment factor results demonstrated that the trace elemental components at these two background sites were largely contributed from the fossil fuel combustion (55.4% in DHS and 44.0% in GGS) and industrial emissions factors (20.1% vs. 26.5%), which are associated with long distance transport from the coastal area of Southeast China and the Northwestern India, respectively, as suggested by the backward air mass trajectory analysis. Local sources from soil dust contributed a minor variance for trace elements in DHS (9.7%) and GGS (13.8%), respectively.