Solid vapor pressure for five heavy PAHs via the Knudsen effusion method

Polycyclic aromatic hydrocarbons (PAHs) are compounds resulting from incomplete combustion and many fuel processing operations, and they are commonly found as subsurface environmental contaminants at sites of former manufactured gas plants. Knowledge of their vapor pressures is the key to predict their fate and transport in the environment. The present study involves five heavy PAHs, i.e. benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and dibenz[a,h]anthracene, which are all as priority pollutants classified by the US EPA. The vapor pressures of these heavy PAHs were measured by using Knudsen effusion method over the temperature range of 364 K to 454 K. The corresponding values of the enthalpy of sublimation were calculated from the Clausius-Clapeyron equation. The enthalpy of fusion for the 5 PAHs was also measured by using differential scanning calorimetry and used to convert earlier published sub-cooled liquid vapor pressure data to solid vapor pressure in order to compare with the present results. These adjusted values do not agree with the present measured actual solid vapor pressure values for these PAHs, but there is good agreement between present results and other earlier published sublimation data.     

Odd-Even Effects on Transport Properties of Polycyclic Arene Molecular Devices with Decreasing Numbers of Benzene Rings

The electron transport properties of polycyclic aromatic hydrocarbons (PAHs) with different numbers of benzene rings tethered to narrow zigzag graphene nanoribbon (ZGNR) electrodes have been investigated. Results show that the transport properties of PAHs are dependent on whether the number of benzene rings in the width direction is odd or even. This effect is strong for narrow width PAHs, but its strength decreases as the width of the PAH is increased. PAHs with an odd number of rings exhibit poor transport properties, whereas the ones having an even number of rings show excellent transport properties coupled with a negative differential resistance (NDR) effect. Moreover, the linkage points and the structure of the molecules have a noticeable effect on the transport properties of the PAH, making the odd-even effect weaker or disappear entirely. Although the PAH with three benzene rings displays poor transport capabilities, it shows excellent rectification behavior compared to the other examined molecules. These studies present a feasible avenue for designing molecular devices with enhanced performance by the careful manipulation of the PAH molecular structure.     

Beyond nC60: strategies for identification of transformation products of fullerene oxidation in aquatic and biological samples

Owing to their exceptional properties and versatility, fullerenes are in widespread use for numerous applications. Increased production and use of fullerenes will inevitably result in accelerated environmental release. However, study of the occurrence, fate, and transport of fullerenes in the environment is complicated because a variety of surface modifications can occur as a result of either intentional functionalization or natural processes. To gain a better understanding of the effect and risk of fullerenes on environmental health, it is necessary to acquire reliable data on the parent compounds and their congeners. Whereas currently established quantification methods generally focus on analysis of unmodified fullerenes, we discuss in this review the occurrence and analysis of oxidized fullerene congeners (i.e., their corresponding epoxides and polyhydroxylated derivatives) in the environment and in biological specimens. We present possible strategies for detection and quantification of parent nanomaterials and their various derivatives.     

Comparing the weathering patterns of six oils using 3-way generalized Procrustes rotation and matrix-augmentation principal components

A case study is presented in which advanced chemical fingerprinting and data interpretation techniques are used to characterize and compare the weathering processes of six oil spillages made under controlled conditions (including the heavy oil released after the Prestige tanker sunk off the Galician coast-NW Spain on 2002). A tiered analytical approach using gas chromatography-flame ionization detection (GC-FID) and gas chromatography-mass spectrometry (GC-MS) was applied along with two different approaches for 3-way analyses; namely, generalized Procrustes rotation, and matrix-augmented principal components analysis. Results showed that the two 3-way chemometric techniques leaded to essentially the same conclusions when analyzing three sets of compounds fingerprinting the spilled hydrocarbons (aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs) and a set of diagnostic ratios). A steady evolution on the weathering of the oils was observed with both techniques, but for the diagnostic ratios. The variables involved on the weathering were the lightest aliphatic hydrocarbons and a general combination of the PAHs, which differentiated mostly among the light and the heavy products (fuel oils).     

Polycyclic aromatic hydrocarbons in the centralized wastewater treatment plant of a chemical industry zone: Removal, mass balance and source analysis

Increased attention has been given to the fate of pollutants such as polycyclic aromatic hydrocarbons (PAHs) introduced to the wastewater treatment plants.Dissolved and adsorbed PAHs were detected in the centralized wastewater treatment plant of a chemical industry zone in Zhejiang Province,China.The most abundant PAHs were the low molecular weight PAHs (e.g.,Acy,Ace,Flu and Phe),accounting for more than 80% of the total 16 PAHs in each treatment stage.Phase partitioning suggested that the removal of PAHs in every treatment stage was influenced greater by the sorption of particles or microorganisms.The removal efficiencies of individual PAHs ranged between 4% and 87% in the primary sedimentation stage,between 1% and 42% in anaerobic hydrolysis stage,between <1% and 70% in aerobic bio-process stage,between 1.5% and 80% in high-density clarifier stage,and between 44% and 97% in the whole treatment process.Mass balance calculations in primary stage showed significant losses for low molecular weight PAHs and relatively good agreements for high molecular weight PAHs as well as in anaerobic hydrolysis,high-density clarifier stage and sludge stream for most PAHs.Great gains of 60%-150% were obtained for high molecular weight PAHs in aerobic bio-process stage due to biosorption and bioaccumulation.Our investigations found that PAHs entering the wastewater treatment plant (WWTP) could be derived from the dyeing chemical processes as the byproducts,and the contribution supported by the largest dyeing chemical group was up to 48%.     

综合模拟风化条件下渤海原油中生物标志物及多环芳烃风化规律研究

该文以渤海原油SZ36-1为研究对象进行综合模拟风化实验,探讨了原油中生物标志物及5类多环芳烃(PAHs)组分的分布情况及风化规律。结果表明:经过30 d风化,渤海原油SZ36-1中大部分生物标志物表现出强的稳定性,部分PAHs的分布发生较大改变,其中萘系列化合物损失最严重,相对浓度的损失达80.34%;菲、二苯并噻吩、、芴系列则相对稳定;经t检验分析风化样品测试数据,生物标志物诊断比值表现出良好的稳定性,所选取多环芳烃新诊断比值中,菲和系列、烷基取代二苯并噻吩类、烷基取代芴类的抗风化能力较强,可用于油源鉴别。     

GC-MS法测定大气样品的前处理研究--碳化纤维树脂捕集大气中痕量多环芳烃

研究了碳化纤维树脂吸附载体采集大气中多环芳烃(PAHs)的性能、样品前处理条件和毛细管气相色谱－质谱联用仪检测PAHs的,地具有代表性的多个采样点进行了实地采样、分析,证明碳化纤维树脂吸附载体是一种性能独特的固相吸附剂,建立的样品前处理方法可行,分析数据可靠,可用于大气中PAHs的检测。     

Source Apportionment Research of Fine Particulate Matter in the Atmosphere by PAHs

Haze weather frequently occurs in many cities in China. Polycyclic aromatic hydrocarbons(PAHs) in fine particulate matter(PM_2.5) can adversely affect the environment and human health. In this paper, PM_2.5 samples were collected at nine sites in a city in northeastern China from September 2013 to October 2014. Sixteen USEPA(US Evironment Protection Agency) priority PAHs in PM_2.5 were analyzed to determine their spatial and temporal distribution characteristics. The source apportionment of PAHs was conducted with the Positive Matrix Factorization(PMF) model. The results indicate that the concentrations of total PAHs(T-PAHs) in PM_2.5 are within the range of 0.26 to 72.48 ng/m³. The seasonal variation of T-PAHs is winter >spring >autumn >summer, and the space distribution of PAHs is JZP >DP >BFH >LP >EESA >IPT >CP >HZMC >JYP. In all types of PAHs, three-ring and five-ring PAHs are significantly prominent(62%) in the heating period due to petrogenic sources and traffic emissions. Middle- and high-ring PAHs in the non-heating period are caused by coal combustion and vehicle exhaust, which accounts for 77% of the total emissions. The source apportionment results obtained by the diagnostic ratio of PAHs reflect that coal burning, traffic and other sources have a distinct influence on PAH emissions in this city. Six factors are defined by PMF v5.0, namely, coke oven emissions(7.7%), biomass burning(44.3%), petrogenic sources(10.7%), coal combustion(10.4%), gasoline engine emissions(16.7%), and diesel engine emissions(10.3%). The results indicate that the PAHs in PM_2.5 in the city are primarily caused by combustion processes and vehicle exhaust.     

Raman spectroscopic analysis of minerals and organic molecules of relevance to astrobiology

Characteristic geological features and hydrated minerals recently found on the surface of Mars by the NASA planetary rovers Spirit and Opportunity suggest that a possible biosphere could have once existed there. Analytical instrumentation protocols for the unequivocal detection of biomarkers in suitable geological matrices are critical for future unmanned explorations, including the forthcoming ESA-ExoMars mission scheduled for 2018. Raman spectroscopy is currently a part of the Pasteur instrumentation suite of the ExoMars mission scheduled for 2018 for the remote detection of extant or extinct life signatures in the Martian surface and subsurface. Terrestrial analogues of Martian sites have been identified, and the biogeological modifications incurred as a result of extremophilic survival activity have been studied. Polyaromatic hydrocarbons (PAHs) are recognised as a class of degradation product that occur from biological processes terrestrially. In this work, various concentrations of polyaromatic hydrocarbons in matrices of gypsum, calcite and quartz have been investigated by Raman microspectrometry to determine the lowest detectable organic levels. The studies are conceived in simulation of their potential PAHs identification in geobiological conditions in Martian scenarios. Two laser source wavelengths, namely, 785 and 633 nm, were adopted to excite Raman spectra from the PAHs, which represent degraded carbons and therefore potentially provide a key bimolecular marker of ancient life.     

土壤中多环芳烃修复技术的研究进展

近年来我国的土壤污染问题日益严重,严重危害着人类的生活环境与身体健康,其中主要的有机污染物之一为多环芳烃(PAHs)。PAHs作为一种持久性有机污染物在全球范围内广泛存在,其主要污染来源于人为因素。由于PAHs复杂的杂环芳环结构、较强的疏水性和较高的热稳定性等,使其在土壤中不易自然降解因而具有较高的持久性。本文综述PAHs的主要污染来源、暴露途径及其对人体的危害,并从物理、化学和生物三个方面简要介绍土壤中PAHs的修复方法,并分析每种方法的优势以及面临的挑战。新兴的修复技术结合三种修复技术的优点,具有更好的修复效果和应用前景,但仍存在着一些亟待解决的问题。期望本文能为土壤中PAHs的修复提供借鉴,并为今后的研究方向提供新的思路。     

META 4. Prediction of the metabolism of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are widely distributed in the environment and are often implicated as potential carcinogens. It is generally believed that the carcinogenic potential of polycyclic aromatic hydrocarbons is linked to the formation of ultimate carcinogens generated by metabolic biotransformations. In this paper we propose a methodology that consists of using both quantum chemical properties and structural features of the reaction sites to predict PAH metabolism. Two essential questions have been answered: at which sites will the reaction take place and does the transformation consist of epoxidation or hydroxylation? This methodology has been successfully implemented into an expert system, META, for the evaluation of metabolic transformations of new chemicals. Received: 3 April 1998 / Accepted: 6 July 1998 / Published online: 7 October 1998     

Environmental aspects of PAH biodegradation

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants, some of which are on the US Environmental Protection Agency priority pollutant list. Consequently, timely clean-up of contaminated sites is important. The lower-mol-wt PAHs are amenable to bioremediation; however, higher-mol-wt PAHs seem to be recalcitrant to microbial degradation. The rates of biodegradation of PAHs are highly variable and are dependent not only on PAH structure, but also on the physicochemical parameters of the site as well as the number and types of microorganisms present. PAHs sorb to organic matter in soils and sediments, and the rate of their desorption strongly influences the rate at which microorganisms can degrade the pollutants. Much of the current PAH research focuses on techniques to enhance the bioavailability and, therefore, the degradation rates of PAHs at polluted sites. Degradation products of PAHs are, however, not necessarily less toxic than the parent compounds. Therefore, toxicity assays need to be incorporated into the procedures used to monitor the effectiveness of PAH bioremediation. In addition, this article highlights areas of PAH research that require further investigation.     

Behaviour of polycyclic aromatic hydrocarbons in dissolved,colloidal, and particulate phases in sedimentary cores

Solid-phase microextraction (SPME) has been successfully used for extracting polycyclic aromatic hydrocarbons (PAHs) from porewater samples from the Mersey Estuary, UK. The majority of the PAHs in porewater samples are associated with colloids due to the high DOC concentrations. The truly dissolved PAH concentrations varied from 66 to 1050?ng?L^?1 in core 2 and from 95 to 740?ng?L^?1 in core 3, and were dominated by naphthalene, fluoranthene, and pyrene. Although absent in the dissolved phase, the high-molecular-mass compounds were found in the colloid-associated fraction of porewater. PAHs in sediments arose from a range of compounds with 4- and 5-ring PAHs dominating. The partitioning of PAHs between sediment and porewater shows that PAHs are enriched in the sediment phase. When the soot carbon content was considered, predictions of the partition behaviour were found to agree more closely with the observed distribution. The results reiterate the importance of evaluating the speciation of organic pollutants in both porewater and sediments in order to accurately predict their environmental fate and potential toxicity.     

Investigation on the binding of polycyclic aromatic hydrocarbons with soil organic matter: a theoretical approach

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants of the terrestrial environment that have been designated as Environmental Protection Agency (EPA) Priority Pollutants. In this study, molecular modeling was used to examine the physical and chemical characteristics of soil organic matter (SOM), fulvic acid (FA) and humic acid (HA), as well as their binding interactions with PAHs. The molecular structures of 18 PAHs were built by using the SYBYL 7.0 program and then fully optimized by a semiempirical (AM1) method. A molecular docking program, AutoDock 3.05, was used to calculate the binding interactions between the PAHs, and three molecular structure models including FA (Buffle's model), HA (Stevenson's model) and SOM (Schulten and Schnitzer's model). The pi-pi interactions and H-bonding interactions were found to play an important role in the intermolecular bonding of the SOM/PAHs complexes. In addition, significant correlations between two chemical properties, boiling point (bp) and octanol/water partition coefficient (Log K(ow)) and final docking energies were observed. The preliminary docking results provided knowledge of the important binding modes to FA, HA and SOM, and thereby to predict the sorption behavior of PAHs and other pollutants.     

Coke wastewater treatment methods: Mini review

Coke wastewater production and its treatment is an alarming issue worldwide. Coke oven produces coke wastewater with a highly loaded and contaminated stream. Coke wastewater with high BOD (biochemical oxygen demand), COD (chemical oxygen demand), and nutrients impart serious threat if disposed of without treatment. It also contains phenol, ammonia, cyanide, thiocyanate & polycyclic aromatic hydrocarbons (PAHs). Because of composition and specificity of coke oven pollutants, appropriate selection of treatment method is a crucial step. The present literature review found that efficient treatment of coke wastewater can be done either by chemical or biological method. The chemical method is mostly performed by coagulation followed by sedimentation or flocculation, while biological method is preferably activated sludge process or nitrification/denitrification processes. An extensive review study on possible treatment methodologies of coke wastewater has been performed. This study focuses on comparison of performance of various treatment methods for coke wastewater.     

Comparison of dopants for charge exchange ionization of nonpolar polycyclic aromatic hydrocarbons with reversed-phase LC-APPI-MS

Atmospheric pressure photoionization (APPI) is capable of ionizing nonpolar compounds in LC/MS, through charge exchange reactions following photoionization of a dopant. Recently, several novel dopants-chlorobenzene, bromobenzene, 2,4-difluoroanisole, and 3-(trifluoromethyl)anisole-have been identified as having properties making them well-suited to serve as dopants for charge exchange ionization under reversed-phase LC conditions. Here, we report the results of experiments comparing their effectiveness to that of established dopants-toluene, anisole, and a toluene/anisole mixture, for the charge exchange ionization of model nonpolar compounds-the 16 polycyclic aromatic hydrocarbons (PAHs) identified by the US EPA as priority pollutants-when using a conventional reversed-phase LC method. Chloro- and bromobenzene were found to be much more effective than toluene for all the PAHs, due to the relatively low reactivity of their photoions with the solvent. Their overall performance was also better than that of anisole, due to anisole's ineffectiveness toward higher-IE compounds. Further, the experiments revealed that anisole's performance for higher-IE compounds can be dramatically improved by introducing it as a dilute solution in toluene, rather than neat. The two fluoroanisoles provided the highest overall sensitivity, by a slim margin, when introduced as dilute solutions in either chloro- or bromobenzene.     

Fate of Petroleum Hydrocarbons in the Sediment of Coastal Water

Assessment of the concentrations of petroleum hydrocarbons and their fate in marine environment is very important and necessary for marine environment scientists. In order to study the ecotoxicological effects of this kind of pollutants on marine ecological system, the fate of petroleum hydrocarbons in sediment of coastal water has been studied under natural conditions by Chromatography-FID.     

Development of a fast analytical tool to identify oil spillages employing infrared spectral indexes and pattern recognition techniques

A fast analytical tool based on attenuated total reflectance mid-IR spectrometry is presented to evaluate the origin of spilled hydrocarbons and to monitor their fate on the environment. Ten spectral band ratios are employed in univariate and multivariate studies (principal components analysis, cluster analysis, density functions - potential curves - and Kohonen self organizing maps). Two indexes monitor typical photooxidation processes, five are related to aromatic characteristics and three study aliphatic and branched chains. The case study considered here comprises 45 samples taken on beaches (from 2002 to 2005) after the Prestige carrier accident off the Galician coast and 104 samples corresponding to weathering studies deployed for the Prestige's fuel, four typical crude oils and a fuel oil. The univariate studies yield insightful views on the gross chemical evolution whereas the multivariate studies allow for simple and straightforward elucidations on whether the unknown samples match the Prestige's fuel. Besides, a good differentiation on the weathering patterns of light and heavy products is obtained.     

Effect of supercritical fluid extraction parameters and clay properties on the efficiency of phenanthrene extraction

Clay soils have specific properties that cause difficulty in the assessment and remediation of contaminated sites. Furthermore, polyaromatic hydrocarbons, when present in soil, are difficult to extract due to their nonpolar, high molecular weight characterization. In this study, the supercritical fluid (carbon dioxide) extraction (SFE) technique, with and without methanol modifier, was used for removal of PAHs (phenanthrene) from kaolinite, illite, and montmorillonite soils. The impact of SFE parameters (fluid pressure, fluid temperature, and time), and of clay properties (such as clay minerals content, initial moisture content, soil porosity or equivalent pores size, clay surface area, cation-exchange capacity, and clay-swelling index) on the removal efficiency of PAHs from clayey soils were investigated. The results of this investigation were used to develop a semi-empirical correlation between the recovery (i.e. the extraction efficiency) at any time and above mentioned parameters and properties.