Compositions and sources of organic acids in fine particles (PM2.5) over the Pearl River Delta region, south China

Organic acids as important constituents of organic aerosols not only influence the aerosols' hygroscopic property, but also enhance the formation of new particles and secondary organic aerosols. This study reported organic acids including C14–C32fatty acids, C4–C9dicarboxylic acids and aromatic acids in PM2.5collected during winter 2009 at six typical urban, suburban and rural sites in the Pearl River Delta region. Averaged concentrations of C14–C32fatty acids, aromatic acids and C4– C9 dicarboxylic acids were 157, 72.5 and 50.7 ng/m3, respectively. They totally accounted for 1.7% of measured organic carbon. C20–C32fatty acids mainly deriving from higher plant wax showed the highest concentration at the upwind rural site with more vegetation around, while C14–C18fatty acids were more abundant at urban and suburban sites, and dicarboxylic acids and aromatic acids except 1,4-phthalic acid peaked at the downwind rural site. Succinic and azelaic acid were the most abundant among C4–C9dicarboxylic acids, and 1,2-phthalic and 1,4-phthalic acid were dominant aromatic acids. Dicarboxylic acids and aromatic acids exhibited significant mutual correlations except for 1,4-phthalic acid, which was probably primarily emitted from combustion of solid wastes containing polyethylene terephthalate plastics. Spatial patterns and correlations with typical source tracers suggested that C14–C32fatty acids were mainly primary while dicarboxylic and aromatic acids were largely secondary. Principal component analysis resolved six sources including biomass burning, natural higher plant wax, two mixed anthropogenic and two secondary sources; further multiple linear regression revealed their contributions to individual organic acids. It turned out that more than 70% of C14–C18fatty acids were attributed to anthropogenic sources, about 50%–85% of the C20–C32fatty acids were attributed to natural sources, 80%–95% of dicarboxylic acids and 1,2-phthalic acid were secondary in contrast with that 81% of 1,4-phthalic acid was primary.     

Fast increasing of surface ozone concentrations in Pearl River Delta characterized by a regional air quality monitoring network during 2006-2011

Based on the observation by a Regional Air Quality Monitoring Network including 16 monitoring stations, temporal and spatial variations of ozone(O3), NO2and total oxidant(Ox) were analyzed by both linear regression and cluster analysis. A fast increase of regional O3concentrations of 0.86 ppbV/yr was found for the annual averaged values from 2006 to 2011 in Guangdong, China. Such fast O3increase is accompanied by a correspondingly fast NOx reduction as indicated by a fast NO2 reduction rate of 0.61 ppbV/yr. Based on a cluster analysis, the monitoring stations were classified into two major categories – rural stations(non-urban) and suburban/urban stations. The O3concentrations at rural stations were relatively conserved while those at suburban/urban stations showed a fast increase rate of 2.0 ppbV/yr accompanied by a NO2 reduction rate of 1.2 ppbV/yr. Moreover, a rapid increase of the averaged O3 concentrations in springtime(13%/yr referred to 2006 level) was observed, which may result from the increase of solar duration, reduction of precipitation in Guangdong and transport from Eastern Central China. Application of smog production algorithm showed that the photochemical O3production is mainly volatile organic compounds(VOC)-controlled. However, the photochemical O3production is sensitive to both NOx and VOC for O3pollution episode. Accordingly, it is expected that a combined NOx and VOC reduction will be helpful for the reduction of the O3 pollution episodes in Pearl River Delta while stringent VOC emission control is in general required for the regional O3 pollution control.     

近10 a来珠江三角洲地区氮收支演变及区域差异分析

采用2000、2005 和2010 年三个不同时期的工业、农业、环保、自然条件和人口等相关数据,通过大量数理统计分析对近10 a 来珠江三角洲（简称“珠三角”）地区的氮收支演变与区域差异进行了评估。结果表明,在过去三个不同时期,珠三角地区氮的年输入、输出量有升有降,但是氮盈余总量却呈现出较显著的增加趋势,单位面积氮盈余量也从2000 年的43.43 kg/（hm²·a）增加到2010 年的51.92 kg/（hm²·a）。整个珠三角地区的负荷氮水平较全国平均水平偏高,但尚低于同样经济发展迅速、人口密集的长江三角洲地区的平均水平。快速的城市化发展和日益增强的人类活动对珠三角地区氮收支变化具有较大影响,且表现出非常显著的内部区域差异,深圳、东莞、佛山和广州等城市均面临较为严峻的氮污染潜势。     

2011年10月珠江三角洲一次区域性空气污染过程特征分析

2011年10月18—25日珠江三角洲地区出现了一次区域性空气污染过程,重污染区域集中在西部,后期向中部转移,PM₁₀为首要污染物.针对本次空气污染过程的研究发现,此次珠江三角洲地区空气污染过程主要受大尺度冷高压活动的影响,一直为下沉气流所控制,500 m以下近地层风速很小,边界层高度较低,存在贴地逆温层,非常不利于污染物的输送和扩散.PM₁₀浓度与风速、能见度呈显著的负相关关系,与温度相关性不显著;且与风速和温度的相关性存在滞后性.稳定天气形势、大范围下沉气流、近地层静小风和贴地逆温是导致这次区域性空气污染过程的气象原因,PM₁₀浓度增加导致珠江三角洲能见度下降.     

2006~2010年珠三角地区SO2特征分析

对广州番禺大气成分站2006~2010年期间的SO2资料进行了分析,讨论了珠江三角洲(珠三角)地区地面SO2体积分数的年、季节、月、日变化特征和概率的分布特征.珠三角地区地面SO2变化特征的分析结果表明,2010年地面SO2体积分数的总体水平相对近年来有一定下降,高浓度事件发生频率降低;冬、春季SO2各项统计值要高于夏、秋季,干季明显高于湿季,可能与大气边界层高度和太阳辐射等因素的季节性变化相关;SO2干湿季的日变化趋势相仿,日最高峰时间相同,只是湿季达次高峰和最低点的时间比干季要提前1 h,这可能与季节性的大气边界层高度和辐射强度变化,以及日照时间长度有关;SO2体积分数的概率分布特征比较复杂,各月谱型分布各有不同,可能与季节性因素的变化规律相关.     

Spatial distribution of perfluoroalkyl acids in the Pearl River of Southern China

An intensive campaign was conducted in September 2012 to collect surface water samples along the tributaries of the Pearl River in southern China. Thirteen perfluoroalkyl acids (PFAAs), including perfluorocarboxylates (PFCAs, C4–C11) and perfluorosulfonates (PFSAs, C4, C6–C8, and C10), were determined using high-performance liquid chromatography/negative electrospray ionization–tandem mass spectrometry (HPLC/(-)ESI–MS/MS). The concentrations of total PFAAs (ΣPFAAs) ranged from 3.0 to 52 ng L⁻¹, with an average of 19 ± 12 ng L⁻¹. The highest concentrations of ΣPFAAs were detected in the surface water of the Dong Jiang tributary (17–52 ng L⁻¹), followed by the main stream (13–26 ng L⁻¹) and the Sha Wan stream (3.0–4.5 ng L⁻¹). Perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorooctane sulfonate (PFOS) were the three most abundant PFAAs and on average accounted for 20%, 24%, and 19% of ΣPFAAs, respectively. PFBS was the most abundant PFAA in the Dong Jiang tributary, and PFOA was the highest PFAA in the samples from the main stream of the Pearl River. A correlation was found between PFBS and PFOA, which suggests that both of these PFAAs originate from common source(s) in the region. Nevertheless, the slope of PFBS/PFOA was different in the different tributaries sampled, which indicates a spatial difference in the source profiles of the PFAAs.     

Heavy metals in bark of <Emphasis Type="Italic">Pinus massoniana</Emphasis> (Lamb.) as an indicator of atmospheric deposition near a smeltery at Qujiang,China

Goal, Scope and Background Rapid urbanization and the expansion of industrial activities in the past several decades have led to large increases in emissions of pollutants in the Pearl River Delta of south China. Recent reports have suggested that industrial emission is a major factor contributing to the damages in current natural ecosystem in the Delta area. Tree barks have been used successfully to monitor the levels of atmospheric metal deposition in many areas, but rarely in China. This study aimed at determining whether atmospheric heavy metal deposition from a Pb-Zn smeltery at Qujiang, Guangdong province, could be accurately reflected both in the inner bark and the outer bark of Masson pine (Pinus massoniana L.). The impact of the emission from smeltery on the soils beneath the trees and the relationships of the concentrations between the soils and the barks were also analyzed. Methods Barks around the bole of Pinus massoniana from a pine forest near a Pb-Zn smeltery at Qujiang and a reference forest at Dinghushan natural reserve were sampled with a stainless knife at an average height of 1.5 m above the ground. Mosses and lichens on the surface barks were cleaned prior to sampling. The samples were carefully divided into the inner bark (living part) and the outer bark (dead part) in the laboratory, and dried and ground, respectively. After being dry-ashed, the powder of the barks was dissolved in HNO₃. The solutions were analyzed for iron (Fe), manganese (Mn), copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni) and cobalt (Co) by inductively coupled plasmas emission spectrometry (ICP, PS-1000AT, USA) and Cadmium (Cd) and lead (Pb) by graphite furnace atomic absorption spectrometry (GFAAS, ZEENIT 60, Germany). Surface soils (0–10 cm) beneath the sample trees were also collected and analyzed for the selected metals. Results and Discussion Concentrations of the selected metals in soils at Qujiang were far above their environmental background values in the area, except for Fe and Mn, whilst at Dinghushan, they were far below their background values, except for Cd and Co. Levels of the metals, in particular Pb and Zn, in the soils beneath the sample trees at Qujiang were higher than those at Dinghushan with statistical significance. The result suggested that the pine forest soils at Qujiang had a great input of heavy metals from wet and dry atmospheric deposition, with the Pb-Zn smeltery most probably being the source. Levels of Cu, Fe, Mn, Zn, Ni and Pb at Qujiang, both in the inner and the outer bark, were statistically higher than those at Dinghushan. Higher concentrations of Pb, Fe, Zn and Cu may come from the stem-flow of elements leached from the canopy, soil splash on the 1.5 m height and sorption of metals in the mosses and lichens growing on the bark, which were direct or indirect results from the atmospheric deposition. Levels of heavy metals in the outer barks were associated well with the metal concentrations in the soil, reflecting the close relationships between the metal atmospheric deposition and their accumulation in the outer bark of Masson pine. The significant (p<0.01) correlations of Fe-Cu, Fe-Cr, Fe-Pb, Fe-Ni, Pb-Ni, and Pb-Zn in the outer barks at Qujiang again suggested a common source for the metals. The correlation only occurred between Pb and Ni, Cd and Co in the outer barks at Dinghushan, which suggested that those metals must possibly have other uncommon sources. Conclusions Atmospheric deposition of the selected metals was great at Qujiang, based on the levels in the bark of Pinus massoniana and on the concentrations in the soils beneath the trees compared with that at Dinghushan. Bark of Pinus massoniana, especially the outer bark, was an indicator of metal loading at least at the time of sampling. Recommendations and Perspectives The results from this study and the techniques employed constituted a new contribution to the development of biogeochemical methods for environmental monitoring particularly in areas with high frequency of pollution in China. The method would be of value for follow up studies aimed at the assessment of industrial pollution in other areas similar with the Pearl River Delta.     

从"珠三角火力发电厂排污交易试验计划"看粤港区域环境管理制度创新机遇

总结排污交易在中国的发展历程,展望"珠三角火力发电厂排污交易试验计划实施方案"实施,粤港区域环境管理将面临着一次新的挑战,也是区域环境保护制度创新的重大机遇.     

Perfluorinated compounds in the Pearl River and Yangtze River of China

A total of 14 perfluorinated compounds (PFCs) were quantified in river water samples collected from tributaries of the Pearl River (Guangzhou Province, south China) and the Yangtze River (central China). Among the PFCs analyzed, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the two compounds with the highest concentrations. PFOS concentrations ranged from 0.90 to 99 ng/l and <0.01–14 ng/l in samples from the Pearl River and Yangtze River, respectively; whereas those for PFOA ranged from 0.85 to 13 ng/l and 2.0–260 ng/l. Lower concentrations were measured for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctanesulfoamide (PFOSA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorononaoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA). Concentrations of several perfluorocarboxylic acids, including perfluorododecanoic acid (PFDoDA), perfluorotetradecanoic acid (PFTeDA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctadecanoic acid (PFOcDA) were lower than the limits of quantification in all the samples analyzed. The highest concentrations of most PFCs were observed in water samples from the Yangtze River near Shanghai, the major industrial and financial centre in China. In addition, sampling locations in the lower reaches of the Yangtze River with a reduced flow rate might serve as a final sink for contaminants from the upstream river runoffs. Generally, PFOS was the dominant PFC found in samples from the Pearl River, while PFOA was the predominant PFC in water from the Yangtze River. Specifically, a considerable amount of PFBS (22.9–26.1% of total PFC analyzed) was measured in water collected near Nanjing, which indicates the presence of potential sources of PFBS in this part of China. Completely different PFC composition profiles were observed for samples from the Pearl River and the Yangtze River. This indicates the presence of dissimilar sources in these two regions.     

珠三角表层沉积物的有机碳及其与卤系阻燃剂的关系

测定了珠江三角洲130个表层沉积物中总有机碳(TOC)和10类卤系阻燃剂(HFRs)的含量,并探讨了TOC与HFRs之间的关系.结果表明:珠三角表层沉积物TOC范围为0.16％～5.76％,平均值为1.25％,呈现明显的空间变化.在工业化程度较高的东莞和广州,沉积物中HFRs与TOC有显著的相关性,而西江和珠江口沉积物中HFRs与TOC的相关性较差,可能与珠江三角洲水动力过程、电子垃圾拆解活动和HFRs不同的来源有关.