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.     

环渤海北部沿海地区表层土壤中PAHs的污染特征及风险评价

系统采集了环渤海北部沿海地区31个表层土壤样品,利用GC/MS分析了16种USEPA优控多环芳烃(PAHs)的含量和组分特征,运用主成分因子载荷法揭示了其污染来源,并初步评价了其风险水平.结果表明,沿海地区65%的土壤已被污染,最高污染样点PAHs含量达920.4ng·g-1,平均含量309.5ng·g-1,与国内外相关研究比较,处于中低等污染水平.各类燃料的不完全燃烧是该地区土壤中PAHs的主要来源,石油类挥发或泄漏对采油区土壤中PAHs的累积影响显著.     

Chemical contamination of soils in the New York City area following Hurricane Sandy

This paper presents a unique data set of lead, arsenic, polychlorinated biphenyl (PCB), and polycyclic aromatic hydrocarbon (PAH) concentrations in soil samples collected from the metropolitan New York City area in the aftermath of Hurricane Sandy. Initial samples were collected by citizen scientists recruited via social media, a relatively unusual approach for a sample collection project. Participants in the affected areas collected 63 usable samples from basements, gardens, roads, and beaches. Results indicate high levels of arsenic, lead, PCBs, and PAHs in an area approximately 800 feet south of the United States Environmental Protection Agency (US EPA) Superfund site at Newtown Creek. A location adjacent to the Gowanus Canal, another Superfund site, was found to have high PCB concentrations. Areas of high PAH contamination tended to be near high traffic areas or next to sites of known contamination. While contamination as a direct result of Hurricane Sandy cannot be demonstrated conclusively, the presence of high levels of contamination close to known contamination sites, evidence for co-contamination, and decrease in number of samples containing measureable amounts of semi-volatile compounds from samples collected at similar locations 9 months after the storm suggest that contaminated particles may have migrated to residential areas as a result of flooding.     

Polycyclic aromatic hydrocarbons in soils around Guanting Reservoir,Beijing, China

The concentrations of 16 polycyclic aromatic hydrocarbons (∑ 16PAHs) were measured by gas chromatography equipped with a mass spectrometry detector (GC-MS) in 56 topsoil samples around Guanting Reservior (GTR), which is an important water source for Beijing. Low to medium levels of PAH contamination (mean=394.2±580.7 ng g^?1 dry weight (d.w.)) was evident throughout the region. In addition, localised areas of high PAH contamination near steel and cement factories were identified, with ∑ 16PAHs concentrations as high as 4110 ng/g, dry weight (d.w.). There was a significant positive correlation (r²=0.570, p<0.01) between total organic carbon content and ∑ 16PAHs concentrations. Phenanthrene was the predominant compound, accounting for 27.2% of the ∑ PAH concentration, followed by chrysene>pyrene>benzo[a]anthracene≈ benzo[b]fluoranthene≈ benzo[a]pyrene. Four-ring PAH homologues (39%) were dominant. The higher proportion of 4–6 ring homologues, molecular indices, and the spatial distribution of PAH indicated that industrial discharges, incineration of wastes and traffic discharges were the major sources of soil PAHs around the water reservoir.     

Verhalten von PAK im system boden/Pflanze

The results of lysimeter experiments conducted since 1991 dealing with the behavior of PAH in soil/plant systems demonstrate that the PAH pollution to cultivated plants may be caused by both atmospheric deposition and by the soil-to-plant transfer observed in contaminated sites. In the latter, a “direct contamination” of plant surfaces with PAH-loaded soil particles and the subsequent PAH turnover by desorption/adsorption processes is seen to dominate—at least for the most relevant PAHs toxic to humans, benzo(a)pyrene and dibenz(a,h)anthracene. Leafy vegetables growing close to the soil surface are therefore endangered most by a PAH contamination of the soil. The soil-to-plant transfer via “direct contamination” can be reduced to a high degree by covering the contaminated soil with different mulch materials. Systematic PAH transfer via root uptake could not generally be observed. From the reported results, a trigger value in the soil of 1 mg·kg^?1 for benzo(a)pyrene is proposed to make a judgement on PAH contaminated soils with regard to the soil-to-plant transfer pathways. Soils with excessive concentrations of benzo(a)pyrene demand special attention when considering the recommendations for the growth and consumption of cultivated vegetables. The “soil”as well as the “deposition pathways” must be integrated into a complete risk assessment of locations with food plant production, especially in urban areas.     

固定化毛霉对工业和农田污染土壤中多环芳烃的降解和生物有效性评价

为了探讨微生物修复不同类型多环芳烃污染土壤的可行性,应用固定化毛霉对多环芳烃污染工业土壤及农田土壤进行微生物修复,用羟丙基-β-环糊精(HPCD)提取模拟评价多环芳烃的微生物可利用性,并分析多环芳烃微生物降解和生物可利用性的相关关系.焦化厂污染土壤中多环芳烃的30 d降解率为77.6%,沈抚灌区污染土壤中多环芳烃的30 d降解率为54.2%,焦化厂土壤和污灌区农田土壤中多环芳烃降解差异明显.焦化厂土壤和污灌区土壤中多环芳烃的30 d降解量和多环芳烃的环糊精可提取量具有相关性,各环数多环芳烃的环糊精可提取量变化解释了焦化厂和污灌区土壤中多环芳烃降解的差异机制,说明可用环糊精提取量预测微生物降解土壤多环芳烃的情况.     

Urban fractionation of polycyclic aromatic hydrocarbons from Dalian soils

This report evidences the fractionation of polycyclic aromatic hydrocarbons (PAHs) from urban to rural areas, and a higher contribution of coal and wood combustion in rural areas. PAHs are persistent semi-volatile organic pollutants in the environment. PAHs originate from the incompleted combustion of fossil fuel and biomass. Cities are usually considered as primary sources of PAHs. Due to different types and loads of fuel consumption in various functional areas of a city, the levels and composition profiles of PAHs are expected to be different. We, therefore, studied the mechanisms ruling PAH distributions in soils from a major Chinese city. Seventeen soil samples were collected in urban traffic areas, residential and park areas, suburban areas and rural areas of Dalian, northeastern China. PAHs were analyzed using a high-performance liquid chromatography. The composition profiles and seasonal variation of PAHs were investigated. Results show that the proportions of low-weight molecular PAHs to total PAHs increased with urban-suburban-rural gradient. This trend is explained by the “urban fractionation” of PAHs. Furthermore, the spring/autumn ratios of PAH concentrations were higher than 1. Specifically, the spring/autumn ratio was 1.79 for two ring PAHs, 1.42 for three ring PAHs, and lower than 1.20 for five and six ring PAHs. The spring/autumn ratios of phenanthrene were higher than 1 and increased with increasing distance from the urban areas. The results imply that the contribution of coal and wood combustion PAHs increases with the urban-suburban-rural gradient.     

Assessment of the effect of environmental pollution in a marina on caged mussels using chemical and genotoxic analysis

An integrated approach using the contamination levels and DNA damage in mussels (Mytilus galloprovincialis) was applied in order to assess the chemical contamination in a marina (Eastern coastline of Aegean Sea). Mussels, which were harvested from a reference site (Foca), were transplanted into a marina situated along the coast of Izmir Bay. The transplanted mussels were collected at the 14th, 30th and 60th day of the experimental period. Polycyclic aromatic hydrocarbon (PAH) levels (27–51?ng?g^?1?wet?weight) detected in the mussels were similar to the levels detected in other coastal areas of the Mediterranean Sea. The marina’s sediment was found to be contaminated with PAHs (∑PAH?=?25?µg?g^?1) of pyrolytic origin and may become a source of pollution and a threat to the marine environment. In order to assess the DNA damage, the haemolymph and gill cells of the mussels were used for the comet analysis and considered as an indicator of exposure to genotoxic chemicals including 16 PAH compounds and metals. The highest levels of DNA damage expressed as %Tail-DNA (%T-DNA) were observed at the end of the experiment (21.5% T-DNA). The correlation analyses conducted between 2-, 3-, 4-ring PAHs in mussels and %T-DNA in haemolymph and gill cells showed a significant positive correlation. This investigation confirmed that transplanted mussel can be a useful tool to determine PAH contamination in marinas.     

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.     

Spatiotemporal multimedia emission inventory for polycyclic aromatic hydrocarbons near petroleum production plants in China based on a 10′ × 10′ grid

A spatiotemporal model was developed to investigate emissions of polycyclic aromatic hydrocarbons (PAHs) in Daqing, a Chinese city with large petroleum industry plants. The model was based on land-use types determined on a 10′?×?10′ grid. A geographic information system and regression analyses were used to characterise spatial and temporal variations in PAH emissions into multiple environmental media. The simulated results were validated using previously published experimental data, and the model was found to function well. PAH emissions to the atmosphere, soil, and surface water between 1998 and 2013 were estimated. The results indicated that PAH emissions to the atmosphere increased but PAH emissions to the soil and surface water decreased over the study period. PAH emissions to the atmosphere were markedly higher in winter than in summer. PAH emissions were concentrated in urban areas and areas near petroleum production plants, indicating that PAH emissions were closely related to industrial activities. The results will support research into the migration and transformation of PAHs and human health and ecological risk assessments. The results may also be useful for developing policies for controlling PAH pollution and managing risks associated with PAHs.     

An approach to uncertainty estimation in determining polycyclic aromatic hydrocarbons in fuel-contaminated soils

An estimation of uncertainty contribution in the entire set of the analytical data of polycyclic aromatic hydrocarbons (PAHs) in soil during a full year is presented. The analyses were performed as part of a project devoted to the assessment of the natural attenuation of selected PAHs in agricultural soil contaminated by a fuel spill. In particular, we investigated the effect of natural attenuation on the PAH dissipation rate in plots of two types of scenarios in agricultural soils. One of them was previously affected by an accidental fuel spill 10 years ago, and the other one was non-affected. The major components for estimating uncertainty contributions have been evaluated based on intermediate precision from different levels of PAH mass fraction, sample locations, and long term data set. An analysis of variance (ANOVA) test was applied to the mass fractions of clean or blank soil sub-samples versus contaminated soil sub-samples for grouping comparable data. Variables of influence in this study were site, month, and lysimeter of sampling (referring to a stainless steel box, with side lengths of 50 cm). Study sites or the spatial arrangement of lysimeter showed a clear effect in sub-sample results with the lowest mass fraction levels for heavier PAH, while monthly sampling was the variable of most significant influence for the more strongly contaminated sub-sample results.

Finally, the results of the PAH mass fractions in contaminated soil sub-samples indicated a monthly variation for which lighter, volatile PAHs rapidly decreased while the less volatile did not change.     

Polycyclic aromatic hydrocarbons (PAHs) in multimedia environment of Heshan coal district,Guangxi: distribution,source diagnosis and health risk assessment

Mining activities are among the major culprits of the wide occurrences of soil and water pollution by PAHs in coal district, which have resulted in ecological fragilities and health risk for local residents. Sixteen PAHs in multimedia environment from the Heshan coal district of Guangxi, South China, were measured, aiming to investigate the contamination level, distribution and possible sources and to estimate the potential health risks of PAHs. The average concentrations of 16 PAHs in the coal, coal gangue, soil, surface water and groundwater were 5114.56, 4551.10, 1280.12 ng g^?1, 426.98 and 381.20 ng L^?1, respectively. Additionally, higher soil and water PAH concentrations were detected in the vicinities of coal or coal gangue dump. Composition analysis, isomeric ratio, Pearson correlation analysis and principal component analysis were performed to diagnose the potential sources of PAHs in different environmental matrices, suggesting the dominant inputs of PAHs from coal/coal combustion and coal gangue in the soil and water. Soil and water guidelines and the incremental lifetime risk (ICLR) were used to assess the health risk, showing that soil and water were heavily contaminated by PAHs, and mean ICLR_{coal/coal-gangue} and mean ICLR_soil were both significantly higher than the acceptable levels (1 × 10^?4), posing high potential carcinogenic risk to residents, especially coal workers. This study highlights the environmental pollution problems and public health concerns of coal mining, particularly the potential occupational health hazards of coal miners exposed in Heshan.     

Polycyclic aromatic hydrocarbons in medicinal plants from Syria

The levels of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (EPA PAHs) in 10 medicinal plants in different used parts of plant (leaves and flowers) have been determined. The analytical method consists of sample preparation by ultrasonic extraction with dichloromethane followed by silica gel clean-up. Subsequently, the analysis was carried out by reversed-phase high-performance liquid chromatography (HPLC) coupled to both ultraviolet and fluorescence detections in series to insure the detection of all 16 EPA PAHs. It was observed that the sum of the 16 PAHs (ΣPAHs) in the investigated medicinal plants ranged from 47 to 890 μg kg^–1 where the highest ΣPAHs was found in Sage plant sample. Light PAHs were dominants in all studied medicinal plants. The sum of eight genotoxic PAHs (ΣPAH8) have shown a better indicator of the degree of contamination with carcinogenic PAHs compared to benzo[a]pyrene in these products.     

北京市某废弃焦化厂不同车间土壤中多环芳烃（PAHs）的分布特征及风险评价

以北京市某废弃焦化厂为研究对象,系统采集了6个车间0～4m深的26个土壤样本,利用GC/MS检测了U.S.EPA优控的16种多环芳烃(PAHs)的含量,分析了PAHs在焦化厂不同车间表层土壤的污染状况和深层土壤中的垂直分布特征并对土壤污染风险进行了评估.结果表明,1)该废弃焦化厂不同车间表层土壤(0～20cm)总PAHs(∑PAHs)的残留量介于672.8～144814.3ng·g-1之间;污染程度排序为:回收车间>老粗苯车间>焦油车间>炼焦车间>水处理车间>制气车间.2)该厂未受扰动的土壤样品显示PAHs主要聚集在表层土壤,并随着土壤深度的增加而迅速减少;其他样点由于土壤扰动,∑PAHs含量最大值出现在第三层土壤(80～180cm);该厂4m深底层土壤仍有高浓度PAHs,∑PAHs含量最高值出现在炼焦车间,达12953.1ng·g-1.3)焦化厂土壤PAHs污染主要集中在3环和4环的PAHs单体上,分别占到污染总量的51.3%和31.7%.4)根据Maliszewska-Kordybach的PAHs总量标准及加拿大土壤PAHs单体治理标准,该厂回收、老粗苯、焦油和炼焦车间表层和深层土壤PAHs含量均达到重污染水平,并对其周围土地带来较大风险,需要治理.     

An interval dynamic multimedia fugacity (IDMF) model for environmental fate of PAHs and their source apportionment in a typical oilfield,China

An interval dynamic multimedia fugacity (IDMF) model with a new validation criterion of interval average logarithmic residual error (IALRE) was developed in this study. The environmental fate of polycyclic aromatic hydrocarbons (PAHs) and their source apportionment in a typical oilfield of China were simulated from 1985 to 2010. The PAH concentrations predicted by the model were in agreement with the measured concentrations, which were indicated by the IALREs calculated at 0.41, 0.63, 0.52, and 0.58 for air, water, soil, and sediment, respectively. The multimedia concentrations of Σ16 PAHs were 29.55, 39.22, 31.98, and 26.69 times greater in 2010 than those in 1985, and were higher than any other year modelled. Additionally, 87.82% of PAHs remained in the soil in 2010. PAH source emission into the soil was the major modelled source, whereas PAH degradation in the air was the major modelled loss pathway; the dominant transfer process between the adjacent compartments was atmospheric deposition from air to soil. It was demonstrated that high-temperature combustion was the major source of PAHs in the air and soil, whereas biomass and coal combustion were attributed to water and sediment compartments. The IDMF model was effective in the dynamic source apportionment of PAHs.     

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。     

Vertical distribution and environmental significance of PAHs in soil profiles in Beijing,China

Vertical distribution of both the concentration and composition of polycyclic aromatic hydrocarbons (PAHs) in ten profiles in Beijing has been investigated. The results showed that PAH concentrations and compositions in topsoil from different sampling sites were different. PAH concentrations were much higher in topsoil of the investigated urban area, industrial region, and paddy field with wastewater irrigation than in other areas. Moreover, PAH concentrations in topsoil were much higher than those at greater depth, where the concentrations were relatively consistent in most soil profiles. The fingerprints of PAHs in the samples from topsoil (0–30 cm) in the same profiles were similar and were obviously different from those at greater depth, suggesting that PAH sources were consistent in topsoil samples and were discriminating between topsoil and deeper soils. PAHs in topsoil mainly arose from mixed sources of combustion of liquid fuel, coal, and/or wood, as well as wastewater irrigation, while those at greater depth were derived from soil genesis and the process of soil formation.     

多环芳烃在水稻植株中的分布

采集了天津东丽区幼穗期、蜡熟期和枯熟期的水稻植株样品,研究了多环芳烃在其不同器官中的分布.研究结果表明,水稻根中PAH15含量在幼穗期之后不断增加,至枯熟期达到土壤浓度的3倍.茎叶中PAH15含量则从幼穗期到枯熟期呈现逐渐下降的一般趋势,且穗梗含量高于稻茎,第一叶含量高于下叶.水稻籽实成熟期间生物量迅速增加,其增速高于PAH15累积,这样的稀释作用造成表观浓度的下降.水稻地上部分各器官PAH15含量与脂含量之间具有显著的正相关关系.图5参12     

Comprehensive characterization of PAHs profile in Serbian soils for conventional and organic production: potential sources and risk assessment

This study presents a comprehensive characterization of occurrence and levels of 16 polycyclic aromatic hydrocarbons (PAHs) in arable soils used for conventional and organic production in northern and central part of Serbia as well as cross-border region with Hungary. Furthermore, this study includes a characterization of PAH sources and carcinogenic/non-carcinogenic human health risk for PAHs accumulated in analysed arable soils. The total concentration of 16 PAHs varied between 55 and 4584 µg kg^?1 in agricultural soil used for conventional production and between 90 and 523 µg kg^?1 in agricultural soil used for organic production. High molecular weight (HMW) PAHs were dominant compounds with similar contribution in both soil types (86% and 80% in conventional and in organic soil, respectively). Principal component analysis and diagnostic ratios of selected PAHs were used for identification of PAH sources in the analysed soils. Additionally, positive matrix factorization was applied for quantitative assessment. The results indicated that the major sources of PAHs were vehicle emissions, biomass and wood combustion, accounting for?~?93% of PAHs. Exposure of farmers assessed through carcinogenic (TCR) and non-carcinogenic (THQ) risk did not exceed the acceptable threshold (TCR?<?10^–6 and THQ?<?1). Oral ingestion was the main exposure route which accounted for 57% of TCR and 80% of THQ. It was followed by dermal contact. This investigation gives a valuable data insight into the PAHs presence in arable soils and reveals the absence of environmental and health risk. It also acknowledges the importance of comprehensive monitoring of these persistent pollutants.

     

Lichens reveal air PAH fractionation in the Himalaya

This paper shows that gas/particulate phase partitioning of polycyclic aromatic hydrocarbons (PAHs) can be monitored using lichens. Anthropogenic sources are responsible for the release of PAHs, which are bioaccumulated in plants at various spatial scales based on their physicochemical properties. Atmospheric PAHs are distributed both in the gaseous and particulate states. Here, a lichen species, Dermatocarpon vellereum Zschacke, has been collected at different altitudes in and around the Rudraprayag valley, located in Central Himalayan region of India, in order to study the spatial distribution of PAHs in the valley. Results show that PAH concentration ranged from 0.136 to 4.96 μg g^?1. Findings reveal that the bioaccumulation of 2- and 3-ringed PAHs was higher in high-altitude samples, whereas bioaccumulation of fluoranthene, a 4-ringed PAH, showed higher concentration in samples from localities away from town centre. 5- and 6-ring PAHs were then confined to the lower altitude at the base of the valley, thus justifying their particulate-bound nature. This is the first report showing the utility of lichen to biomonitor PAHs in the Himalayan ecosystem.