空气中多环芳烃的研究现状

本文比较系统地讨论了空气中多环芳烃（ＰＡＨｓ）的研究现状。重点介绍了空气颗粒物及气相中多环芳烃的采样分析新办法，城市大气及居民室内外空气中多环芳烃的污染状况及其来源，简单介绍了人体接触多环芳烃的水平，指标及空气中多环芳烃的健康风险评价的研究概况。共引文献１２９篇。     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples - impact of sources and meteorological conditions

Urban aerosol was collected in a summer and a winter campaign for 7 and 3 days, respectively. Low volume samples were taken with a time resolution of 160 min using a filter/sorption cartridge system extended by an ozone scrubber. Concentrations of mainly particle associated polycyclic aromatic hydrocarbons (PAH) and oxidised PAH (O-PAH) were determined by gas chromatography/high resolution mass spectrometry. The sampling site was located in the city centre of Augsburg, Germany, near major roads with high traffic volume. The daily concentrations and profiles were mainly governed by local emissions from traffic and domestic heating, as well as by the meteorological conditions. During the winter campaign, concentrations were more than 10 fold higher than during the summer campaign. Highest concentrations were found concurrent with low boundary layer heights and low wind speeds. Significant diurnal variation of the PAH profiles was observed. Enhanced influences of traffic related PAH on the PAH profiles were evident during daytime in summer, whereas emissions from hot water generation and domestic heating were obvious during the night time of both seasons. A general idea about the global meteorological situation was acquired using back trajectory calculations (NOAA ARL HYSPLIT4). Due to high local emissions in combination with low air exchange during the two sampling campaigns, effects of mesoscale transport were not clearly observable.     

Sizing of atmospheric particulates with a high volume cascade impactor

This article describes the development of a high volume cascade impactor with a sampling rate of 20 ft³/min that can be powered by high volume blowers in common use for air sampling. With this impactor it is now possible to collect enough sample of atmospheric particulates in a 24 hour period to conveniently determine an aerodynamic size distribution of suspended particulates by gravimetric analysis. The impactor has four stages and an after-filter and separates particles from the air stream by inertial impaction. The effective cutoff diameters for the stages are 7.0, 3.3, 2.0, and 1.1 microns. The after-filter traps the submicron material.     

Sampling Submicrometer Particles Suspended in Near Sonic and Supersonic Free Jets

This paper is concerned with sampling submicrometer particles in perisonic flows. The study employed a high volume (30-45 L/min) condensation aerosol generator to produce stearic acid particles having a mean diameter of 0.8μm and a geometric standard deviation of 1.28. The aerosol was diluted with dry air and accelerated to Mach 0.6, 0.8, 1.26, or 1.47 through a flow nozzle. Aerosol mass concentrations were determined using a small bore probe in the jet and by a large bore probe sampling isokinetically upstream of the jet nozzle. The results of both samples were compared to compute the sampling error associated with I ho high spood jot sample. The mass of stearic acid colloctod on polycarbonate mombrono flltors was determined by gravimoirlc and chromalogrophlc mothods. Studies at Mach 0.8 with four sampling probes having Inlet wall to bore area ratios ranging from 3.8 to 0.28 (a knife edge) demonstrated that probe wall thickness effects are not significant when the sample is extracted isokinetically. Subisokinetic experiments using the knife edged probe showed relative errors of 124 ± 12% when sampling at 2 0% of the isokinetic condition. The subisokinetic results are compared favorably with the extended empirical results of other authors. For the supersonic cases it is shown that the subsonic velocity downstream of the sampling probe bow shock can be used in estimating the sampling error.     

The utility of distributed air volume sets when sampling ambient air using solid adsorbents

Use of solid adsorbents for air sampling always raises questions of adequate retention, blank corrections and artifact formation. Universally valid answers to these questions are unavailable. Collection of a small set of data by sampling over a large range of air volume can provide situation-specific indications of data quality not possible with the more usual tandem bed approach. Further, it does so in a direct simple way that is especially useful in monitoring applications. The distributed air volume sampling approach is illustrated using Tenax as the adsorbent.     

Validation of a flow-through sampler for pesticides and polybrominated diphenyl ethers in air

At locations without access to the electrical grid, a flow-through sampler (FTS) collects large volumes of air for the analysis of semi-volatile organic compounds (SVOCs). To test its performance under field conditions, an FTS and a traditional pumped high volume air sampler, both using polyurethane foam (PUF) as sampling medium, were co-deployed at the campus of the University of Toronto Scarborough from August 2006 to June 2007. Polybrominated diphenyl ethers (PBDEs) and various pesticides were quantified in the samples taken by both samplers to test the FTS's applicability to relatively non-volatile and slightly polar SVOCs. Air concentrations in samples taken with the FTS over five 2-week periods compare favourably with the average of the concentrations in several 24-h active high volume samples taken during the same period. In particular, time trends, temperature dependence relationships, and isomer ratios show a reasonable agreement between the two sampling techniques. An empirical linear solvation energy relationship for predicting the apparent theoretical plate number of the PUF assembly used in the FTS illustrates the effect of chemical properties, as well as temperature and wind speed, on sampling efficiency. In the absence of electrical power, the FTS can collect SVOCs from large air volumes as reliably and quantitatively as traditional HiVol samplers, although without separating gas and particle phase.     

A high efficiency all glass sampling and concentration device for adsorptive semivolatile organics

A low-volume, inert sampling and enrichment device for semivolatile organic vapors is described. The device consists of two concentric fused silica capillaries. A small portion of the inter-capillary volume, cooled with a burst of compressed carbon dioxide, serves as a trap for the semivolatile organics. The low mass of the trap permits rapid sampling and desorption cycles suitable for applications requiring fast monitoring of semivolatile chemicals. The device is devoid of switching valves in the sampling train and consequently does not suffer from analyte loss due to irreversible adsorption or interference resulting from cross contamination. The device was successfully used for sampling low concentrations of highly adsorptive nitroaromatic compounds and is applicable for polychlorinated dibenzo-p-dioxins (PCDDs) and polyaromatic hydrocarbons (PAHs).     

High-Volume Sampling: Effect of Windborne Particulate Matter Deposited during Idle Periods

For high volume air sampling, New York State uses a random once every six days schedule. To avoid double travel, this usually requires leaving filters mounted for five days before the actual sampling period of 24 hr. The starting and stopping of the sampling is controlled by a 7 day timer. (At the maximum, it is possible that a filter could be in place for 10 days with the motor idle.) The purpose of this investigation was to determine whether the filter collects a significant weight of particulate matter during the period the motor is idle, and what effect the collected windborne particulate matter has on computed TSP concentrations.     

Apparent reaction products desorbed from tenax used to sample ambient air

Ambient air was sampled using distributed air volume sets of tandem Tenax beds. In situ estimates of retention volumes were made and sometimes found to differ greatly from literature values. Inconsistent sets of apparent concentrations not due to contamination, operating errors or blanks were often observed. Unidentified chemical reactions during sampling and/or thermal desorption are implicated. It is concluded that empirical evaluation of data from Tenax sampling of ambient air is warranted in each sampling situation.     

Adaptive sampling based on the cumulative distribution function of order statistics to delineate heavy-metal contaminated soils using kriging

Correctly classifying "contaminated" areas in soils, based on the threshold for a contaminated site, is important for determining effective clean-up actions. Pollutant mapping by means of kriging is increasingly being used for the delineation of contaminated soils. However, those areas where the kriged pollutant concentrations are close to the threshold have a high possibility for being misclassified. In order to reduce the misclassification due to the over- or under-estimation from kriging, an adaptive sampling using the cumulative distribution function of order statistics (CDFOS) was developed to draw additional samples for delineating contaminated soils, while kriging. A heavy-metal contaminated site in Hsinchu, Taiwan was used to illustrate this approach. The results showed that compared with random sampling, adaptive sampling using CDFOS reduced the kriging estimation errors and misclassification rates, and thus would appear to be a better choice than random sampling, as additional sampling is required for delineating the "contaminated" areas.     

On the efficiency of impingers with fritted nozzle tip for collection of ultrafine particles

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (～30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.     

Can pine needles indicate trends in the air pollution levels at remote sites?

Data from ten years of integrated monitoring were used here to evaluate whether pine needles are a feasible tool for an assessment of long-term trends of the atmospheric contamination. Pine needles collected once a year were compared to high volume air samples collected for 24 h, every 7 days, and passive air samples integrated over 28-day periods. Results showed the same concentration patterns of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) captured in needles and high volume samples. Passive air samplers were less efficient in sampling the particle-bound compounds. Theoretical air volume equivalent to each needle sample (V_EQ) was calculated as a ratio of the needle concentration over the mean air concentration. Results indicated different equivalent volumes for PAHs and organochlorines, possibly due to the faster degradation rates of PAHs in needles. The most important finding is that in the long term a needle monitoring gives very similar information on temporal trends of the atmospheric pollution as does a high volume air monitoring.     

Time course of isocyanate emission from curing polyurethane adhesives

The time course of isocyanate emission from curing polyurethane (PUR) resins and adhesives was studied in two different emission test chambers. The measured emissions were strongly dependent on the type of experiment. The adhesives under investigation contained different types of diisocyanates and are used for different applications, e.g. for fixing of textile floor coverings. The influence of the curing mechanism on emission was studied by comparing the emission curves of one-component adhesives (OCA) and two-component adhesives (TCA). For TCA, the decrease in isocyanate emission was found to follow a two-step process during curing. In the first step, the emission is dominated by surface evaporation, and the decay of emission is mainly caused by the decrease in monomer content due to reaction. In the second step, the release is limited by internal diffusion. The influence of monomer reactivity on the emission profile could be demonstrated for 2,4′- and 4,4′-MDI. The less-reactive 2,4′-MDI caused prolonged emission. A strong dependence of emission rates on temperature and adhesive viscosity was also obvious. The evaluation of emission rates of different commercially available PUR adhesives showed the highest emission from systems that are applied at high temperatures. The high reactivity of diisocyanates requires special techniques for sampling and analysis. Therefore, an analytical method using HPLC–MS/MS was developed that enables limits of quantitation of <5 ng/m³ with a sampling volume of 100 l.     

Sampling and analysis of particulate and gaseous polycyclic aromatic hydrocarbons from coal tar sources in the working environment

A sampling method for polycyclic aromatic hydrocarbons (PAH) in workplace atmospheres using a standard glass fiber filter with a back-up section of Amberlite XAD-2 is described. Filters and XAD are solvent-desorbed and, without further clean-up, the solutions are submitted to high performance liquid chromatographic analysis using fluorimetric detection. Recovery of PAH from XAD-2 was studied, and was found to be in the range 80–100%. The sampling method was evaluated in a coke plant, an aluminium plant and in a creosote impregnating plant. The method described is rapid and sensitive for the determination of the most important workplace PAH, and accounts for both particulate and gaseous PAH.     

Measurements of selected PCBs in open urban ambient air of Madrid (Spain)

The focus of this study was to characterize the concentration levels of selected PCBs and compare them to compiled data in order to contribute to the international database. The sampling site is located in the outskirts of Madrid and can be considered an open urban area. 32 samples of air were taken from February 1998 to June 1998 by using a high volume air sampler. Glass fiber filters and polyurethane foam (PUF) were used to collect the paniculate and gas phase material, respectively. PUF plugs were Soxhlet extracted and filters were ultrasonically extracted by using pesticide-grade hexane and dichloromethane, respectively. The cleanup procedure was carried out on a florisil column with hexane and hexane/dichloromethane as elution solvents. GC/MS in a selected ion monitoring mode was used for quantification and 29 selected PCBs congeners were analyzed.     

甲基橙分光光度法测定环境空气及工业废气中游离溴

以０．００５‰甲基橙溶液富集吸收,用分光光度法测定环境空气和工业废气中的游离溴,并对样品的采集、保存和最佳测定条件进行了研究。结果表明,方法的采样效率〉９７％,线性良好,精密度和准确度均较高,方法灵敏,按２０Ｌ采样体积计,方法的最低检出浓度为０．０２５ｍｇ／ｍ＾３。     

High Volume Sampling: Errors Incurred during Passive Sample Exposure Periods

The current Federal EPA reference method for the determination of total suspended particulate matter (TSP) in the atmosphere is the high volume method (hi-vol).¹ The hi-vol sampler is normally operated for a 24 hr period by drawing air through an 8 X 10 in. glass fiber filter at an air sampling flow rate of between 40-60 cfm. TSP samples are presently collected in this manner every 6th day (61 samples/year). Results are used to determine compliance with existing National Primary Ambient Air Quality Standards for TSP (i.e., 260 µg/m³, maximum 24 hr average, not to be exceeded more than once a year; 75 µg/m³, annual geometric mean). However, when the sampling frequency is diminished to only 61 out of a possible 365 measurements each year, the degree of certainty associated with meeting these air quality standards is also decreased.^2,3 This partial sampling schedule also introduces other sampling errors. One such error caused by the exposure of the collection filter both prior and subsequent to the desired sampling day is the subject of the following discussion.     

Main particulate matter components in Saxony (Germany)

Aerosol filter samples have been collected nearby the industrialised basin of Leipzig in Saxony (Germany) at the research station Melpitz of the Institut für Troposphärenforschung e.V. (IfT). Time series (1992–1998) and a three year comparison (1995–1997) of two different aerosol filter sampling systems, the Sierra-Andersen-PM 10 high volume sampler (daily sample, PM 10 inlet) and the Rupprecht and Patashnik Co. Inc. Model Partisol 2000 (weekly sample, PM 10 and PM 2.5 inlet) are presented and discussed. The comparison of the different sampling systems and strategies yields small differences between the daily and weekly samples for mass and different ions, which may be influenced by sampling duration and flow rates. A general trend of change in aerosol composition was observed: Soot and Sulphate concentrations decreased whereas Nitrate and Ammonium concentrations increased. During summers the mass of coarse particles is higher than in other seasons. One reason could be found in the occurence of longer periods of dry ground surfaces enabling reemission of crustal and biological material. The time series have been integrated in a longer historical aerosol mass trend for Saxony and do show a good agreement. Since 1990 a significant downward trend in gravimetric mass concentration was found.     

Fluorescent dye imaging of the volume sampled by single well forced-gradient tracer tests evaluated in a laboratory-scale aquifer physical model

This study presents a new method to visualise forced-gradient tracer tests in 2-D using a laboratory-scale aquifer physical model. Experiments were designed to investigate the volume of aquifer sampled in vertical dipole flow tracer tests (DFTT) and push-pull tests (PPT), using a miniature monitoring well and straddle packer arrangement equipped with solute injection and recovery chambers. These tests have previously been used to estimate bulk aquifer hydraulic and transport properties for the evaluation of natural attenuation and other remediation approaches. Experiments were performed in a silica glass bead-filled box, using a fluorescent tracer (fluorescein) to deduce conservative solute transport paths. Digital images of fluorescein transport were captured under ultraviolet light and processed to analyse tracer plume geometry and obtain point-concentration breakthrough histories. Inorganic anion mixtures were also used to obtain conventional tracer breakthrough histories. Concentration data from the conservative tracer breakthrough curves was compared with the digital images and a well characterised numerical model. The results show that the peak tracer breakthrough response in dipole flow tracer tests samples a zone of aquifer close to the well screen, while the sampling volume of push-pull tests is limited by the length of the straddle packers used. The effective sampling volume of these single well forced-gradient tests in isotropic conditions can be estimated with simple equations. The experimental approach offers the opportunity to evaluate under controlled conditions the theoretical basis, design and performance of DFTTs and PPTs in porous media in relation to measured flow and transport properties.