Uptake and depuration of PAHs and chlorinated pesticides by semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis)

Semi-batch seawater experiments were conducted to follow the uptake and release of selected PAHs (anthracene, fluorathene, pyrene and B[a]P) and organochlorine pesticides (-HCH, aldrin, dieldrin, p,p′-DDT) in semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis). Mathematical models were applied to describe the uptake and elimination curves of the contaminants for SPMDs, and kinetic parameters, such as uptake rate constants, and equilibrium triolein/water partitioning coefficients were calculated. SPMD data showed a good fit to estimate rate constant and partition coefficient equations, but only those contaminants which partitioned mainly in the dissolved phase (-HCH and dieldrin) were well explained for mussels. Poor conformity of the other contaminants indicated mussels uptake by routes other than diffusion, such as ingestion of algae. An apparent equilibrium state was only noted for -HCH in mussels. Aldrin was not detected in mussels in the first few days of exposure, indicating potential metabolism of this compound. B[a]P was not detected in the triolein of SPMDs, which suggests that the membrane may act as a reservoir. Loss of spiked B[a]P from the triolein was evident in a depuration experiment, which may indicate transfer to the membrane. Rate constants for mussels were higher than those for SPMDs, but the reverse was true for partition coefficients. Overall, mussels and SPMDs had similar uptake rates for all compounds in this study, excluding p,p′-DDT and dieldrin. Contaminant elimination took place more rapidly in mussels, implying that SPMDs are better candidates for detecting episodic discharge of organic contaminants.     

Uptake and depuration of PAHs and chlorinated pesticides by semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis)

Semi-batch seawater experiments were conducted to follow the uptake and release of selected PAHs (anthracene, fluorathene, pyrene and B[a]P) and organochlorine pesticides (α-HCH, aldrin, dieldrin, p,p′-DDT) in semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis). Mathematical models were applied to describe the uptake and elimination curves of the contaminants for SPMDs, and kinetic parameters, such as uptake rate constants, and equilibrium triolein/water partitioning coefficients were calculated. SPMD data showed a good fit to estimate rate constant and partition coefficient equations, but only those contaminants which partitioned mainly in the dissolved phase (α-HCH and dieldrin) were well explained for mussels. Poor conformity of the other contaminants indicated mussels uptake by routes other than diffusion, such as ingestion of algae. An apparent equilibrium state was only noted for α-HCH in mussels. Aldrin was not detected in mussels in the first few days of exposure, indicating potential metabolism of this compound. B[a]P was not detected in the triolein of SPMDs, which suggests that the membrane may act as a reservoir. Loss of spiked B[a]P from the triolein was evident in a depuration experiment, which may indicate transfer to the membrane. Rate constants for mussels were higher than those for SPMDs, but the reverse was true for partition coefficients. Overall, mussels and SPMDs had similar uptake rates for all compounds in this study, excluding p,p′-DDT and dieldrin. Contaminant elimination took place more rapidly in mussels, implying that SPMDs are better candidates for detecting episodic discharge of organic contaminants.     

Historical records of organic pollutants in sediment cores

Analyses of sediment core samples are primary sources of historical pollution trends in aquatic systems. Determining organic compounds, such as POPs, in the dated sediments enables the estimation of their temporal concentration changes and the identification of the contaminant origin in local regions. Wars, large-scale fires, economical transitions, and bans on certain chemicals are reflected in the sediment organic compound concentrations. The high POP concentrations in surficial sediments suggest that these chemicals, even after being banned, remain in the environment. Furthermore, vertical profiles can help in understanding the sedimentation process and in estimating effective countermeasures against pollution. Moreover, studies published during the period 1991–2013 on PAHs, PCBs, OCPs, dioxins and dioxin-like compound concentrations in sediment core samples are reviewed.     

Field validation of antioxidant enzyme biomarkers in mussels (Perna viridis) and clams (Ruditapes philippinarum) transplanted in Hong Kong coastal waters

Green-lipped mussels, Perna viridis, and Manila clams, Ruditapes philippinarum were sourced from “clean” sites in the Hong Kong region, depurated in a laboratory using uncontaminated filtered seawater for 8 days, and transplanted to a suspected gradient of chemically polluted sites in Hong Kong. After 14- and 28-days of field exposure, several antioxidant parameters including glutathione S transferase (GST), catalase (CAT), glutathione peroxidase (GPx), and glutathione (GSH) were quantified in gill and hepatopancreas tissues. Whole body tissue concentrations of polycyclic aromatic hydrocarbons (PAHs), petroleum hydrocarbons (PHCs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) were determined in pooled site samples. Chemical analyses indicated that: (a) clams had higher levels of PAHs, PHCs, DDTs and PCBs, whereas mussels had higher hexachlorocyclohexane (HCHs) and there was no difference between species for dieldrin and remaining OCs; (b) Kat O should not be continued as a “clean” reference site for Hong Kong, because of the levels of contaminants measured and (c) PAH concentrations in the current survey were similar to those previously measured. Toxicological conclusions were: (a) antioxidant responses were different between species; (b) CAT and GST have highest utility in clams for field use in Hong Kong, whereas CAT in both gill and hepatopancreas tissue showed most potential in mussels; (c) significant induction of antioxidant responses over day 0 (excluding GPx in both tissues, and GST in mussel hepatic tissue); (d) groups of contaminants do not consistently induce antioxidant responses and (e) organochlorines and PCBs correlated significantly with CAT and GST in clam hepatopancreas and with CAT in mussel gill and hepatic tissue. Multivariate statistical techniques indicated little relationship between the site patterns for antioxidant responses and the contaminant gradients identified in body burden analysis.     

Field validation of antioxidant enzyme biomarkers in mussels (Perna viridis) and clams (Ruditapes philippinarum) transplanted in Hong Kong coastal waters

Green-lipped mussels, Perna viridis, and Manila clams, Ruditapes philippinarum were sourced from “clean” sites in the Hong Kong region, depurated in a laboratory using uncontaminated filtered seawater for 8 days, and transplanted to a suspected gradient of chemically polluted sites in Hong Kong. After 14- and 28-days of field exposure, several antioxidant parameters including glutathione S transferase (GST), catalase (CAT), glutathione peroxidase (GPx), and glutathione (GSH) were quantified in gill and hepatopancreas tissues. Whole body tissue concentrations of polycyclic aromatic hydrocarbons (PAHs), petroleum hydrocarbons (PHCs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) were determined in pooled site samples. Chemical analyses indicated that: (a) clams had higher levels of PAHs, PHCs, DDTs and PCBs, whereas mussels had higher hexachlorocyclohexane (HCHs) and there was no difference between species for dieldrin and remaining OCs; (b) Kat O should not be continued as a “clean” reference site for Hong Kong, because of the levels of contaminants measured and (c) PAH concentrations in the current survey were similar to those previously measured. Toxicological conclusions were: (a) antioxidant responses were different between species; (b) CAT and GST have highest utility in clams for field use in Hong Kong, whereas CAT in both gill and hepatopancreas tissue showed most potential in mussels; (c) significant induction of antioxidant responses over day 0 (excluding GPx in both tissues, and GST in mussel hepatic tissue); (d) groups of contaminants do not consistently induce antioxidant responses and (e) organochlorines and PCBs correlated significantly with CAT and GST in clam hepatopancreas and with CAT in mussel gill and hepatic tissue. Multivariate statistical techniques indicated little relationship between the site patterns for antioxidant responses and the contaminant gradients identified in body burden analysis.     

Reconstruction of pollution history of organic contaminants in the upper Gulf of Thailand by using sediment cores: first report from Tropical Asia Core (TACO) project

This paper reports the first reconstruction of a pollution history in tropical Asia from sediment cores. Four sediment core samples were collected from an offshore transect in the upper Gulf of Thailand and were analyzed for organic micropollutants. The cores were dated by measurement of (137)Cs and geochronometric molecular markers (linear alkylbenzenes, LABs; and tetrapropylene-type alkylbenzenes, TABs). Polychlorinated biphenyl (PCB) concentrations showed a subsurface maximum in layers corresponding to the 1970s, indicating the effectiveness of regulation of PCBs in Thailand. LAB concentrations increased over time, indicating the increase in input of sewage into the Gulf during the last 30 years. Hopanes, biomarkers of petroleum pollution, also increased over time, indicating that the inputs of automobile-derived hydrocarbons to the coastal zone has been increasing owing to the increased number of cars in Thailand since the 1950s. Polycyclic aromatic hydrocarbons (PAHs) increased in the layers corresponding to the 1950s and 1960s, probably because of the increased inputs of automobile-derived PAHs. PAH concentrations in the upper layers corresponding to the 1970s and later remained constant or increased. The absence of a subsurface maximum of PAHs contrasts with results observed in industrialized countries. This can be explained by the facts that the Thai economy did not depend on coal as an energy source in the 1960s and that economic growth has continued since the 1970s to the present. The deposition flux of PAHs and hopanes showed a dramatic offshore decrease, whereas that of LABs was uniform.     

Contamination of polycyclic aromatic hydrocarbons (PAHs) in surface sediments and plants of mangrove swamps in Shenzhen,China

The concentrations of 16 individual and total polycyclic aromatic hydrocarbons (∑PAHs) in sediments, roots and leaves of three mangrove swamps in Shenzhen, China, namely Futian, Baguang and Waterlands, were determined. The mean concentration of ∑PAHs in Futian (4480 ng g⁻¹) was significantly higher than that in Baguang (1262 ng g⁻¹) and Waterlands (2711 ng g⁻¹). Among the 16 PAHs, the concentration of naphthalene was the highest. Based on the ratios of phenanthrene/anthracene and fluoranthene/pyrene, PAHs in Futian and Waterlands came from petrogenic and pyrolytic sources, while Baguang was mainly from pyrolytic. More PAHs were accumulated in leaves, as reflected by its higher mean concentration of ∑PAHs (3697 ng g⁻¹) and bioconcentration factor of PAHs (BCF) (>1.5) than that in roots. The BCF values in plants collected from Futian were significantly higher than that from Waterlands. These results indicated that more attention should be paid to the PAH contamination in Futian.     

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides in water columns from the Pearl River and the Macao harbor in the Pearl River Delta in South China

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) were measured in suspended particles and dissolved phase from the Baiertang water column and the Macao water column samples as collected from the Guangzhou channel of the Pearl River and the Macao harbor, where the sediments were heavily contaminated with organic pollutants. Total OCPs concentration varies from 23.4 to 61.7 ng/l in Baiertang water column and from 25.2 to 67.8 ng/l in Macao column, while total PAHs concentration varies from 987.1 to 2878.5 ng/l in the Baiertang water column and from 944.0 to 6654.6 ng/l in the Macao column. The vertical distribution profiles of pollutants and the partition of pollutants between particles and dissolved phases indicate that the sediments in Baiertang act as an important source of selected pollutants, and the pollutants in water of this region were mainly originated from the release and re-suspension of contaminants residing in the sediments. The sediments in Macao harbor act as a reservoir for organochlorine pesticides, such as DDTs mainly introduced by river inflow from Xijiang and PAHs input by brackish water from the Lingdingyang estuary. Combustion of fossil fuels and petroleum input are the main sources of PAHs in the Macao water column, while combustion of fossil fuels and coal is responsible for the PAHs in the Baiertang water column. The ratios of DDT/(DDD+DDE) for the Macao water column samples demonstrate that such chemicals were input into this region in recent times.     

Effect of Co‐culture and Nutrients Supplementation on Bioremediation of Crude Petroleum Sludge

Ex‐situ bioremediation of real‐field crude petroleum sludge was evaluated to elucidate the role of co‐culture (bioaugmentation) and external nutrients supplementation (biostimulation) under anaerobic microenvironment. Maximum removal of total petroleum hydrocarbons (TPH) was observed by integrating biostimulation with bioaugmentation (R5, 44.01%) followed by bioaugmentation alone (R4, 34.47%), co‐substrate supplemented operations [R6, 23.36%; R3, 16.5%; R2, 9.88%] and control (R1, 4.36%). Aromatics fraction showed higher degradation in all the conditions studied. Fate of six selected polycyclic aromatic hydrocarbons (PAHs) was evaluated during bioremediation. Among these, four ring PAHs compounds showed good degradation by integration of biostimulation with bioaugmentation (R5) while bioaugmentation alone (R4) documented good degradation of three ring PAHs. Lower ring PAHs compounds showed good degradation with the application of biostimulation (R6). Fluorescent in situ hybridization (FISH) detected the presence of known PAHs degrading microorganisms viz., Bacillus, Pseudomonas, Acido bacteria, Sulphur reducing bacteria Firmicutes, etc. Application of biostimulation and bioaugmentation strategies alone or in combinations documented noticeable influence on the degradation of petroleum sludge.     

Antioxidant responses to polycyclic aromatic hydrocarbons and organochlorine pesticides in green-lipped mussels (Perna viridis): Do mussels “integrate” biomarker responses?

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCs) are generally present in the marine environment in complex mixtures. The ecotoxicological nature of contaminant interactions, however, is poorly understood, with most scientific observations derived from single contaminant exposure experiments. The objective of this experiment was to examine dose-response relationships between antioxidant parameters and body contaminant levels in mussels exposed to different exposure regimes under laboratory conditions. Accordingly, the green-lipped mussel, Perna viridis, was challenged with a mixture of PAHs (anthracene, fluoranthene, pyrene, benzo[a]pyrene) and OC pesticides (α-HCH, aldrin, dieldrin, p,p′-DDT) over a 4 week period. Contaminants were delivered under four different dosing regimes, with all treatments receiving the same total contaminant load by the end of the exposure period. Antioxidant biomarkers were measured after 1, 2, 3 and 4 weeks, including glutathione (GSH), gluathione-S-transferase (GST), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), glutathione reductase (GR) and lipid peroxidase (LPO). GST and CAT were induced in hepatic tissues in most of the exposure regimes, with the majority of significant induction occurring in a constant exposure regime and a two-step alternate exposure regime. Significant differences among exposure regimes were detected in the body burden of contaminants after 28 days. Hepatic CAT and GSH are proposed as potentially useful biomarkers as they showed good correlation with target contaminants and were not readily affected by different dosing patterns.     

Distribution and sources of polycyclic aromatic hydrocarbons in surface sediments of the Hormuz strait,Persian Gulf

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the sediment from the Hormuz strait, Persian Gulf. The sum of 16 PAHs (ΣPAH) concentrations varied from 72.17 to 277.77 ng g⁻¹ dry weight, with an average value of 131.20 ± 59.29 ng g⁻¹ dry weight. An ecological risk assessment of PAHs, indicated that adverse biological effects caused by acenaphthene and acenaphthylene occasionally may take place in the sediment of Hormuz strait. PAH source identification showed that the PAHs in the sediments come from pyrogenic and mixed origin. Based on classification of pollution levels, sediments from Hormuz strait could be considered as low to moderately polluted with PAHs.     

Brown mussels (Perna perna) and semi-permeable membrane devices (SPMDs) as indicators of organic pollutants in the South African marine environment

A distinct lack of historical and current data on the status of organic pollutant contaminants within the South African marine environment is evident. This has highlighted the need for more current organic pollutant assessments. Reference mussels and SPMDs were transplanted at five South African harbour sites to assess organic bioaccumulation in brown mussels (Perna perna) and semi-permeable membrane devices (SPMDs). Spatial patterns of PAH and PCB contaminants were determined by GC-MS and GC-ECD after appropriate sample preparation. Significant (p<0.05) spatial differences were observed between the sites. Results indicate no correlations between the passive device and the transplanted mussels; however the SPMDs provided complementary information on the presence of dioxin-like PCBs within the environment not detected by the mussel. The results indicate that information provided by both the mussels and SPMDs allow for a more in depth scrutiny of environmental conditions as a result of anthropogenic influence.     

Vertical profile,sources, and equivalent toxicity of polycyclic aromatic hydrocarbons in sediment cores from the river mouths of Kaohsiung Harbor,Taiwan

Six sediment cores collected at four contaminated river mouths and two harbor entrances in Kaohsiung Harbor (Taiwan) were analyzed to evaluate the sources and potential toxicity of polycyclic aromatic hydrocarbons (PAHs). PAHs presented the wide variations ranging from 369 ± 656 to 33,772 ± 14,378 ng g⁻¹ at the six sampling sites. The composition of PAHs presented a uniform profile reflecting the importance of atmospheric input from vehicle exhausts or coal combustion in the river mouths. PAHs diagnostic ratios indicated a stronger influence of coal combustion in the Salt River mouth and the prevalence of petroleum combustion and mixed sources in the other rivers and harbor entrances. PAHs toxicity assessment using the mean effect range-median quotient (m-ERM-q: 0.011–1.804), benzo[a]pyrene-toxicity equivalent (TEQ^carc: 22–2819 ng TEQ g⁻¹), and dioxin-toxicity equivalent (TEQ^fish: 37–5129 pg TEQ g⁻¹) identified the Salt River mouth near the industrial area of the harbor as the most affected area.     

Biological risk and pollution history of polycyclic aromatic hydrocarbons (PAHs) in Nansha mangrove,South China

Chinese government has taken various measures to alleviate pollution caused by polycyclic aromatic hydrocarbons (PAHs) in the region of Pearl River Delta since the economic reform in 1978, but the effectiveness of these measures remains largely unknown. This study aimed to elucidate the biological risk and pollution history of PAHs by measuring the concentrations of 28 PAHs in the surface and core sediments, respectively, in Nansha mangrove. Results found that the biological risk of PAHs was low without obvious spatial variation. The PAH concentration along the depth gradient indicated that PAH pollution was stabilized since the early 1990s while the source of PAHs has gradually changed from combustion of coal to petroleum products. This implied that the mitigation measures taken by the Chinese government were effective. Compared to marine bottom sediment, we propose that using mangrove sediment can provide a more accurate and precise estimate of pollution history of PAHs.     

PAHs contamination and bacterial communities in mangrove surface sediments of the Jiulong River Estuary, China

Sixteen sediment samples collected from eight transects in a mangrove swamp of the Jiulong River Estuary, Fujian, China were investigated for their content of polycyclic aromatic hydrocarbons (PAHs) and the biodegradation potential of the indigenous microorganisms. The bacterial community structures in the mangrove sediments and in enrichment cultures were also investigated. The results showed that the total PAHs concentration of mangrove sediments ranged from 280 to 1074 ng g(-1) dry weight, that the PAHs composition pattern in the mangrove sediments was dominated by high molecular weight PAH components (4-6 rings), and that Benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene were the most dominant at different stations. Abundant PAH-degrading bacteria were found in all the stations, the values of phenanthrene-degrading bacteria ranged from 5.85 x 10(4) to 7.80 x 10(5) CFU g(-1) dry weight, fluoranthene-degrading bacteria ranged from 5.25 x 10(4) to 5.79 x 10(5) CFU g(-1) dry weight, pyrene-degrading bacteria ranged from 3.10 x 10(4) to 6.97 x 10(5) CFU g(-1) dry weight and the benzo(a)pyrene-degrading bacteria ranged from 5.25 x 10(4) to 7.26 x 10(5) CFU g(-1) dry weight. DGGE analysis of PCR-amplified 16S rDNA gene fragments confirmed that there was a remarkable shift in the composition of the bacterial community due to the addition of the different model PAH compound phenanthrene (three ring PAH), fluoranthene(four ring PAH), pyrene(four ring PAH) and benzo(a)pyrene(five ring PAH) during enrichment batch culture. Eleven strains were obtained with different morphology and different degradation ability. The presence of common bands for microbial species in the cultures and in the native mangrove sediment DNA indicated that these strains could be potential in situ PAH-degraders.     

Occurrence and phase distribution of polycyclic aromatic hydrocarbons in riverine runoff of the Pearl River Delta, China

The occurrence and phase distribution of polycyclic aromatic hydrocarbons (PAHs) in waters at the eight riverine outlets of the Pearl River Delta (China) were examined based on a monthly sampling program from March 2005 to February 2006. The total concentrations of PAHs in the aqueous phase and suspended particulate matter (SPM) combined ranged from 55.5 to 522 ng/L, at the mid level of the global values in rivers and estuaries. No clear temporal and spatial trends of PAH concentrations were found. However, the concentrations of PAHs associated with SPM coincided with the monthly precipitation of Guangzhou, indicating the importance of atmospheric deposition. The PAHs found in the region were likely derived from a combined pyrolytic and petrogenic origin, as suggested by the molecular indices of PAHs. Normalized partition coefficient (K(oc)) between water and SPM was correlated with octanol-water partition coefficient (K(ow)) to understand the environmental behavior of PAHs.     

巢湖表层沉积物中多环芳烃分布特征及来源

于2010年,采用野外采样调查、色谱分析与统计比较的方法,研究巢湖表层沉积物中27个采样点中多环芳烃(PAHs)分布特征及污染来源.结果表明:巢湖表层沉积物中检测出的14种优控PAHs总浓度为116.0~2832.2 ng/g(DW),平均值为898.9±791.0 ng/g(DW).多环芳烃组成主要以5~6环PAHs为主,占总量的32%~58%.沉积物中总有机碳含量与PAHs总量呈现良好相关性.利用蒽/(蒽+菲)与苯并[a]蒽/(苯并[a]蒽+屈)比值法对PAHs来源进行解析得出,巢湖表层沉积物中PAHs主要来源为燃烧源.与国内其它水体PAHs含量对比表明,巢湖沉积物中PAHs污染处于中等水平.生态风险评估得出南淝河表层沉积物中PAHs存在生态风险,其它采样点表层沉积物中PAHs生态风险均较低.     

多环芳烃在城市湖泊气-水界面上的交换

利用大流量采样器和半渗透膜装置对广州麓湖大气中气态多环芳烃和水体中溶解态多环芳烃进行了连续一年的观测,在此数据基础上,依据国内外通用的双膜理论计算了多环芳烃在广州麓湖水面上的交换通量.结果显示萘、苊、二氢苊的交换通量方向是由湖水挥发进入大气,其它主要化合物都是从大气进入水体;在单个化合物的交换通量中,以菲的通量值为最大,平均达13137.1ng/(m2·d),最高达到21211.22ng/(m2·d),其次为萘、荧蒽、蒽、芘、芴、二氢苊和苊等.各化合物交换通量的季节变化特点大部分都是在夏季达到最大值,在冬季交换通量降到最小值,但唯一例外的是芴,其交换通量却是在夏季降到最低值.     

Assessing the spatial variability,level and source of organic chemical contaminants in bivalve fishing grounds on the Galician coast (NW Spain)

Polychlorinated biphenyls, organochlorine pesticides, organotin compounds and triazines were quantified in sediments and bivalves collected in four areas on the Galician coast. One or several species were analysed at each site depending on their availability, including mussels (Mytilus galloprovincialis), cockles (Cerastoderma edule), clams (Venerupis pullastra and Ruditapes decussatus) and razor shells (Ensis siliqua). The general spatial distribution of contaminants was consistent in spite of the different sources of contamination. High inter-species variability was also observed. M. galloprovincialis and V. pullastra showed the highest levels of contaminants and intra-spatial variability, which highlights them as suitable species to be used as sentinel organisms. The area of O Burgo showed some worrisome results: PCB sediment concentrations were within the range that could cause biological effects. Also the level of heptachlor observed in V. pullastra was above limits accepted on edible seafood. Finally TBT concentration in mussels correlated with concentrations causing imposex in snails.     

广州麓湖水-气界面多环芳烃的通量分析

利用干湿沉降采样器、大流量采样器和半渗透膜装置对广州麓湖大气干湿沉降、大气中气态和颗粒态多环芳烃以及水体中溶解态多环芳烃进行了连续一年的采样监测,并在此数据基础上依据多环芳烃在大气和水体间的作用规律,计算了广州麓湖水-气界面上多环芳烃的交换通量．结果显示,每年大气将向麓湖中输送约1300g的多环芳烃,主要以菲为主,占总量的60%以上．而湖水向大气挥发约220g的多环芳烃,主要以萘为主,占总挥发的95%．不同化合物在气水交换中的主要作用方式是不同的,2-3环的化合物主要以气水界面交换为主,5-6环的化合物以颗粒物沉降为主．而4环的化合物则以三种方式并存．不同季节,除了4环的化合物的各种作用方式所占地比重有所变化外,其它化合物变化不大．