Simultaneous determination of gaseous and particulate chlorinated polycyclic aromatic hydrocarbons in emissions from the scorching of polyvinylidene chloride film

An analytical method for the determination of gaseous and particulate chlorinated polycyclic aromatic hydrocarbons (ClPAHs) was investigated. By means of this method, concentrations and isomer profiles of the 27 target ClPAHs could be analyzed. To evaluate the usefulness of the method for analyzing ClPAH emissions, laboratory-scale scorching tests were performed on polyvinylidene chloride (PVDC) plastic wrap over a flame of the gas burner. Only seven of the target ClPAHs were detected, and all compounds detected had 2, 3, or 4 rings. The detected ClPAHs were present in both the particulate phase and the gaseous phase, but they were present at higher concentrations in the gaseous phase than in the particulate phase. Relationships between the number of chlorine substituents on the naphthalene/phenanthrene rings and the overall concentration and the percentage in the particulate phase were also investigated.     

GC/MS法测定润滑油基础油中多环芳烃

对润滑油基础油中多环芳烃的气相色谱/质谱(GC/MS)测定方法进行了研究,探讨了样品的提取,固相萃取柱净化等前处理方法,同时也对仪器测定条件进行了优化.结果表明,在检测润滑油基础油中多环芳烃时,经优化的GC/MS法的加标回收率和精密度均达到较满意的水平.     

超声波萃取-GC/MS法测定橡胶轮胎中的多环芳烃

建立了超声波萃取-气相色谱/质谱(GC/MS)联用测定轮胎制品中多环芳(PAHs)的分析方法.优化了超声波萃取条件,采用MS的选择离子检测方式对PAHs进行定性定量分析.结果表明,16种PAHs的平均加标回收率为75.4%～88.0%,相对标准偏差(n=5)为0.66%～11.90%,方法检出限在1.0～4.0 ng/mL.     

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.     

Determination of polycyclic aromatic hydrocarbons and substitutes (Nitro-, Oxy-PAHs) in urban soil and airborne particulate by GC-MS and NCI-MS/MS

A method involving high resolution gas chromatography combined with ion trap (HRGC-MS/MS) and negative chemical ionisation (NCI) was developed for the determination of nitrated or oxygenated polycyclic aromatic hydrocarbons (nitro-PAHs, oxy-PAHs) and other electrophilic substitutes in soil samples. Efficient clean-up was achieved by a combination of methods for the determination of PAHs in soil and nitro-PAHs in aerosol using solid phase extraction (SPE) and semipreparative high performance liquid chromatography (HPLC). In samples of surface soil from the city of Basle (Switzerland), nitro-PAHs (mainly 3-nitrofluoranthene and 1-nitropyrene) were found in concentrations between 30 and 800 ng/kg dry weight. Oxy-PAHs and parent PAHs revealed 10²-10⁴-fold higher levels. Nitro-PAHs which are up to 10⁵ times more mutagenic seem to be less persistent in soil than the parent forms, although their entire mutagenic potential has to be estimated as being on the same order of magnitude. In urban air particulate matter, the amounts of nitro-PAHs (2–62 pg/m³) were 10–100 times lower than oxyPAHs and parent PAHs which were both found in a similar range. 3-nitrobenzanthrone, a recently described suspected human carcinogen has not yet been detected. Using multivariate statistical analysis, it was possible to elucidate similarities or special characteristics of substances in a given matrix reflecting their chemical properties or specific emission sources.     

加速溶剂萃取-GC/MS法研究济南市环境空气颗粒物中的多环芳烃

以济南市为研究区域,利用TH-150C型智能中流量总悬浮颗粒物采样器采集了7个点位环境空气颗粒物样品,采用加速溶剂萃取、旋转蒸发、硅胶柱层析、氮吹仪氮吹后用GC/MS测定的实验研究方法,获得了济南市7个点位环境空气颗粒物中16种PAHs的质量浓度和ΣPAHs值.结果表明,7个点位环境空气颗粒物中ΣPAHs的含量在103...     

Ultra trace simultaneous determination of 50 polycyclic aromatic hydrocarbons in biota using pMRM GC-MS/MS

Abstract

A saponification extraction method with gas chromatography pseudo-MRM (pMRM) mass spectrometry detection was developed for the determination of 50 total polycyclic aromatic hydrocarbons (TPAH50, a combination of parent and alkylated homologues) in biota. The method was aimed at monitoring and identification of potential TPAH contaminants in bitumen impacted environments. Alkylated PAHs were determined by multi-level, quantitative calibration using parent PAHs. The developed and thoroughly validated method required only one injection for TPAH50 analysis which represents significant saving of time and expensive authentic alkylated standards. The current method was tested with certified reference mussel tissue NIST 1974c and performed well. In a comparison study, the method reached a limit of quantitation (LOQ) for the TPAH50 between 0.1 and 0.2?ng g^?1, while the QuEChERs enhanced matrix removal – lipid (EMR) kit produced by Agilent showed an LOQ of 5–10?ng g^?1. The current method relied on response factors (RF) for the quantitation of alkylated PAHs determined against parent PAHs. These RFs were shown to be stable and consistent over the course of 1 year, during which over 200 routine environmental biota monitoring samples were analyzed. The environmental biota monitoring samples analyzed include muscle, carcass and liver, with an average total PAH50 concentration of 13, 90 and 135?ng g^?1, respectively. Results show significant differences in the distributions of 1 ringed, 2 ringed, 3 ringed, 4 ringed, and 5+ ringed TPAHs between the types of biota samples.     

Behavior and prediction of photochemical degradation of chlorinated polycyclic aromatic hydrocarbons in cyclohexane

The photochemical degradation of 11 chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and the corresponding 5 parent PAHs was examined to simulate the compound’s fate on aerosol surfaces. All the ClPAHs and PAHs decayed according to the first-order reaction rate kinetics. The photolysis rates of ClPAHs varied greatly according to the skeleton of PAHs; the rates of chlorophenanthrenes (ClPhes) and 1-chloropyrene were higher than those of corresponding parent PAHs, whereas chlorofluoranthenes, 7-chlorobenz[a]anthracene and 6-chlorobenzo[a]pyrene were more stable under irradiation compared to respective parent PAH. Considering the photoproducts of ClPhes detected, the oxidation could occur immediately at positions of the highest frontier electron density. Finally, the quantitative structure-property relationship models were developed for direct photolysis half-lives and average quantum yields of the ClPAHs and parent PAHs, in which the significant factors affecting photolysis were E_LUMO+1, total energy and surface area, and E_LUMO, E_LUMO − E_HOMO and total energy, respectively.     

Characterization of particulate polycyclic aromatic hydrocarbons in the east of France urban areas

Background

Air samples collected on three different urban sites in East of France (Strasbourg, Besan?on, and Spicheren), from April 2006 to January 2007, were characterized to measure the concentrations of polycyclic aromatic hydrocarbons (PAHs) in the particulate phase (PM₁₀) and to examine their seasonal variation, diurnal variations, and emission sources.

Results

The average concentrations of ??PAHs were 12.6, 9.5, and 8.9?ng?m^?3 for the Strasbourg, Besan?on, and Spicheren sites, respectively. Strong seasonal variations of individual PAH concentrations were found at the three sampling sites, with higher levels in the winter that gradually decreased to the lowest levels in the summer. The diurnal variations of PAH concentrations in summer presented highest concentrations during the morning (04:00?C10:00) and the evening (16:00?C22:00) times, indicating the important contribution from vehicle emissions, in the three sampling sites. Furthermore, the ratio of BaP/BeP suggests that the photochemical degradation of PAHs can suppress their concentrations in the midday/afternoon (10:00?C16:00), time interval of highest global irradiance. In winter, concentrations of PAH were highest during the evening (16:00?C22:00) time, suggesting that domestic heating can potentially be an important source for particulate PAH, for the three sampling sites.

Conclusion

Diagnostic ratios were used to identify potential sources of PAHs. Results showed that vehicle emissions may be the major source of PAHs, especially in summer, with a prevalent contribution of diesel engines rather than gasoline engines at the three sites studied, independently of the seasons.     

柴油机排放多环芳香烃气/颗粒相分配研究

为了对柴油机排放PAHs在气相和颗粒相中的分配进行研究,采用了滤膜串联＂PUF/XAD-2/PUF＂吸附柱的方法采集柴油机排气中的气相和颗粒相PAHs,使用程序升温挥发（PTV）技术结合气相色谱-质谱联用（GC-MS）方法对PAHs进行了定性和定量分析。所用分析方法重复性的相对标准偏差（RSD）低于6.1%,检出限范围...     

The characterisation of polycyclic aromatic hydrocarbons emissions from burning of different firewood species in Australia

Four kinds of woods used for residential heating in Australia were selected and burned under two burning conditions in a domestic wood heater installed in a laboratory. The selected wood species included pine (Pinus radiata), red gum (Eucalvptus camaldulensis), sugar gum (Eucalyptus cladocalyx) and yellow box (Eucalyptus melliodora). The two different burning conditions represented fast burning and slow burning, with the air inlet of the combustion chamber respectively 'full open' and 'half open'. By sampling and analysing particulate and gaseous emissions from the burning of each load of wood under defined experimental conditions, PAHs emissions and their profiles in the particulate and gaseous phases were obtained. 16 species out of the 18 selected PAHs were detected. Of these, seven species were detected in the gaseous phase and most were lower molecular weight compounds.Similarly, more than 10 species of PAHs were detected in the particulate phase and these were mostly heavier molecular weight compounds. Under both burning conditions, emission levels for total PAHs and total genotoxic PAHs were the highest for pine and lowest for sugar gum, with red gum being the second highest, followed by yellow box. Using the specific sampling method, gaseous PAHs accounted for above 90% mass fraction of total PAHs in comparison to particulate PAHs (10%). The majority of the genotoxic PAHs were present in the particulate phase. PAHs emission levels in slow burning conditions were generally higher than those in fast burning conditions.     

Distribution of polycyclic aromatic hydrocarbons in agricultural soils in South Korea

The content and type of polycyclic aromatic hydrocarbons (PAH) in soils from paddy fields and upland areas in South Korea were determined using gas chromatography linked to mass spectrometry (GC–MS). The distribution map of total PAH content was obtained as a contour plot using a geographical information system. The overall distribution of PAH was found to be closely related to the pollution sources, the size of city and the type of industry. The average content of total PAH in all samples was 236 μg kg⁻¹, and the range was from 23.3 to 2834 μg kg⁻¹. The highest concentrations were found in soils sampled near iron processing plants. The concentration of PAH decreased in the order fluoroanthene>benzo(b)fluoroanthene>pyrene. Special PAH compound ratios, such as phenanthrene/anthracene and fluoroanthene/pyrene, were calculated to evaluate the origin. The collected data suggested that the pyrogenic origins such as motor vehicle exhaust and heavy industry emission were the dominant source of PAH in Korean soils.     

Characterization and concentrations of polycyclic aromatic hydrocarbons in emissions from different heating systems in Damascus,Syria

Traffic has long been recognized as the major contributor to polycyclic aromatic hydrocarbon (PAH) emissions to the urban atmosphere. Stationary combustion sources, including residential space heating systems, are also a major contributor to PAH emissions. The aim of this study was to determine the profile and concentration of PAHs in stack flue gas emissions from different kinds of space heaters in order to increase the understanding of the scale of the PAH pollution problem caused by this source. This study set out to first assess the characteristics of PAHs and their corresponding benzo[a]pyrene equivalent emissions from a few types of domestic heaters and central heating systems to the urban atmosphere. The study, enabled for the first time, the characterization of PAHs in stationary combustion sources in the city of Damascus, Syria. Nine different types of heating systems were selected with respect to age, design, and type of fuel burned. The concentrations of 15 individual PAH compounds in the stack flue gas were determined in the extracts of the collected samples using high-performance liquid chromatography system (HPLC) equipped with ultraviolet–visible and fluorescence detectors. In general, older domestic wood stoves caused considerably higher PAH emissions than modern domestic heaters burning diesel oil. The average concentration of ΣPAH (sum of 15 compounds) in emissions from all types of studied heating systems ranged between 43?±?0.4 and 316?±?1.4 μg/m³. Values of total benzo[a]pyrene equivalent ranged between 0.61 and 15.41 μg/m³.     

Emission factors of particulate matter,polycyclic aromatic hydrocarbons,and levoglucosan from wood combustion in south-central Chile

In south-central Chile, wood stoves have been identified as an important source of air pollution in populated areas. Eucalyptus (Eucalyptus globulus), Chilean oak (Nothofagus oblique), and mimosa (Acacia dealbata) were burned in a single-chamber slow-combustion wood stove at a controlled testing facility located at the University of Concepción, Chile. In each experiment, 2.7–3.1 kg of firewood were combusted while continuously monitoring temperature, exhaust gases, burn rate, and collecting particulate matter samples in Teflon filters under isokinetic conditions for polycyclic aromatic hydrocarbon and levoglucosan analyses. Mean particulate matter emission factors were 2.03, 4.06, and 3.84 g/kg dry wood for eucalyptus, oak, and mimosa, respectively. The emission factors were inversely correlated with combustion efficiency. The mean emission factors of the sums of 12 polycyclic aromatic hydrocarbons in particle phases were 1472.5, 2134.0, and 747.5 μg/kg for eucalyptus, oak, and mimosa, respectively. Fluoranthene, pyrene, benzo[a]anthracene, and chrysene were present in the particle phase in higher proportions compared with other polycyclic aromatic hydrocarbons that were analyzed. Mean levoglucosan emission factors were 854.9, 202.3, and 328.0 mg/kg for eucalyptus, oak, and mimosa, respectively. Since the emissions of particulate matter and other pollutants were inversely correlated with combustion efficiency, implementing more efficient technologies would help to reduce air pollutant emissions from wood combustion.

Implications: Residential wood burning has been identified as a significant source of air pollution in populated areas. Local wood species are combusted for home cooking and heating, which releases several toxic air pollutants, including particulate matter, carbon monoxide, and polycyclic aromatic hydrocarbons. Air pollutant emissions depend on the type of wood and the technology and operational conditions of the wood stove. A better understanding of emissions from local wood species and wood stove performance would help to identify better biomass fuels and wood stove technologies in order to reduce air pollution from residential wood burning.     

Oxidation of polycyclic aromatic hydrocarbons by fungal isolates from an oil contaminated refinery soil

BACKGROUND AND OBJECTIVE: Indigenous soil microorganisms are used for the biodegradation of petroleum hydrocarbons in oily waste residues from the petroleum refining industry. The objective of this investigation was to determine the potential of indigenous strains of fungi in soil contaminated with petroleum hydrocarbons to biodegrade polycyclic aromatic hydrocarbons (PAH). MATERIALS AND METHODS: Twenty one fungal strains were isolated from a soil used for land-farming of oily waste residues from the petrochemical refining industry in Singapore and identified to genus level using laboratory culture and morphological techniques. Isolates were incubated in the presence of 30 mg/L of phenanthrene over a period of 28 days at 30 degrees C. The most effective strain was further evaluated to determine its ability to oxidise a wider range of PAH compounds of various molecular weight i.e acenaphthene, fluorene, fluoranthene, chrysene, benzo(a)pyrene and dibenz(ah)anthracene RESULTS AND DISCUSSION: After 28 days of incubation, 18 of the 21 fungal cultures were capable of oxidising over 50% of the phenanthrene present in culture medium, relative to abiotic controls. Fungal isolate, Penicillium sp. 06, was able to oxidise 89% of the phenanthrene present. This isolate could also oxidise more than 75% of the acenaphthene, fluorene and fluoranthene after 30 days of incubation. However, the oxidation of high molecular weight PAH i.e. chrysene, benzo(a)pyrene and dibenz(ah)anthracene by the Penicillium sp. 06 isolate was limited, where the extent of oxidation was inversely proportional to PAH molecular weight. CONCLUSIONS: Fungal isolate, Penicillium sp. 06, was effective at oxidising a range of PAH in petroleum contaminated soils, but higher molecular weight PAH were more recalcitrant. RECOMMENDATIONS AND OUTLOOK: There is potential for the re-application of this fungal strain to soil for bioremediation purposes.     

采油废水中多环芳烃的生态风险评价

先利用C-18固相萃取小柱富集大港油田港东联合处理站污水处理站的采油废水中16种多环芳烃(PAHs,即萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、茚并[1,2,3-cd]芘、二苯并[a,h]蒽和苯并[g,h,i]苝),再用气相色谱/质谱(GC/MS)分析测定其浓度,以评价PAHs的去除率和生态风险。结果表明:(1)采油废水经处理后,COD、石油类去除率分别达到82.27%、91.06%;外排水COD、石油类达到《污水综合排放标准》(GB 8978—1996)一级标准要求,优于中国采油废水处理的一般水平。(2)采油废水主要以2、3环的PAHs为主,约占总量的93%以上。(3)苯并[a]芘超过《地表水环境质量标准》(GB 3838—2002)中限值。(4)处理前的采油废水中蒽、菲和苯并[a]芘具有一定的生态风险;处理后的外排水中萘、蒽、菲、荧蒽、苯并[a]芘的暴露浓度(PEC)/预测无效应浓度(PNEC)均小于1,目前尚未对环境造成威胁。但是8种PAHs(苊烯和苯并类PAHs除外)总和表现出较大的毒性,需要引起重视。     

Distribution of polycyclic aromatic hydrocarbons in water, suspended particulate matter and sediment from Daliao River watershed, China

This study investigated the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in surface water, suspended particulate matter (SPM) and sediment of Daliao River watershed composed of the Hun River, Taizi River, and Daliao River. The sources of PAHs were evaluated employing ratios of specific PAHs compounds and principal component analysis (PCA). The total concentrations of PAHs ranged from 946.1 to 13448.5 ng l(-1) in surface water, from 317.5 to 238518.7 ng g(-1) dry weight in SPM, and from 61.9 to 840.5 ng g(-1) dry weight in sediments. The levels of PAHs are relatively higher in water and SPM, and lower in sediments, in comparison with those reported for other rivers and marine systems around the world. The composition of PAHs in these mediums was mainly 4-6 rings PAHs. The higher contents of low molecular weight PAHs in the water and SPM suggest a relatively recent local source of PAHs, entered into the river via wastewater discharge and atmospheric way. On the other hand, the heavy pollution of PAHs in sediment and water near heavy industrial area suggests that PAHs have been released from industrial wastewater.     

Occurrence of gaseous and particulate polycyclic aromatic hydrocarbons in the urban atmosphere: study of sources and ambient temperature effect on the gas/particle concentration and distribution

The presence of polycyclic aromatic hydrocarbons (PAHs) in an urban region (Heraklion, Greece) and processes that govern their atmospheric fate were studied from November 2000 until February 2002. Sixteen samples were collected, by using an artifact-free sampling device, on a monthly basis and the concentration of PAHs in gas and particulate phase was determined. The most abundant members (gas + particles) were phenanthrene (20.0+/-7.0 ng m(-3)), fluoranthene (6.5+/-1.7 ng m(-3)), pyrene (6.6+/-2.4 ng m(-3)), and chrysene (3.1+/-1.5 ng m(-3)). Total concentration (gas+particulate) of PAH ranged from 44.3 to 129.2 ng m(-3), with a mean concentration of 79.3 ng m(-3). Total concentration of PAHs in gas phase ranged from 31.4 to 84.7 ng m(-3) with non-observable seasonal variation. Conversely, maximum PAH concentrations in the particulate phase occurred during winter months. Particulate concentration varied from 11.4 to 44.9 ng m(-3), with an average of 25.2 ng m(-3). PAH distribution between gas and particulate phase was in agreement with the sub-cooled vapor pressure. Shift in gas/particle distribution due to difference in ambient temperature elucidated to some extent the seasonal variation of the concentration of PAHs in particles.     

Emission factors and particulate matter size distribution of polycyclic aromatic hydrocarbons from residential coal combustions in rural Northern China

Coal consumption is one important contributor to energy production, and is regarded as one of the most important sources of air pollutants that have considerable impacts on human health and climate change. Emissions of polycyclic aromatic hydrocarbons (PAHs) from coal combustion were studied in a typical stove. Emission factors (EFs) of 16 EPA priority PAHs from tested coals ranged from 6.25 ± 1.16 mg kg^?1 (anthracite) to 253 ± 170 mg kg^?1 (bituminous), with NAP and PHE dominated in gaseous and particulate phases, respectively. Size distributions of particulate phase PAHs from tested coals showed that they were mostly associated with particulate matter (PM) with size either between 0.7 and 2.1 μm or less than 0.4 μm (PM_0.4). In the latter category, not only were more PAHs present in PM_0.4, but also contained higher fractions of high molecular weight PAHs. Generally, there were more than 89% of total particulate phase PAHs associated with PM_2.5. Gas-particle partitioning of freshly emitted PAHs from residential coal combustions were thought to be mainly controlled by absorption rather than adsorption, which is similar to those from other sources. Besides, the influence of fuel properties and combustion conditions was further investigated by using stepwise regression analysis, which indicated that almost 57 ± 10% of total variations in PAH EFs can be accounted for by moisture and volatile matter content of coal in residential combustion.     

Spatial and temporal variations and mobile source emissions of polycyclic aromatic hydrocarbons in Quito, Ecuador

Motor vehicles are a major source of air pollution in Quito, Ecuador; however, little work has been done to characterize spatial and temporal variations in traffic-related pollutants, or to measure pollutants in vehicle emissions. We measured PAH continuously for one year at two residential sites in Quito, and PAH and traffic patterns for one week near a busy roadway. Morning rush-hour traffic and temperature inversions caused daily PAH maxima between 06:00 and 08:00. SO₂, NO_x, CO, and PM_2.5 behaved similarly. At the residential sites PAH levels during inversions were 2-3-fold higher than during the afternoon, and 10-16-fold higher than 02:00-03:00 when levels were lowest. In contrast, at the near-roadway site, PAH concentrations were 3-6-fold higher than at the residential sites, and the effects of inversions were less pronounced. Cars and buses accounted for >95% of PAH at the near-roadway site. Near-roadway PAH concentrations were comparable to other polluted cities.