室内空气有机污染的研究现状

主要讨论了室内空气中有机物污染的研究现状。重点介绍了室内空气中多环芳烃 (PAHs)、挥发性有机物(VOCs)、醛类化合物等的污染状况及来源。简要叙述了室内空气污染的影响因素及对人体的健康风险评价。     

Passive sampling: partition coefficients for a silicone rubber reference phase

Silicone rubber sheeting can be used as a passive sampling device for hydrophobic organic contaminants in the environment to determine the available concentrations in water and sediments. Reliable sampler-water partition coefficients are required to determine the sampling rates and the dissolved contaminant concentrations in water and in sediment pore water. Log partition coefficients (logK(sr,w)) for silicone rubber-water have been estimated for 32 polycyclic aromatic hydrocarbons (PAHs), 2 deuterated PAH analogues and 32 chlorobiphenyls (CBs) using the cosolvent method, with methanol as cosolvent. Strong linear relationships were found with literature values for the corresponding log octanol-water partition coefficients (logK(ow)) for both CBs and PAHs, confirming that partitioning into the silicone rubber is strongly determined by the hydrophobicity of the compounds, which suggests logK(ow) is a good predictor of logK(sr,w) and that absorption is the main mechanism for accumulation of analytes into the silicone rubber polymer.     

Evaluation of poly-aromatic hydrocarbons (PAHs) in the aquatic species of Suez Gulf water along El-Sokhna area to the Suez refineries

The Egyptian Red Sea environment especially along El-Sokhna area to the Suez refineries (Suez) is severely contaminated with organic compounds, as well as overfishing. This may be well contributory to recent serious declines in fish stocks. Fish embryos are also particularly vulnerable to oil exposure, even at extremely low concentrations of less than one part per billion. Consequently, even traces of oil pollution at levels often considered safe for wildlife can cause severe damage to fish. Sixteen polycyclic aromatic hydrocarbons (PAHs) were investigated in ten fish species of aquatic species by high performance liquid chromatography (HPLC). The compositions of PAHs determined in all samples were measured in order to use them as chemical markers for identifying different sources of PAH pollutants in the studied region. The total content of these16 PAHs ranged from 399.616 up to 67,631.779 ng/g wet weight. The data show that these values are considered to be alarmingly high enough to cause lethal toxicity effect by accumulation. All studied aquatic species samples are characterized by relatively high concentrations of the six-membered ring PAHs. The origin of PAHs in the collected samples is either petrogenic, biogenic, or mixed petrogenic and biogenic.     

PAHs in soils and estimated air�Csoil exchange in the Pearl River Delta, South China

In this study, 74 soil samples collected from the Pearl River Delta were analyzed for polycyclic aromatic hydrocarbons (PAHs). The PAH mixture in the soils is mainly of low molecular weight compounds, with naphthalene (21.4%) and phenanthrene (21.8%) being dominant. Soil PAH levels from the Pearl River Delta are relatively low (28?C711 ng/g, averaged 192 ng/g) compared to those from urban soils in temperate regions. The mean concentration of ??PAHs generally decrease with increasing distance from the city center, with ??PAHs of paddy soils > crop soil > natural soil. PAHs in the air were measured during a year-round sampling campaign using semipermeable membrane devices, and the transfer of chemicals between the soil and air compartments were estimated. Soil?Cair fugacity quotient calculations showed a highly uncertain equilibrium position of PAHs, with net volatilization of naphthalene and fluorene, whereas net deposition of phenanthrene, fluoranthene, and pyrene, indicating a capacity for the air to supply the soil with more substances.     

Ambient Air Quality at the Site of a Former Manufactured Gas Plant

Prior to the 1950's, manufactured gas was commerciallyproduced from the pyrolysis of coal, coke, and oil atfacilities that are termed manufactured gas plants (MGPs). The constituents of residual coal tar present on many MGPsites are an environmental health concern because of theirtoxicity and the possibility for their off-site migration viawater and air. Atmospheric concentrations of five volatileorganic compounds (VOCs, e.g., benzene), sixteen polycyclicaromatic hydrocarbons (PAHs, e.g., naphthalene), and particulate matter less than 10 microns in aerodynamicdiameter (PM₁₀) were measured at the site of a former MGP. Air samples were obtained before, during, and after excavationof subterranean coal tar at the site. The results of thisinvestigation indicate that subterranean coal tar was not aprimary source of VOCs and PAHs in the local atmosphere beforeor after remediation of the site. However, excavation,treatment, blending, and transfer of the coal tar duringremediation generated concentrations of selected aromatic andsemi-volatile organic compounds that were substantiallygreater than typical ambient levels. In addition, these datasuggest that blending and mixing of coal tars could lead toexceedance of the U.S. National Ambient Air Quality Standardfor PM₁₀, although additional research is required to fullyevaluate this possibility. Nuisance odors associated with thesite remediation were likely the result of naphthalene andpossibly isomers of xylene. Air pollutant concentrationsmeasured adjacent to the excavation area and at the siteperimeter during remediation activities were less than therelevant occupational and environmental exposure limits.     

Assessment of non-occupational exposure to polycyclic aromatic hydrocarbons through personal air sampling and urinary biomonitoring

Non-occupational inhalation and ingestion exposure to polycyclic aromatic hydrocarbons (PAHs) has been studied in 8 non-smoking volunteers through personal air sampling and urinary biomonitoring. The study period was divided into 4 segments (2 days/segment), including weekdays with regular commute and weekends with limited traffic related exposures; each segment had a high or low PAH diet. Personal air samples were collected continuously from the subjects while at home, at work, and while commuting to and from work. All urine excretions were collected as individual samples during the study. In personal air samples, 28 PAHs were measured, and in urine samples 9 mono-hydroxylated metabolites (OH-PAHs) from 4 parent PAHs (naphthalene, fluorene, phenanthrene and pyrene) were measured. Naphthalene was found at higher concentrations in air samples collected at the subjects' residences, whereas PAHs with four or more aromatic rings were found at higher levels in samples taken while commuting. Urinary OH-PAH biomarker levels increased following reported high inhalation and/or dietary exposure. On days with a low PAH diet, the total amount of inhaled naphthalene during each 24-hour period was well correlated with the amount of excreted naphthols, as was, to a lesser extent, fluorene with its urinary metabolites. During days with a high dietary intake, only naphthalene was significantly correlated with its excreted metabolite. These findings suggest that this group of non-occupational subjects were exposed to naphthalene primarily through indoor air inhalation, and exposed to other PAHs such as pyrene mainly through ingestion.     

Biological monitoring versus air monitoring strategies in assessing environmental-occupational exposure

Assessment of environmental and occupational exposure to chemicals can be performed with environmental monitoring (EM) and biological monitoring (BM). Biological monitoring was for a long time considered as a method complementary to environmental monitoring. At present this attitude is changing and in certain areas biological monitoring is applied as the method of choice for exposure and health-risk assessment. This paper examines advantages and disadvantages of those two approaches. In occupational settings environmental monitoring of exposure to VOCs seems to be superior to biological monitoring (possibility of simultaneous determination of components of mixtures, simple interpretation, possibility of evaluation of short-term exposure to local irritants). In the case of this group of compounds BM can be useful in selected cases such as evaluation of dermal absorption or efficiency of protective measures. In the case of metals both forms of monitoring can be used depending on the available methods for interpretation of results. BM of exposure may be considered as superior for evaluating the effects of exposure to lead, cadmium and mercury. However, quantitative evaluation of cancer risk after exposure to arsenic or chromium is possible only on the basis of determination in the air and the use of unit risk values. Both environmental and biological monitoring are useful for evaluation of occupational and environmental exposure to polycyclic aromatic hydrocarbons (PAHs). In certain areas such as evaluation of exposure to external tobacco smoking, cytostatic drugs, and pesticides, biological monitoring is the method of choice used for individual exposure assessment or tracing the trends of environmental exposure.     

Evaluation of a simultaneous sampling method of PAHs, PCDD/Fs and dl-PCBs in ambient air

The Stockholm Convention on Persistent Organic Pollutants (POPs) was signed in May 2001 by 127 countries. Currently, 12 substances are regulated by the convention, and the work on finding new candidate chemicals to the convention has started. Among these 12 substances, dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are the objects of this study. There are no European standard methods for the simultaneous determination of these microorganic compounds, together with polycyclic aromatic hydrocarbons (PAHs) in ambient air--they must be referred to three different methods developed by the U.S. Environmental Protection Agency (EPA). The quali-quantitative analysis of these microorganic pollutants is an important challenge due to the low concentrations at which they may be present. In this study, the development of a simplified, alternative, fast and affordable sampling method for the determination of PAHs, PCDDs, PCDFs and PCBs in ambient air was performed. The sampling time was extended from 24 h to 7 d in order to enrich the sample, to fall within the instrumental limits of detection and to reduce the number of samples to be processed and, therefore, errors that may arise. First of all, experiments with labelled standards were conducted in the research area of Montelibretti (rural station, which is sited about 20 km northeast of Rome), with the purpose of optimizing sampling efficiency. Finally, the method was applied to the analysis of these compounds in the air of a suburban area with small industrial plants in order to evaluate the feasibility of the proposed sampling method system, by comparing concentrations of native compounds acquired during simultaneous daily and weekly sampling.     

A source study of atmospheric polycyclic aromatic hydrocarbons in Shenzhen, South China

Air pollution has become a serious problem in the Pearl River Delta, South China, particularly in winter due to the local micrometeorology. In this study, atmospheric polycyclic aromatic hydrocarbons (PAHs) were monitored weekly in Shenzhen during the winter of 2006. Results indicated that the detected PAHs were mainly of vapor phase compounds with phenanthrene dominant. The average vapor phase and particle phase PAHs concentration in Shenzhen was 101.3 and 26.7 ng m^???3, respectively. Meteorological conditions showed great effect on PAH concentrations. The higher PAHs concentrations observed during haze episode might result from the accumulation of pollutants under decreased boundary layer, slower wind speed, and long-term dryness conditions. The sources of PAHs in the air were estimated by principal component analysis in combination with diagnostic ratios. Vehicle exhaust was the major PAHs source in Shenzhen, accounting for 50.0% of the total PAHs emissions, whereas coal combustion and solid waste incineration contributed to 29.4% and 20.6% of the total PAHs concentration, respectively. The results clearly indicated that the increasing solid waste incinerators have become a new important PAHs source in this region.     

Kinetic of Biomarker Responses in Juveniles of the Fish Sparus aurata Exposed to Contaminated Sediments

Sediments in the National Park of the Atlantic Islands (Galicia, Spain) were affected by the spill of the tanker Prestige (November, 2002) and still present high levels of Polycyclic aromatic hydrocarbons. The adverse effects associated with the contaminants in sediments were tested using a chronic bioassay, exposing juveniles of the fish Sparus aurata (seabream). A toxicokinetic approach is proposed to evaluate sediment quality by linking chemical and ecotoxicological data along the time. Sediment samples were physicochemically characterized and the concentration of contaminants (Polycyclic aromatic hydrocarbons – PAHs – and metals) was measured. Fishes were exposed to contaminated sediments, and samples from different tissues were collected every 15 days throughout the 60 days that lasted the experiment. A biomarker of exposure (ethoxyresorufin O-deethylase activity – EROD activity) and a biomarker of effect (histopathology) were analyzed during the exposure period. Results show a relationship between the biomarkers and the concentrations in sediments of polycyclic aromatic hydrocarbons—PAHs. Besides, the toxicokinetic approach links biomarkers response providing information about the relationship between the detoxification process and the damages observed in the different tissues. The frequency of the histological damage is highest when the EROD activity slightly decreases in accordance with the mechanism of detoxification of this enzymatic system against PAHs and other organic contaminants.     

Enrichment of organic pollutants in the sea surface microlayer (SML) at Terra Nova Bay, Antarctica: influence of SML on superficial snow composition

Concentrations of dissolved and particle-associated n-alkanes, phthalates and polycyclic aromatic hydrocarbons (PAHs) were measured in sea surface microlayer (SML) and sub-surface water (SSL) samples collected in the coastal area of Terra Nova Bay, Antarctica, during the Austral spring 1998/1999. SML concentrations of the selected organic compounds were higher than SSL values and the enrichment factors were greater in the particulate phase than in the dissolved phase. During the same campaign, "fresh" snow samples, collected at different altitudes (from sea level up to 2670 m) near the coast on Mt Melbourne, immediately after a snowy event, were analysed in order to provide more information on air/sea exchange processes. The same classes of organic compounds found in sea water were also present in "fresh" snow samples. The surfactant fluorescent organic matter (SFOM), adsorbed on the microdrop aerosol surface, could be considered the main constituent of the enrichment and the carrier at higher altitudes of organic compounds. In fact, hydrocarbons (n-alkanes and PAHs), which are not surfactants like phthalates, could interact with SFOM and follow the same fate.     

南京某县空气、土壤中多环芳烃的分布及来源

采用建立的采样及分析监测程序对南京某县空气、土壤中的多环芳烃进行了调查监测,探讨了多环芳烃在空气、土壤中的分布特征、相关性及可能的污染来源.     

Polycyclic aromatic hydrocarbons study and toxic equivalency factor (TEFs) in Tehran, IRAN

Polycyclic aromatic hydrocarbons (PAHs) are toxic pollutants released by various urban combustion sources. Benzo[a]pyrene (BaP) is a representative member of the class of PAHs. Health risk assessment associated with inhalatory PAHs uptake is often estimated on the basis of the BaP concentrations in air. Atmospheric particulate PAHs concentrations were measured at five locations in Tehran, Iran. Sixteen PAHs were extracted from the airborne particles and analyzed by HPLC. Total PAHs concentrations (16 compounds) at five station Arjanteen, Enghelab, Azadi, Bahman, Haft Houz were respectively, 70.2, 96.5, 130, 79.1, 44.1 ng/m(3). The information obtain from the present study indicated that mean of human carcinogens are: benzo[a]antheracene (0.17-4.76 ng/m(3)), chrysene (1.74-3.62 ng/m(3)), benzo[b]fluoranthene (0-5.25 ng/m(3)), benzo[k]fluoranthene (0.32-1.72 ng/m(3)), benzo[a]pyrene (1.41-3.82 ng/m(3)), dibenzo[a,h]anthracene (0.33-2.13 ng/m(3)), and indeno[1,2,3-cd]pyrene (0.25-11.08 ng/m(3)). The development and the establishment of a toxicity equivalency factor (TEF) are used in the assessment of mixtures containing PAHs. The contribution of the carcinogenic potency of BaP alone is in the range of 49.6-76.3% of the total carcinogenic activity. The annual number of lung cancer cases (persons per million) among Tehran residents (population = 10 millions) attributable to these carcinogenic PAHs compounds in 2005 was estimated at 58 persons per million. In Tehran urban areas vehicular emission are the primary contributor to PAHs concentrations, with additional local contributors like industrials emissions.     

Road pavers' occupational exposure to asphalt containing waste plastic and tall oil pitch

Waste plastic (WP) and tall oil pitch (T), which are organic recycled industrial by-products, have been used as a binder with bitumen in stone mastic asphalt (SMA) and asphalt concrete (AC). We compared the exposure over one workday in 16 road pavers participating in a survey at four paving sites, using mixes of conventional asphalt (SMA, AC) or mixes containing waste material (SMA-WPT, AC-WPT). The concentrations of 11 aldehydes in air were 515 and 902 microg m(-3) at the SMA-WPT and AC-WPT worksites, being 3 and 13 times greater than at the corresponding worksites laying conventional asphalt. Resin acids (2-42 microg m(-3)), which are known sensitizers, were detected only during laying of AC-WPT. The emission levels (microg m(-3)) of total particulates (300-500), bitumen fumes (60-160), bitumen vapour (80-1120), naphthalene (0.59-1.2), phenanthrene (0.21-0.32), pyrene (<0.015-0.20), benzo(a)pyrene (<0.01) and the sum of 16 PAHs (polycyclic aromatic hydrocarbons, 1.28-2.00) were similar for conventional and WPT asphalts. The dermal deposition of 16 PAHs on exposure pads (on workers' wrist) was low in all pavers (0.7-3.5 ng cm(-2)). Eight OH-PAH biomarkers of naphthalene, phenanthrene and pyrene exposures were quantified in pre- and post-shift urine specimens. The post-shift concentrations (mean +/- SD, micromol mol(-1) creatinine) of 1- plus 2-naphthol; 1-,2-,3-,4- plus 9-phenanthrol; and 1-hydroxypyrene were, respectively, for asphalt workers: 18.1+/- 8.0, 2.41 +/- 0.71 and 0.66+/- 0.58 (smokers); 6.0+/- 2.3, 1.70+/- 0.72 and 0.27+/- 0.15 (non-smokers); WPT asphalt workers: 22.0+/- 9.2, 2.82+/- 1.11 and 0.76+/- 0.18 (smokers); 6.8+/- 2.6, 2.35+/- 0.69 and 0.46+/- 0.13 (non-smokers). The work-related uptake of PAHs was low in all pavers, although it was significantly greater in smokers than in non-smokers. The WPT asphalt workers complained of eye irritation and sore throat more than the pavers who had a much lower exposure to aldehydes and resin acids.     

Polycyclic aromatic hydrocarbons (PAHs) in the air of Chinese cities

Polycyclic aromatic hydrocarbons (PAHs) were determined in the air of 37 cities and 3 rural locations across China during the winter, spring, summer and autumn of 2005, using polyurethane foam (PUF) disks as passive air samplers (PAS). Winter and autumn concentrations in cities exceeded spring and summer values. Concentrations were amongst the highest in the world; seasonally averaged autumn/winter values in some cities in the north and north-west of China exceeded proposed European Union air quality standards. Several factors, acting in combination, influenced air concentrations. A significant negative correlation was found between average annual city concentrations and the annual average temperature, while winter time PAH concentrations correlated with estimated coal consumption. The highest total PAH concentrations and loadings of high molecular weight compounds generally occurred in major cities located on higher land (500-2000 m), where relatively cold winters and higher coal consumption occurs. Lower values occurred in cities located in the south and east China and along the coastal regions. Molecular markers indicated incomplete combustion of fossil fuels dominated the urban air and gave evidence for photo-decomposition of selected compounds.     

Characterization of polycyclic aromatic hydrocarbons in fog-rain events

Atmospheric polycyclic aromatic hydrocarbons (PAHs) mainly originate from incomplete combustion or pyrolysis of materials containing carbon and hydrogen. They exist in gas and particle phases, as well as dissolved or suspended in precipitation (fog or rain). Current studies in atmospheric PAHs are predominantly focused on fog and rainwater samples. Some sampling difficulties are associated with fog samples. This study presented the first observation of the characteristics of PAHs in fog samples using a solid phase microextraction (SPME) technique. Eighteen fog samples were collected during ten fog events from March to December 2009 in the Shanghai area. PAHs were extracted by SPME and analyzed by gas chromatography-mass spectrometry (GC-MS). As the compounds were partially soluble in water, with solubility decreasing with increasing molecular weight, low molecular weight (LMW) PAH compounds were universally found in the fog water samples. Naphthalene (NaP), phenanthrene (Phe), anthracene (Ant) and fluoranthene (Flo) were dominant compounds in fog water. The total PAH concentration in fog water ranged from 0.03 to 6.67 μg L(-1) (mean of 1.06 μg L(-1)), and was much higher in winter than in summer. The concentration of PAHs in fog or rain water decreased after undergoing a pre-rain or pre-fog wash. The average concentration of PAHs was higher in fog than in rain. Diagnostic ratio analysis suggested that petroleum and combustion were the dominant contributors to PAHs in urban Shanghai. Backward trajectories were calculated to determine the origin of the air masses, showing that air masses were mostly from the northeast territory.     

The distribution of polynuclear aromatic hydrocarbons in ambient air particulates in Singapore

Ambient air particulates were collected using high volume samplers at seven locations throughout Singapore. The particulates were analyzed for eleven polynuclear aromatic hydrocarbons (PAH) using high performance liquid chromatography (HPLC) with fluorescence detection. Several sample preparation techniques were used to determine which method would yield the most PAHs from the bulk sample matrix. PAH profiles (standardised against the concentration of benzo(a)pyrene) were obtained to characterise the different sampling sites chosen.     

Exposure of garbage truck drivers and maintenance personnel at a waste handling centre to polycyclic aromatic hydrocarbons derived from diesel exhaust

Exposure to diesel exhaust was evaluated in summer and winter by measuring vapour and particle phase polycyclic aromatic hydrocarbons (PAHs). Fifteen PAHs were simultaneously determined from the air samples obtained from truck drivers collecting household waste and maintenance personnel at a waste handling centre. The major compounds analysed from the personal air samples of exposed workers were naphthalene, phenanthrene and fluorene. The total PAH exposure (sum of 15 PAHs) of garbage truck drivers ranged from 71 to 2,660 ng m(-3) and from 68 to 900 ng m-3 in the maintenance work. The exposure of garbage truck drivers to benzo[a]pyrene (B[a]P) ranged from the mean of 0.03 to 0.3 ng m(-3) whereas no B[a]P in control samples or in those collected from maintenance workers was detected. A statistically significant difference in diesel-derived PAH exposure between the garbage truck drivers and the control group in both seasons (in summer p = 0.0022, degrees of freedom (df) 70.5; and in winter p < 0.0001, df = 80.4) was observed. Also, a significant difference in PAH exposure between the garbage truck drivers and the maintenance workers (in summer p < 0.0001, df = 50.1; and in winter p < 0.0001, df = 44.2) was obtained.     

福建省茶园土壤中多环芳烃的分布、来源分析及生态风险评价

利用高效液相色谱分析技术对福建省茶园土壤中16种多环芳烃进行了定量分析,结果表明,PAHs的总量在0.622~812.0μg/kg之间,平均值为48.4μg/kg。其组成以3环的为主,4环次之,主成分分析和PAHs特征参数分析发现,福建省茶园土壤中多环芳烃主要以燃油、木柴和煤燃烧来源为主,部分样点存在油类排放污染。生态风险评价结果显示,福建省茶园土壤中多环芳烃已具有不利生物影响效应。