珠三角秋季臭氧污染来源解析

秋季是珠三角臭氧污染最严重的季节,选取2004年秋季珠三角典型臭氧污染过程,运用臭氧来源解析技术等分析手段,研究珠三角臭氧污染特性,分析并量化各排放源区各类源对受体点的臭氧贡献。结果表明,东莞市对珠江口地区的臭氧峰值有重大贡献,下午2-3点东莞市前体物的臭氧贡献最大可达40ppb;而广州市区的前体物排放主要影响顺德区和南海区。在珠三角,排放源区一般对下风向40km范围内的地区臭氧贡献最大。秋季大多数情况下珠三角西部(江门东湖)臭氧受中部主要排放源区臭氧前体物排放与输送的影响很大,广州和佛山地区对江门东湖的臭氧峰值贡献达50ppb左右。交通尾气排放对珠三角各受体点的臭氧贡献最大,交通源对重污染区受体点臭氧的贡献最高可达40ppb~50ppb。     

Tissue distribution of organochlorine pesticides in fish collected from the Pearl River Delta, China: implications for fishery input source and bioaccumulation

Fish tissues from different fishery types (freshwater farmed, seawater farmed and seawater wild) were analyzed for organochlorine pesticides (OCPs), with the aim to further our understanding of bioaccumulation, and reflect the state of different fishery environments. Significantly higher SigmaOCP levels were found in seawater farmed fish than others, and among three freshwater farmed species, the lowest levels occurred in filter-feeding fish (bighead carp). Liver contained the highest SigmaOCP levels, while no significant differences were found among other tissues. Among DDT components, p,p'-DDT was abundant in seawater fish, while for freshwater fish, p,p'-DDE was the predominant congeners, except for northern snakehead (34% for p,p'-DDE and 30% for p,p'-DDT). The new source of DDTs to freshwater fish ponds was partly attributed to dicofol, whereas sewage discharged from the Pearl River Delta and anti-fouling paint were likely the DDTs sources to seawater farmed fish.     

Occurrence, source diagnosis, and biological effect assessment of DDT and its metabolites in various environmental compartments of the Pearl River Delta, South China: A review

This review summarizes and analyzes available data in the literature (mostly after 2000) on the occurrence of dichlorodiphenyltrichloroethane (DDT) and its main metabolites, dichlorodiphenyldichloroethane (DDD) and chlorodiphenyldichloroethylene (DDE), in the environment of the Pearl River Delta (PRD), South China. Generally, the concentration levels of the sum of DDT, DDD, and DDE, designated as DDTs thereafter, have not significantly declined since 1983. However, the composition of DDTs residues has changed with time. DDTs in soil, freshwater sediment and freshwater fish species were mainly residues from chronological use. There is evidence that new point sources, such as dicofol and anti-fouling paint, may have contributed DDTs to various environmental compartments. Risk assessment against existing criteria indicated that the levels of DDTs in water and some fish species may pose adverse effects to humans or wildlife, and those in sediment/soil may also cause negative impacts to the eco-environment of the PRD.     

Occurrence and distribution of sediment-associated insecticides in urban waterways in the Pearl River Delta, China

Sediment-associated pesticides, including organochlorine (OCP), organophosphate (OP), and pyrethroid insecticides, were analyzed in urban waterways in three cities (Guangzhou, Dongguan, and Shenzhen) in the Pearl River Delta (PRD), China. The OCPs represented 27.2% of the detectable insecticides in sediment, and chlordanes, DDTs, and endosulfans were the most frequently detected OCPs. The currently used insecticide chlorpyrifos was the only OP detected above the reporting limit (RL), with concentrations ranging from <RL to 100 ng g⁻¹ dry weight (dw). Additionally, pyrethroids were detected in all sediments with the sum pyrethroid concentrations ranging from 4.26 to 384 ng g⁻¹ dw and this represented 64.9% of the sum insecticide concentration. Despite their widespread use, no studies have been conducted investigating the occurrence and distribution of pyrethroids in China. As the first report of pyrethroids in urban waterways in China, the current study found cypermethrin was the most abundant insecticide detected in the PRD at concentrations ranging from 1.44 to 219 ng g⁻¹ dw. Spatially, sediment from more populous and urbanized areas (Shenzhen and Tianhe district in Guangzhou) had higher insecticide residues than less populous agricultural areas. In the more modernized city of Shenzhen, the OCPs were seldom detected, whereas more diverse patterns of pyrethroids were observed. Potential sources of these insecticides, especially the frequently detected pyrethroids, were most likely from pest control during urban landscaping maintenance and from abatement programs targeting mosquitoes and ants. Results suggested that a shift in application pattern and elevated urbanization increased accumulation of currently used insecticides like pyrethroids in sediment, and made them the predominate insecticides in the PRD urban waterways.     

Spatial trend and pollution assessment of total mercury and methylmercury pollution in the Pearl River Delta soil, South China

Total mercury (THg) and methylmercury (MeHg) were measured in large number of soil samples collected from areas with different types of land use, different depth in the Pearl River Delta (PRD) of South China. THg and MeHg concentrations ranged from 16.7 to 3320 ng g⁻¹ and 0.01 to 1.34 ng g⁻¹, respectively. THg levels are highest in the top 0-20 cm soil layer, and decrease from the surface to bottom layer soil. Spatial variation was observed with different types of land use. Urban parks had the highest concentrations and the other areas tended to decrease in the order of residential areas, industrial areas, vegetable fields, cereal fields, and woodlands. Temporal variation was also noted, and two relatively high THg contamination zones located in the northwestern part of the PRD have significantly expanded over the last two decades. Both THg and MeHg concentrations were correlated significantly with soil organic matter (OM), but not with soil pH. THg pollution status was evaluated using two assessment methods.     

Regional dynamics of persistent organic pollutants (POPs) in the Pearl River Delta, China: implications and perspectives

The mass transport budgets of 1,1,1-trichloro-2,2-bis(chlorophenyl)ethane (p,p′-DDT) and decabromodiphenyl ether (BDE-209) in the Pearl River Delta, South China were calculated based on previously collected data. Residual p,p′-DDT, mostly related to historical use, has largely settled into soil (780,000 kg), while the soil BDE-209 inventory (44,000 kg) is considerably smaller. Conversely, large amounts of BDE-209 currently used in numerous commercial products have resulted in a much higher atmospheric depositional flux of BDE-209 (28,100 kg/yr) relative to p,p′-DDT (310 kg/yr). The soil inventory of p,p′-DDT is predicted to decrease to half of its current value after 22 years, and the percent area containing soil p,p′-DDT at levels exceeding the effects range-medium (27 ng/g) will decrease from 40% to 20%. Finally, soil BDE-209 inventory will reach an equilibrium value of 940 tons in ∼60 years, when BDE-209 levels in 50% of soil will be above an equivalent risk guideline value (125 ng/g).     

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.     

Linear alkylbenzenes in riverine runoff of the Pearl River Delta (China) and their application as anthropogenic molecular markers in coastal environments

The average concentrations of ∑LABs (sum of C₁₀-C₁₃-LABs) in runoff samples collected from the eight major riverine outlets of the Pearl River Delta (PRD) of China ranged from 1.4 to 6124 ng/L in the dissolved phase and from 0.01 to 11.4 μg/g dry weight in the particulate phase during March 2005-February 2006. The annual riverine flux of ∑LABs from the PRD to the coastal ocean was estimated at approximately 14 tons/yr. The inventories of ∑LABs in agricultural lands of Guangdong Province ranged from 313 to 1825 kg/yr. The early and late rice fields were the major sink of LABs, accounting for approximately 68% of total LABs inventory in agricultural lands. The social-economically estimated annual discharge of LABs from household detergents in the PRD was ∼696 tons/yr, more than an order of magnitude higher than that estimated from field measurements (about 14 tons/yr), which was attributed to several factors.     

Characterization of ambient volatile organic compounds at a landfill site in Guangzhou,South China

Ambient air monitoring was conducted at Datianshan landfill, Guangzhou, South China in 1998 to investigate the seasonal and horizontal variations of trace volatile organic compounds (VOCs). Twelve sampling points over the Datianshan landfill were selected and samples were collected simultaneously using Carbontrap(TM) adsorption tubes. Thirty eight VOCs were detected in the winter, whereas 60 were detected in the summer. The VOC levels measured in summer were alkanes, 0.5-6.5 microg/m(3); aromatics, 2.3-1667 microg/m(3); chlorinated species, 0.2-31 microg/m(3); terpines, 0.1-34 microg/m(3); carbonyl species, 0.3-5.6 microg/m(3) and naphthalene and its derivatives, 0.4-27 microg/m(3). Compared to the summer samples the VOC levels in winter were much lower (mostly 1-2 orders of magnitude lower). The aromatics are dominant VOCs in landfill air both in winter and summer. High levels of alkylbenzene and terpines such as methyl-isopropylbenzene (max 1667 microg/m(3)) and limonene (max 162 microg/m(3)) cause undesirable odor. The similar correlation coefficients of BTEX in summer and winter suggest VOCs emissions were from landfill site sources. The variation of BTEX ratio at landfill site is different from that in the urban area of Guangzhou. It shows that the ambient VOCs at landfill site were different from the urban areas.     

Fate of polybrominated diphenyl ethers in the environment of the Pearl River Estuary, South China

Ninety-six riverine runoff samples collected at eight major outlets in the Pearl River Delta (PRD), South China, during 2005-2006 were analyzed for 17 brominated diphenyl ether (BDE) congeners (defined as Σ₁₇PBDE). Fourteen and 15 congeners were detected, respectively, in the dissolved and particulate phases. These data were further used to elucidate the partitioning behavior of BDE congeners in riverine runoff. Several related fate processes, i.e. air-water exchange, dry and wet deposition, degradation, and sedimentation, within the Pearl River Estuary (PRE), were examined to estimate the inputs of Σ₁₀PBDE (sum of the target BDE congeners, BDE-28, -47, -66, -85, -99, -100, -138, -153, -154, and -183) and BDE-209 from the PRD to the coastal ocean based on mass balance considerations. The results showed that annual outflows of Σ₁₀PBDE and BDE-209 were estimated at 126 and 940 kg/year, respectively from the PRE to coastal ocean. Besides sedimentation and degradation, the majority of Σ₁₀PBDE and BDE-209 discharged into the PRE via riverine runoff was transported to the coastal ocean.     

Fate of linear alkylbenzenes and benzothiazoles of anthropogenic origin and their potential as environmental molecular markers in the Pearl River Delta, South China

The mass emissions of linear alkylbenzenes (LABs), benzothiazole (BT), and 2-[4-morpholinyl]benzothiazole (24MoBT) from anthropogenic activities within one year were estimated according to the population and the number of automobiles in the Pearl River Delta (PRD), South China. Based on the estimation, the distribution of these compounds among various environmental media was simulated with a mass balance box model established in the present study. The results showed that 79% of LABs generated in the PRD was stored in sediment while only 1.3% of LABs was presumably transported to the adjacent South China Sea (SCS). On the contrary, 47% of BT and 77% of 24MoBT generated in the region were carried with riverine runoff to the coastal ocean. The results from the present study suggest that hydrophobic compounds tend to stay in the watershed of the PRD, whereas hydrophilic ones mainly outflow to the coastal ocean.     

Species- and tissue-specific accumulation of Dechlorane Plus in three terrestrial passerine bird species from the Pearl River Delta, South China

Little data is available on the bioaccumulation of Dechlorane Plus (DP) in terrestrial organisms. Three terrestrial passerine bird species, light-vented bulbul, long-tailed shrike, and oriental magpie-robin, were collected from rural and urban sites in the Pearl River Delta to analyze for the presence of DP and its dechlorinated products in muscle and liver tissues. The relationships between trophic level and concentration and isomeric composition of DP in birds were also investigated based on stable nitrogen isotope analysis. DP levels had a wide range from 3.9 to 930 ng g⁻¹ lipid weight (lw) in muscle and from 7.0 to 1300 ng g⁻¹ lw in liver. Anti-Cl₁₁-DP and syn-Cl₁₁-DP, two dechlorinated products of DP, were also detected in bird samples with concentrations ranged between not detected (nd)-41 and nd-7.6 ng g⁻¹ lw, respectively. DP preferentially accumulated in liver rather than in muscle for all three bird species. Birds had significantly higher concentrations of DP in urban sites than in rural sites (mean, 300 vs 73 ng g⁻¹ lw). The fractions of anti-DP (f_anti) were higher in birds collected in rural sites than in urban sites. Significant positive correlation between DP levels and δ¹⁵N values but significant negative correlation between f_anti and δ¹⁵N values were found for birds in both urban and rural sites, indicating that trophic level of birds play an important role in determining DP level and isomeric profile.     

珠江三角洲地区土壤中二噁英污染水平及其分布特征研究

应用高分辨气相色谱/高分辨质谱(HRGC/HRMS)对珠江三角洲地区土壤中二噁英(PCDD/Fs)的浓度及其分布特征进行了研究。结果表明,土壤样品中PCDD/Fs为118~2 304pg/g,平均值为743pg/g;WHO2005-TEQ为1.09~5.56pg/g,平均值为3.25pg/g。珠江三角洲地区土壤中PCDD/Fs浓度较往年相比稍有下降,且大部分地区土壤中PCDD/Fs污染并不严重。土壤中PCDD/Fs同系物分布以OCDD为主要的特征单体,毒性单体贡献最大的是1,2,3,7,8-PeCDD和2,3,4,7,8-PeCDF,平均占总毒性当量的28.9%和16.3%。对珠江三角洲地区土壤中PCDD/Fs的源分析表明,土壤中PCDD/Fs受污染源影响较小,可能主要来自大气沉降。     

Organochlorine pesticides and polychlorinated biphenyls in riverine runoff of the Pearl River Delta, China: assessment of mass loading, input source and environmental fate

A large-scale sampling program was conducted to simultaneously collect water samples at the eight major riverine runoff outlets of the Pearl River Delta (PRD), South China to assess the importance of riverine runoff in transporting anthropogenic pollutants from terrestrial sources to the coastal ocean. The concentrations of ∑₂₁OCPs (sum of 21 OCP components) and ∑₂₀PCBs (sum of 20 PCB congeners) were 2.57-41.2 and 0.12-1.47 ng/L, respectively. Compositional distributions of DDTs suggested the possibility of new input sources in the study area, but contributions from dicofol seemed considerably low. The annual inputs of ∑₂₁OCPs and ∑₂₀PCBs were 3090 and 215 kg, with those of total HCHs and DDTs being 1110 and 1020 kg, respectively. A mass balance consideration indicated that riverine runoff is the major mode carrying OCPs from the PRD to the coastal ocean, and the majority of OCPs is further dissipated to open seas.     

Estimation of the annual scavenged amount of polycyclic aromatic hydrocarbons by forests in the Pearl River Delta of Southern China

Leaves of six main tree species from the Pearl River Delta (PRD) in Southern China were collected to identify the interspecific variability, the spatial variability and the seasonal variations of polycyclic aromatic hydrocarbons' (PAHs) concentrations, and to calculate the amount of PAHs removed by leaves. PAHs concentrations in pine needles were much higher than in broad-leaves and leaves from urban/industrial areas (Baiyunshan and Heshan) exhibited two times greater concentrations than leaves from the rural area (Dinghushan). Seasonal variations of PAHs in leaves occurred with lesser concentrations in September. Leaves in PRD scavenged 3.7 ± 0.9 t PAHs y⁻¹, accounting for about 10% of the total amount emitted in this region. This result suggests that forests play an important role in the fate of PAHs.     

Impact of biogenic VOC emissions on a tropical cyclone-related ozone episode in the Pearl River Delta region,China

For quantitative estimate of biogenic volatile organic compound emissions (BVOCs) in South China and their impact on the regional atmospheric chemistry, a 3-day tropical cyclone-related ozone episode was modeled using chemical transport model CMAQ, which was driven by the mesoscale meteorological model MM5. Hourly biogenic emission inventories were constructed using the Sparse Matrix Operator Kernel Emissions (SMOKE) model. The simulation results show good agreement with observation data in air temperature, ozone and NO_x levels. The estimated biogenic emissions of isoprene, terpene, and other reactive VOCs (ORVOCs) during this tropical cyclone-related episode are 8500, 3400, and 11 300 ton day⁻¹, respectively. The ratio of isoprene to the total BVOCs was 36.4%. Two test runs were carried out with one incorporated biogenic emissions and the other without. The simulations show that Guangdong province, particularly the Pearl River Delta (PRD) region, was the area most reactive to biogenic emissions in South China. More ozone was produced in all layers under 1500 m when biogenic emissions were included in comparison to that without BVOCs. The net formation of ozone from 9:00 to 15:00 h was the highest near the surface and could reach 38 ppb, which include 4 ppb attributed to biogenic impact. The enhanced ozone due to biogenic emissions first appeared in the PRD region and slowly spread to a greater area in South China. Process analysis indicated that the surface ozone budget was dominated by the vertical transport and dry deposition. The horizontal transport and gas-phase chemical production were relatively small in the surface layer. Presumably, ozone was produced in upper layers within the atmospheric boundary layer and convected down to surface where it is destroyed. When BVOCs was included, apart from the enhancement of gas-phase chemical production of ozone, both the surface deposition and vertical transport were also augmented.     

天津市挥发性有机物污染特征与来源及其O3生成潜势

为深入了解天津市大气挥发性有机物(VOCs)来源及对O3的影响,基于2020年天津市VOCs在线监测数据,统计分析了VOCs污染特征,用主成分分析法对天津市VOCs的来源进行解析,用最大增量反应活性法分析VOCs的O3生成潜势(OFP).结果表明:2020年天津市VOCs的年均质量浓度总和为56.56μg/m3,其中,...     

成都市夏季大气挥发性有机物污染及其对二次有机气溶胶生成的贡献

于2014年7月8日至8月13日在成都市城区和工业区选取两个点位开展挥发性有机物(VOCs)样品采集工作,分析结果显示,成都市夏季城区大气中VOCs质量浓度在34.1~458.8μg/m3,平均值为(137.3±91.8)μg/m3;工业区大气中VOCs质量浓度在26.7~474.9μg/m3,平均值为(135.9±103.5)μg/m3。早高峰时段(7:00~10:00)两个点位VOCs的浓度水平均高于其他时段,说明VOCs浓度受机动车排放的影响较为明显。用·OH消耗速率和臭氧生成潜势评估VOCs大气化学反应活性,结果显示,芳香烃和烯烃是影响大气化学反应活性的关键组分。城区和工业区的二次有机气溶胶(SOA)的生成潜势分别为4.859、4.559μg/m3,芳香烃不仅是臭氧生成潜势的关键活性组分,同时也是SOA的重要前体物。     

Evaluation of the optimum volatile organic compounds control strategy considering the formation of ozone and secondary organic aerosol in Seoul, Korea

The characteristics of volatile organic compounds (VOCs) and their annual trends in Seoul, Korea were investigated, with their optimal control strategy suggested. The annual concentration of VOCs (96.2–121.1 ppbC) has shown a decreasing trend from 2004 to 2008, suggesting the control strategy via the “Special Measures for Metropolitan Air Quality Improvement,” which was implemented in 2005, has been successful. The contributions of individual VOC to the production of ambient ozone and secondary organic aerosol (SOA) are discussed to assess the adequacy of current control strategies. The contribution of aromatics (C6–C10) to the production of ozone accounted for 38.7–46.3 % of the total ozone production, followed by low carbon alkanes (C2–C6) (27.0–35.9 %). The total SOA formation potential of VOCs was found to range from 2.5 to 3.5 μg m^?3, mainly as a result of aromatics (C6–C10) (over 85 %). Considering the contributions from ozone and SOA production, it was concluded that solvent use was the most important emission source, followed by vehicle exhaust emissions. Thus, the current emission control strategy focused on these two emission sources is appropriate to reduce the VOCs related pollution level of the Seoul Metropolitan Region. Still, an additional control strategy, such as controlling the emissions from meat cooking, which is an emission source of high carbon alkanes (C7–C10), needs to be considered to further reduce the VOCs related pollution level in Seoul.