Analysis of polycyclic aromatic hydrocarbons by sensitized room temperature phosphorescence

Direct and selective simultaneous determination of several polycyclic aromatic hydrocarbons by sensitized room temperature phosphorescence in sodium dodecylsulphate micellar solutions was studied. This approach improved, for example, the selectivity factor in determining pyrene in the presence of fluoranthene by a factor of 350, and determined benz[a]anthracene and anthracene in the presence of pyrene with the selectivity factors as high as 200–220. Triphaflavine and acridine orange as triplet energy donors, thallium (I) nitrate as a heavy atom, and sodium sulphite were used as scavengers of oxygen. A comparative study of linear concentration ranges, detection limits and selectivity factors is presented here for pyrene, benz[a]anthracene and anthracene determination by fluorescence, phosphorescence and sensitized phosphorescence. Electronic Publication     

Transmembrane transport of polycyclic aromatic hydrocarbons by bacteria and functional regulation of membrane proteins

• Explaintheadsorption, uptake and transmembrane transport of PAHs by bacteria. • Analyze functional regulation of membrane proteins inthe transmembrane transport. • Proteomics technology such as iTRAQ labeling was used to access expressed proteins. • Single cell analysis technology wereused to study the morphological structure. In recent years, increasing research has been conducted on transmembrane transport processes and the mechanisms behind the microbial breakdown of polycyclic aromatic hydrocarbons (PAHs), including the role of membrane proteins in transmembrane transport and the mode of transmission. This article explains the adsorption, uptake and transmembrane transport of PAHs by bacteria, the regulation of membrane protein function during the transmembrane transport. There are three different regulation mechanisms for uptake, depending on the state and size of the oil droplets relative to the size of the microbial cells, which are (i) direct adhesion, (ii) emulsification and pseudosolubilization, and (iii) interfacial uptake. Furthermore, two main transmembrane transport modes are introduced, which are (i) active transport and (ii) passive uptake and active efflux mechanism. Meanwhile, introduce the proteomics and single cell analysis technology used to address these areas of research, such as Isobaric tags for relative and absolute quantitation (iTRAQ) technology and Nano Secondary ion mass spectrometry (Nano-SIMS). Additionally, analyze the changes in morphology and structure and the characteristics of microbial cell membranes in the process of transmembrane transport. Finally, recognize the microscopic mechanism of PAHs biodegradation in terms of cell and membrane proteins are of great theoretical and practical significance for understanding the factors that influence the efficient degradation of PAHs contaminants in soil and for remediating the PAHs contamination in this area with biotechnology.     

Distribution of polycyclic aromatic hydrocarbons in Datuo karst Tiankeng of South China

Levels of polycyclic aromatic hydrocarbons (PAHs) were measured in surface soils of Datuo karst Tiankeng (large sinkholes) in South China with the use of a gas chromatography-mass spectroscopy (GC-MS) system. This paper provides data on the levels and distribution of PAHs from the top to the bottom of the Datuo karst Tiankeng. The results showed that the sum of the 16 EPA priority PAHs from the sampled locations from top to bottom had a relative increment in PAHs concentration. summation operatorPAHs ranged from 16.93 ng/g to 68.07 ng/g with a mean concentration of 42.15 ng/g. The correlated results showed the bottom of the large sinkhole, which accounts for the higher concentrations, probably acts like a trap for the PAHs. Thus, the low evaporation rate at the bottom may play a key role in controlling the high concentration of PAHs at the bottom.     

Concentration of some polycyclic aromatic hydrocarbons in rain,soil and ground water around Ismailia,Egypt

Residues of acenaphthylene, fluorene, anthracene, pyrene, chrysene, benzo(b)fluoranthene and benzo(k)fluoranthene were monitored in rain, soil and groundwater around Ismailia, in northeast Egypt. Residues detected in rain water in 1995 and 1996 were mainly of relatively low molecular weight. Both acenaphthylene and fluorene were detected in rain for the two consecutive years. Top soil has shown a wider spectrum and higher concentrations of (PAHs) than those detected in deep soil, rain and ground water. Only three compounds, acenaphthylene, fluorene and anthracene were detected in samples collected at 50 cm depth. While no traces of PAHs were detected at 1 m depth detectable concentrations of fluorene and anthracene were monitored in groundwater.     

红树林生态系统多环芳烃的污染研究进展

多环芳烃（PAHs）是一类广泛存在于天然环境中的持久性有机污染物,对生态环境和人类健康造成严重的潜在威胁。文章介绍了红树林生态系统PAHs污染的研究现状;总结了红树林生态系统PAHs的污染分布及其来源,以及PAHs污染胁迫对红树植物生长的影响;评述了红树植物对PAHs的直接吸收、红树林湿地微生物对PAHs的降解等研究;最后,对红树林生态系统PAHs污染的研究趋势进行了分析和展望,提出了今后可能的研究方向,主要包括：（1）综合应用多学科交叉研究典型PAHs在红树林生态系统中的环境行为;（2）结合双光子激光共焦扫描显微技术等原位研究手段,开展红树植物对典型PAHs的吸收、存赋形态、转运等相关研究;（3）结合激光诱导时间分辨荧光光谱测定系统,实现对现场红树林生态系统中PAHs等有机污染物的原位检测。     

Source apportionment of polycyclic aromatic hydrocarbons in Lake Baikal water and adjacent air layer

The composition of polycyclic aromatic hydrocarbons (PAHs) in Lake Baikal water and adjacent air layer and PAH emission composition profiles of possible sources were investigated. Analysis of emission composition data showed that the source profiles could not be grouped by fuel type or pyrogenic/petrogenic origin. Because of the similarity of source PAH profiles, the drawing of 3D mixing diagrams was the only way to check whether some of the potential PAH sources were the true sources. The mixing diagrams showed that the sources of air pollution were paper mills and wood burning and that the sources of water pollution were coal-fired and oil-fired boilers. The common source for both air and water was only oil and petroleum products. To determine the locations of PAH sources, their contributions to air and water pollution were calculated and mapped. Based on the results, air and water were polluted from both local and regional sources. The location of the zone influenced by a particular source was conditioned by physical properties of source emission, direction of air/water flows that transfer PAHs and temperature differences between mixing air/water flows.     

Enrichment and transfer of polycyclic aromatic hydrocarbons (PAHs) through dust aerosol generation from soil to the air

● Compositional patterns of PAHs in dust aerosol vary from soil during dust generation. ● The EF of PAH in dust aerosol is affected by soil texture and soil PAH concentration. ● The sizes of dust aerosol play an important role in the enrichment of HMW-PAHs. Polycyclic aromatic hydrocarbons (PAHs) are major organic pollutants in soil. It is known that they are released to the atmosphere by wind via dust aerosol generation. However, it remains unclear how these pollutants are transferred through the air/soil interface. In this study, dust aerosols were generated in the laboratory using soils (sandy loam and loam) with various physicochemical properties. The PAH concentrations of these soils and their generated dust aerosol were measured, showing that the enrichment factors (EFs) of PAHs were affected by soil texture, PAH contamination level, molecular weight of PAH species and aerosol sizes. The PAHs with higher EFs (6.24–123.35 in dust PM_2.5; 7.02–47.65 in dust PM₁₀) usually had high molecular weights with more than four aromatic rings. In addition, the positive correlation between EFs of PAHs and the total OC_aerosol content of dust aerosol in different particle sizes was also statistically significant (r = 0.440, P < 0.05). This work provides insights into the relationship between atmospheric PAHs and the contaminated soils and the transfer process of PAHs through the soil-air interface.     

土壤多环芳烃污染根际修复研究进展

多环芳烃(polycyclicaromatichydrocarbons,PAHs)是环境中普遍存在的具有代表性的一类重要持久性有机污染物,具“三致性”、难降解性,在土壤环境中不断积累,严重危害着土壤的生产和生态功能、农产品质量和人类健康。修复土壤多环芳烃污染已成为研究的焦点。根际修复是利用植物-微生物和根际环境降解有机污染物的复合生物修复技术,是目前最具潜力的土壤生物修复技术之一。对国内外学者近年来在土壤多环芳烃污染根际修复的效果、根际修复机理和根际修复的影响因素方面的研究进展作了较系统的综述,并分别分析了单作体系、混作体系、多进程根际修复系统和接种植物生长促进菌根际修复系统对土壤多环芳烃的修复效果。指出根际环境对PAHs的修复主要有3种机制:根系直接吸收和代谢PAHs;植物根系释放酶和分泌物去除PAHs,增加根际微生物数量,提高其活性,强化微生物群体降解PAHs。并讨论了影响根际修复PAHs的环境因素如植物、土壤类型、PAHs理化性质、菌根真菌以及表面活性剂等。植物-表面活性剂结合的根际修复技术、PAHs胁迫下根际的动态调节过程、运用分子生物学技术并结合植物根分泌物的特异性筛选高效修复植物以及植物富集的PAHs代谢产物进行跟踪与风险评价将成为未来研究的主流。     

Monitoring of environmental exposure to polycyclic aromatic hydrocarbons: a review

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds with two or more fused aromatic rings. They have a relatively low solubility in water, but are highly lipophilic. Most of the PAHs with low vapour pressure in the air are adsorbed on particles. When dissolved in water or adsorbed on particulate matter, PAHs can undergo photodecomposition when exposed to ultraviolet light from solar radiation. In the atmosphere, PAHs can react with pollutants such as ozone, nitrogen oxides and sulfur dioxide, yielding diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively. PAHs may also be degraded by some microorganisms in the soil. PAHs are widespread environmental contaminants resulting from incomplete combustion of organic materials. The occurrence is largely a result of anthropogenic emissions such as fossil fuel-burning, motor vehicle, waste incinerator, oil refining, coke and asphalt production, and aluminum production, etc. PAHs have received increased attention in recent years in air pollution studies because some of these compounds are highly carcinogenic or mutagenic. Eight PAHs (Car-PAHs) typically considered as possible carcinogens are: benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene (B(a)P), dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene and benzo(g,h,i)perylene. In particular, benzo(a)pyrene has been identified as being highly carcinogenic. The US Environmental Protection Agency (EPA) has promulgated 16 unsubstituted PAHs (EPA-PAH) as priority pollutants. Thus, exposure assessments of PAHs in the developing world are important. The scope of this review will be to give an overview of PAH concentrations in various environmental samples and to discuss the advantages and limitations of applying these parameters in the assessment of environmental risks in ecosystems and human health. As it well known, there is an increasing trend to use the behavior of pollutants (i.e. bioaccumulation) as well as pollution-induced biological and biochemical effects on human organisms to evaluate or predict the impact of chemicals on ecosystems. Emphasis in this review will, therefore, be placed on the use of bioaccumulation and biomarker responses in air, soil, water and food, as monitoring tools for the assessment of the risks and hazards of PAH concentrations for the ecosystem, as well as on its limitations.     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

汕头经济特区土壤中优控多环芳烃的分布

运用气相色谱-质谱方法对汕头经济特区131个土样中的美国EPA优控多环芳烃(PAHs)进行定性、定量测定,讨论了PAHs的分布特征。结果表明,该区表层土壤中优控PAHs的总质量分数范围从22.1 ng/g到1256.9 ng/g之间,平均质量分数为(317.3210.2) ng/g。其分布随采样点的位置不同而有显著变化:工业区附近多环芳烃的质量分数最高,城市中心次之,郊区最低。大多数样点中?PAHs质量分数和单种PAH质量分数都呈现w(5~20 cm)> w(0~5 cm)>w(20~40 cm)>w(40~100 cm)的垂直分布规律。该区土壤PAHs以3环和4环化合物为主,单种PAH以萘、菲和苯并[b]萤蒽为主。     

Analyses of PAHs (polycyclic aromatic hydrocarbons) and mutagenicity in raw and chlorinated water

Both raw water and chlorinated drinking water samples were collected from and the Liu‐Du water treatment plant in northern Taiwan from October 1990 to April 1992. The polycyclic aromatic hydrocarbons (PAHs) and mutagenicity in these water samples were analyzed by GC/MS and Ames test. The Mutagenicity/DMSO (Dimethyl Sulfoxide) ratio in S. typhimurium TA98 and TA100 with or without S9 mixture increased, even higher than 2, following the sequence of unit process. It was observed that the mutagenicity with TA98 (S9+) was highly related to most of PAHs in the raw water; while the mutagenicity with TA98 (S9+) was only correlated with DbA and BghiPr in the treated water. It could be expected that the mutagenicity level was controlled by other predominant components after the raw water was treated, for example, the chlorination process.     

Distribution and behaviour of polycyclic aromatic hydrocarbons in subtropical river estuary,Okinawa, Japan

Surface water samples were collected along the salinity gradient of Manko estuary in Okinawa, Japan, between January and November 2012, to examine spatial and temporal variability in the distribution, composition, behaviour, and sources of particulate polycyclic aromatic hydrocarbons (PAHs). Concentrations of total particulate PAHs ranged from 169.7?ng?g^?1 at riverine station (N1) in November 2012 to 922?ng?g^?1 at another riverine station (K3) in May 2012. Based on observed environmental behaviour, particularly relationships to organic matter, the PAHs appear divisible into two groups: group I (low molecular weight) PAHs were characterised by low particles affinity and strong correlations with a pool of autochthonous organic matter (e.g. high concentrations of polyunsaturated fatty acids), reflecting processes controlling their delivery to the estuary; and, in contrast, group II (high molecular weight) PAHs were characterised by high particles affinity and exhibited estuarine distribution primarily controlled by suspended solid load and inputs from terrigenous sources through river inflows. This relationship, coupled with isomer ratios indicative of combined mixed sources from petroleum and petroleum combustions, indicates that terrestrial run-off is the dominant mode of delivery of particulate PAHs in the estuary. The relationships between distinct groups of PAHs and lipid biomarkers demonstrated in this study suggest that very specific pools of particulate organic matter, as opposed to concentrations of particulate organic carbon alone, can be important in the transport and fate of hydrophobic contaminants.     

北京市郊农业土壤中多环芳烃的污染分布和来源

采集了3个北京市郊发展新区(昌平区、大兴区、房山区)共计20个不同类型表层农业土壤样品,通过微波萃取和高效液相色谱分析其中多环芳烃(PAHs)含量.结果显示,研究区表层土壤已受到不同程度的污染,16种优先控制的多环芳烃总含量为1.20—3.35μg.g-1,表层土壤中的多环芳烃主要源于燃烧源,且受燃汽油型汽车尾气的影响更显著.     

Revealing the factors affecting occurrence and distribution of polycyclic aromatic hydrocarbons in water and sediments of Lake Baikal and its tributaries

The concentrations of polycyclic aromatic hydrocarbons (PAH), total carbon (TC), total organic carbon (TOC), total nitrogen (TN) and dissolved inorganic nitrogen (DIN) in water and sediments of Lake Baikal and its tributaries were measured. It was found that according to existing water and sediment quality standards limiting permissible PAH concentrations, both surface waters and sediments in Lake Baikal watershed can be considered as unpolluted with PAHs compounds. Nevertheless, the spatial distribution of PAH concentrations in lake water indicates the existence of some point PAH sources in and around the lake. These sources were natural oil seeps and communal facilities such as residential coal-fired and oil-fired boilers. It was observed that concentrations of PAHs in both water and sediments are controlled by organic matter content and organic matter mineralisation degree, as indicated by PAH-to-carbon and nitrogen-to-carbon ratios respectively. It was found that PAH/TOC and PAH/TC ratios characterise PAH loading on water and sediments respectively, whereas DIN/TOC and TN/TC ratios characterise self-purification of water and sediments respectively. It was proved that PAH/TOC and DIN/TOC ratios can be used as tracers to evaluate the PAH contributions from tributaries to Lake Baikal.     

Removal of high concentrations of polycyclic aromatic hydrocarbons from contaminated soil by biodiesel

Solubilizing experiments were carried out to evaluate the ability of biodiesel to remove polycyclic aromatic hydrocarbons (PAHs) from highly contaminated manufactured gas plant (MGP) and PAHs spiked soils with hydroxypropyl-β-cyclodextrin (HPCD) and tween 80 as comparisons. Biodiesel displayed the highest solubilities of phenanthrene (420.7 mg·L^-1), pyrene (541.0 mg·L^-1), and benzo(a)pyrene (436.3 mg·L^-1). These corresponded to several fold increases relative to 10% HPCD and tween 80. Biodiesel showed a good efficiency for PAH removal from the spiked and MGP soils for both low molecular weight and high molecular weight PAHs at high concentrations. Biodiesel was the best agent for PAH removal from the spiked soils as compared with HPCD and tween 80; as over 77.9% of individual PAH were removed by biodiesel. Tween 80 also showed comparable capability with biodiesel for PAH solubilization at a concentration of 10% for the spiked soils. Biodiesel solubilized a wider range of PAHs as compared to HPCD and tween 80 for the MPG soils. At PAH concentrations of 229.6 and 996.9 mg·kg^-1, biodiesel showed obvious advantage over the 10% HPCD and tween 80, because it removed higher than 80% of total PAH. In this study, a significant difference between PAH removals from the spiked and field MGP soils was observed; PAH removals from the MGP soil by HPCD and tween 80 were much lower than those from the spiked soil. These results demonstrate that the potential for utilizing biodiesel for remediation of highly PAH-contaminated soil has been established.     

土壤和地下水中多环芳烃生物降解研究进展

多环芳烃是一类普遍存在于环境中的难降解的危险性"三致"有机污染物。受污染的土壤和地下水中的多环芳烃,生物降解是其归宿的主要途径。研究表明,对于土壤中低分子量多环芳烃类化合物,微生物一般以唯一碳源方式代谢;而大多数细菌和真菌对四环或四环以上的多环芳烃的降解作用一般以共代谢方式开始。文章重点论述了多环芳烃的来源、降解多环芳烃的微生物、生物降解机理、影响生物降解的因素以及生物修复方法。认为今后的研究方向是高分子量多环芳烃的降解机理与降解途径,基因工程技术在多环芳烃生物降解方面的应用,以及生物表面活性剂产生的机理及其在实际处理中的应用等。     

Aryl hydrocarbon receptor activities of hydroxylated polycyclic aromatic hydrocarbons in recombinant yeast cells

Hydroxylated polycyclic aromatic hydrocarbons (OH-PAH) with less than four rings are frequently found in the environment, whereas the toxicities associated with these compounds remain unclear. In this study, aryl hydrocarbon receptor (AhR)–ligand binding activities of OH-PAH were investigated by using a recombinant yeast assay system. The majority of the OH-PAH tested showed AhR–ligand binding activities, especially, when the hydroxylated derivatives of naphthalene were incubated with recombinant yeast. The structure–activity relationship between AhR activity and molecular weight or the octanol–water partition coefficient value of OH-PAH displayed significant correlations. These findings indicate that the site and number of hydroxy-groups substituted on PAH skeleton apparently influenced the AhR – ligand binding activity in the recombinant yeast assay.     

新乡市地表水中多环芳烃的分布特征及生态风险

利用GC-MS测定了新乡市地表水中15种多环芳烃(PAHs)的含量,分析了其组成特征,并通过安全阈值(MOS10)法评价了新乡市地表水中PAHs的生态风险.结果表明,新乡市地表水中PAHs的含量为369—4248 ng·L,与国内其他河流相比,污染水平较高.PAHs的组成以3环和4环为主,分别占总量的41.3%和40.3%.新乡市地表水中单种PAHs对水生生物的生态风险大小依次为蒽(Ant)菲(Phe)芘(Pyr)苯并[a]芘(Ba P)荧蒽(Flua)芴(Flu)苊(Ace),其中Ant和Phe的暴露浓度超过影响10%水生生物的概率分别为30.2%和10.4%,具有潜在生态风险;Ace、Flu、Flua、Pyr和Ba P的暴露浓度超过影响10%的水生生物的概率分别为0.85%、1.96%、4.26%、6.71%和5.69%,生态风险较低.联合生态风险评价结果表明,新乡市地表水中∑PAH7等效浓度超过影响10%水生生物的概率为43.7%,大于任何单种PAHs对水生生物的生态风险,主要河流的生态风险从大到小依次为金堤河(56.6%)共产主义渠(43.0%)天然文岩渠(16.4%).     

Distribution of Airborne polycyclic aromatic hydrocarbons (PAH) in the area of Thessaloniki,Greece

The aim of this research work is to investigate the temporal and regional behaviour of the PAH in the Thessaloniki's area. During a period of six months, airborne particulate matter was collected twice a week and PAH were determined by HPLC. Profiles as well as concentrations of selected cancerogenic PAH differ in some cases from area to area and have characteristic, temporal changes of concentration.